Pu Review

Progress in Materials Science 52 (2007) 9151015 www.elsevier.
com/locate/pmatsci
Synthesis methods, chemical structures and phase structures of linear polyurethanes. Properties and applications of linear polyurethanes in polyurethane elastomers, copolymers and ionomers
Piotr Krol
*
Department of Polymer Science, Faculty of Chemistry, Rzeszow University of Technology, Al. Powstancow Warszawy 6, 35-959 Rzeszow, Poland Received 5 September 2006; received in revised form 25 October 2006; accepted 23 November 2006
Abstract Chemical and supermolecular structures occurring in linear polyurethanes were presented and they were referred to the analysis of the reactions connected with the step-growth polyaddition process of diisocyanates and polyols. Based on the general kinetic model of the step-growth polyaddition process, which is available in papers, inclusive of our own reports published on that subject, and based on experimental verication of that model by GPC chromatography and MALDI-ToF spectrometry, the inuence was discussed of reactivity specications of the diisocyanate and polyol monomers, and of intermediate products (urethane oligomers), on the size of molecules and on molecular weight distribution in linear polyurethane products. The applicability of such research methods as SAXS, SEM, AFM and DSC for the analysis of phase structures and micro-phase separation in the linear polyurethanes was presented. Also, the inuence of phase separation on thermal and mechanical properties of the polyurethane products was addressed. Special attention was paid to the inuence of polarity of polyurethane chemical structures, dispersion interactions, hydrogen bonding and ionic interactions on the value of free surface energy of polyurethane anionomers and cationomers. The eects on chemical and biological stability of those products were considered, too. Derived from the above analysis, the latest trends were provided for the applications of linear
Tel.: +48 17 86 51579; fax: +48 17 85 43655. E-mail address: pkrol@prz.rzeszow.pl
0079-6425/$ - see front matter 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.pmatsci.2006.11.001
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P. Krol / Progress in Materials Science 52 (2007) 9151015
polyurethanes: as liquid crystalline materials, urethaneacrylic and polyurethanesiloxane copolymers in electronics, medicine and civil engineering, and as environmentally friendly elastomers in protective coatings produced from waterborne polyurethane dispersions. 2006 Elsevier Ltd. All rights reserved.
Contents 1. 2. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Basic raw materials for the production of linear polyurethanes . . . . . . . . . . . . . . . . . 2.1. Diisocyanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. Polyols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.1. Aliphatic linear polyethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.2. Aromatic polyethers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.3. Aliphatic saturated polyesters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3. Difunctional chain extenders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4. Catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Reaction mechanisms occurring in the polyurethane production process . . . . . . . . . . 3.1. Reaction of isocyanates with hydroxyl compounds kinetics. . . . . . . . . . . . 3.2. Effects of solvents on the kinetics of the reaction of isocyanates and polyols . . General kinetic model of the diisocyanates and polyols polyaddition process . . . . . . 4.1. Kinetic scheme of the polyaddition process, inclusive of substitution effects in diisocyanates and urethaneisocyanate oligomers . . . . . . . . . . . . . . . . . . . . . . . 4.2. Assumptions for the kinetic model based on Florys theory. . . . . . . . . . . . . 4.3. Modelling possibilities for chemical compositions of reaction mixtures . . . . . Principal reactions utilised in the polyurethane technology . . . . . . . . . . . . . . . . . . . . Manufacturing methods for polyurethane elastomers . . . . . . . . . . . . . . . . . . . . . . . . 6.1. Single-stage and prepolymer-based methods . . . . . . . . . . . . . . . . . . . . . . . . 6.2. Multi-stage polyaddition process with recovery of unreacted monomers . . . . Non-isocyanate methods for the synthesis of N-substituted linear polyurethanes. . . . Determination of molecular weights of linear polyurethanes by gel-permeation chromatography (GPC) and mass spectrometry (MS) methods . . . . . . . . . . . . . . . . . Polyurethane ionomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9.1. Anionomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9.2. Cationomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Examples of copolymers with linear polyurethanes . . . . . . . . . . . . . . . . . . . . . . . . . . 10.1. Acrylic-polyurethane copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10.2. Polysiloxanepolyurethane copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . Micro-phase separation in polyurethane elastomers. Glass transition temperatures. Analysis of phase structures by DSC, SAXS and AFM methods . . . . . . . . . . . . . . . . Intermolecular interactions. Hydrogen bonding. Free surface energy. . . . . . . . . . . . . Thermal properties of linear polyurethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Modern trends in applications for linear polyurethanes. . . . . . . . . . . . . . . . . . . . . . . 14.1. Elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14.2. Biomedical materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14.3. Protective coatings, waterborne ecological lacquers, adhesives and binders. Polyurethane ionomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14.4. Modern materials for ceramics and electronics . . . . . . . . . . . . . . . . . . . . . . 14.5. Biodegradable materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 918 921 921 923 923 924 925 925 927 927 927 930 932 932 935 937 944 946 947 949 953 954 966 966 969 971 971 974 978 991 995 1003 1004 1008 1008 1009 1009
3.
4.
5. 6.
7. 8. 9.
10.
11. 12. 13. 14.
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15.
Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1009 1010
Notations PU polyurethane 2,4-TDI and 2,6-TDI toluene-2,4- and toluene-2,6-diisocyanate MDI 4,4 0 -methylenebis(phenyl isocyanate) HDI 1,6-diisocyanatohexane HMDI hydrogenated MDI IPDI isophorone diisocyanate POG poly(oxyethylene) glycol PTMO poly(oxytetramethylene) glycol PCD polycaprolactone diol BD 1,4-butanediol HMDA 1,6-hexamethylenediamine DMPA 2,2-bis(hydroxymethyl)propionic acid N-MDA N-methyldiethanolamine HEA 2-hydroxyethyl acrylate DABCO 1,4-diazabicyclo-[2.2.2]-octane TEA triethanolamine D-RE Desmodure RE PDMS poly(dimethylsiloxanes) IPN interpenetrating polymer networks A, B hydroxyl and isocyanate monomers [R2OH], [R1NCO] temporary concentrations of the hydroxyl and isocyanate reagents (33) k rate constant (33) t time (33) [OH], [NCO] temporary concentrations of functional groups (42) AnBm urethane oligomer (44) [OH]0, [NCO]0 initial concentrations of functional groups D, d OH groups in monomers and urethanehydroxyl oligomers (46)(49) E, e NCO groups at position 4 in 2,4-TDI and in isocyanate prepolymers F, f NCO groups at position 2 in 2,4-TDI and in isocyanate prepolymers F1, F2, . . . , F5 PU fractions [F1]0 initial concentrations of monomers (fraction F1) [mol/dm3] kij second order rate constant (i = D, d; j = E, e, F, f) (53) p1, p2 kinetic constant for substitution eect in TDI or (52) and (53) i, j, n natural numbers r index for functional groups (58), (68) [Fn] concentration of oligomer fraction of n order [mol/dm3] (59) a(t) temporary conversion degree of monomer (60) and (68) Mn number-average molecular weight of polymer [g/mol] (61) c(t) molar fraction of PU fraction (61) Pn polymerisation degree (68)
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DP polydispersity degree MWD molecular weight distribution ATRP atom transfer radical polymerisation CRP controlled radical polymerisation GPC gel permeation (size exclusion) chromatography TEM electron microscopy SEM scanning electron microscopy AFM atomic force microscopy DSC dierential scanning calorimetry DTA dierential thermal analysis TG thermogravimetric analysis DTG dierential thermogravimetric analysis SAXS small angle X-ray scattering WAXS wide angle X-ray scattering MALDI-ToF matrix-assisted laser desorption spectrometry method ESI electrospray ionisation spectrometry method IR infrared spectrum glass transition temperature Tg Tm melting point free surface energy (96) cS E elastic (Youngs) modulus G shear (Kirchhos) modulus K bulk (Helmholtz) modulus
1. Introduction Linear polyurethanes (PU) are polymers in which the principal chain structure is composed of aliphatic or aromatic sections R1 and R2 xed together with polar urethane groups (formula (1)):
O ~ R1 NH C O R2 ~
wherein R1 makes an aliphatic, aromatic or alicyclic radical derived from the isocyanate monomer, and R2 is a more complex group derived from the polyol component (polyether or polyester). The commercial manufacture of polyurethanes is nearly solely based on the polyaddition process which involves diisocyanates and bi-functional or multi-functional polyols with hydroxyl terminal groups (Eq. (2)): nOCNR1 NCO + nHOR2 OH ! (OR2 OOCNHR1 NHCO)n 2
The possible presence of multi-functional components, e.g. triisocyanates obtained from the trimerisation process of isocyanate monomers, or the use of branched hydroxyl polyols, will yield polyurethanes with three-dimensional cross-linking. The structure of PU chains can be additionally diversied by the polyaddition process regime, and in particular by the relative sequence of charging individual feeds. It is a frequent practice that a prepolymer is synthesised initially and an excess amount of one
919
component is used, e.g. too much diisocyanate (B) in relation to polyol (A). When the polyol component is added to diisocyanate, the molar ratio of the reacting substances is decisive for the obtained size of the isocyanate prepolymer macro-molecule (Eq. (3)): 2B A ! BAB 3B 2A ! BABAB
etc:
The synthesised urethaneisocyanate prepolymer BAB or BABAB can be further extended at the next reaction step by means of a low-molecular weight diol, e.g. 1,4-butanedion (BD) or other compound which has active hydrogen atom(s) in its structure. High-molecular weight polyurethanes are produced in this way, and the size of the nal macro-molecule when there are no diusion constraints is controlled by the molar ratio of the reacting functional groups (Eq. (4)): nOCNBABABNCO + nHOCH2 CH2 CH2 CH2 OH ! (OCONHBABABNHCOOCH2 CH2 CH2 CH2 )n 4
It is also possible to synthesise polyurethanes in a single-stage process. The molar ratios for diisocyanate, polyol and extender should be carefully selected then, yet the chain structure will not be so precisely dened in that case. PU chains will not contain only urethane structures (formula (1)), ether groups and ester groups derived from polyols. Depending on the specications of feeds (i.e. purity), and on the method adopted for the polyaddition process, one can nd also urea groups, biuret groups, allophanate groups, carbodiimide groups, aromatic hydrocarbon rings, azaheterocyclic (isocyanurate) structures or oxazolidone structures, and even ionic groups in some cases. Polyurethane plastics were initially synthesised by Bayer [1], and they have been known to users for nearly 60 years now, predominantly as elastomers and foams. The rst polyurethane, Perlon U, was obtained in 1937, in the reaction of 1,6-diisocyanatohexane and 1,4-butanediol [1]. Polyurethane products were introduced into the market in late 1940s and they quickly established a strong position there, mostly as elastomers and foamed materials. The essential distinguishing criterion for polyurethanes against other plastics is density of the former. Polyurethane plastics belong now to the group of important materials applicable in numerous elds of engineering [2]. If the volumes of polyurethane products and raw materials needed for that production are considered, PUs shall be put among the prime polymeric materials, and namely they shall be ranked 5, after the unquestionably dominant polyolens (polyethylene, polypropylene), after PVC, polystyrene and diene rubber. Very wide applicability of PUs results from the fact that their performance properties can be widely modied by selecting appropriate raw materials, catalysts and auxiliary compounds, by employing various production methods and/or by employing various methods for further processing and/or for shaping the nal products. Resulting from their specic micro-phase structure, which is formed by rigid chain segments and exible chain segments, polyurethanes oer very good elasticity with reasonably high mechanical strength and abrasion resistance at the same time, and also controllable hardness. Polyurethanes can be available both as relatively rigid plastomers and as exible elastomers with compact or foamed structures. There are two inhibiting factors for applicability of
920
polyurethanes: their limited stability at temperatures above 90 C, and their ammability. That should be in particular referred to foamed polyurethanes. PUs are produced in the form of foamed plastics, structural elastomers and coating elastomers, adhesives, leather-like materials and auxiliary agents. Flexible cellular PU elastomers became inherent in comfort-providing elements, especially in furniture making and automotive industry. On the other hand, rigid foamed PUs can be converted into lightweight elements with structural stability and superior thermal insulation performance (closed-cell foams) and/or acoustic insulation performance (open-cell foams). Which is worthy of notice is that thermoplastic elastomers (PUT) are also available. These can be processed as typical thermoplastics due to thermal restoration of their allophanate groups [37]. A newer trend in application of PUs is the production 1of biodegradable ionomers. These make the feedstocks for aqueous dispersions which need no external emulsiers and which nd their outlets as environmentally friendly lacquers [8,9]. Combination of emulsions of PU ionomers and emulsions of other polymers, like poly(vinyl alcohol) or poly(vinyl acetate), yields interpenetrating polymer networks (the so-called semi-IPNs) with very good adhesion to metallic and ceramic substrates, and with improved resistance to water [10]. Another interesting application is the production of typical IPNs with the use of PUs and other chain polymers, like poly(methyl methacrylate) [11], polystyrene [12], or with condensation polymers, like unsaturated polyesters [13], epoxy resins [14] and polysiloxanes [15], with no covalent bonds between the IPN components. The use of vegetable raw materials: starch [16], castor oil [17], natural rubber [18], lignin, wood our, molasses, cellulose, glucose, fructose or saccharose, makes it possible to obtain relatively easily biodegradable PUs. The exceptional combination of physical properties, hydrolytic stability as well as low in vitro protein adsorption and platelet adhesion to PUs enables some medical applications for PUs where the contact with body uids, e.g. plasma and blood, is required [19,20]. Polyurethanes generally oer advantageous performance properties and ease of processing, good resistance to water, to atmospheric conditions, of oils, greases, organic solvents, diluted acids and alkalies, and in case of non-aromatic PUs also resistance to photo-oxidative ageing. All that makes them applicable in numerous elds of technology, economy and in everyday life [21,22]. The above advantages classify polyurethanes as modern organic polymeric plastics and they attract considerable interest of materials engineering, i.e. that branch of science which deals with implementation and commercialisation of new materials which satisfy more and more sophisticated requirements reported from the automotive industry, medicine, economy in general, and even everyday life. The duty of polymer technology, in this context, is to design, to synthesise and to commercially produce the materials based on high-molecular weight compounds, which in this specic case means to provide the adequate and more complex than for other polymers stock of raw materials, and to develop the ecient and cost-eective processes for the production of polyurethanes. It should be noted that it is just the need for modern polyurethane materials that for over 50 years has been giving inspiration to develop new processes for the production of feed materials, to develop new polymerisation processes, and to develop new processing methods, like reaction injection moulding (RIM) wherein intermediates are subjected to nal conversion. No progress in those methods could be possible without many years of basic research within
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kinetics, synthesis of urethane oligomers and polyaddition processes. A number of fundamental issues for that technology could be successfully resolved recently, owing to modern analytical and numerical methods which made it possible to run complex kinetic research programmes [23]. The purpose of this volume is to submit a summarising outlook on some issues of the polyurethane manufacturing processes after 50 years of application of PUs. By necessity, it will have to be limited, yet it has been intended to present a review which is retrospective and possibly comprehensive at the same time. That task, which is rather dicult to do because of vast literature sources within chemistry and technology of polyurethanes, has not been approached to with the aim to present the history. Most attention has been focused on the problems of synthesis, structures and properties of linear polyurethanes, i.e. nal products but in most cases intermediates for modern polyurethane materials. That presentation of the subject, with due consideration of the dicult but fundamental points in chemical foundations and structural constraints, which are important for that group of polymers, should be useful also for those interested in the materials technology, who are involved mainly in the production of nal products of polyurethane plastics. Whenever individual synthesis methods or properties of linear polyurethanes were discusses, essential interests of potential readers were kept in mind, hence the discussion was frequently referred to the application issues, i.e. most important problems for materials engineering. Within that area, special attention was paid to possible use of the polymers in question as modern structural elastomer materials, e.g. in medical implants, environmentally friendly lacquer coatings and binders, and in special materials for electronics, like liquid crystal polymers, ion exchange membranes, polymeric lling compounds for integrated circuits, etc. 2. Basic raw materials for the production of linear polyurethanes The basic pool of feeds applicable in the manufacture of polyurethanes is made up of: diisocyanates, polyether polyols or polyester polyols, diols, diamines employed as lowmolecular-weigh extenders of isocyanate prepolymer chains, catalysts for polyaddition process of diisocyanates and compounds with unstable hydrogen atoms (water, alcohols, amines), and auxiliary substances selected for specic processes, e.g. blowing agents for foamed polyurethanes, multi-functional amines or isocyanates as cross-linking agents, or organophosphorus antipyrene compounds which are widely used in foamed polyurethanes. The choice of those materials was discussed in detail in numerous review papers intended to present production processes of individual polyurethane products [2,22]. Basic isocyanate and polyol feedstocks were also mentioned in this work, just for regularity, but what was more stressed here is their structural characteristics and chemical reactivity resulting therefrom as the key feature for the step-growth polyaddition processes. 2.1. Diisocyanates The only technically reasonable method today for the production of PU plastics is the polyaddition process of diisocyanates and polyols. Hence, the manufacturing methods and properties of the isocyanate feedstocks make the deciding factor for the production of polyurethanes. The situation is so critical that the biggest polyurethane producers have their captive production of isocyanate raw materials at the same time.
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Those compounds have their beginning in the synthesis of phenyl isocyanate, developed by Homann, and based on thermal dehydrogenation of di(N-phenyl)oxamide (Eq. (5)): C6 H5 NHCOCONHC6 H5 ! 2C6 H5 NCO + H2 5
Diisocyanates can be obtained in a laboratory by rearrangement of compounds with electron deciency at the nitrogen atom (nitrenes). The Curtius method can be used for that purpose (rearrangement of acyl azides) or alternatively amides can be subjected to Homann rearrangement. Commercially, however, only the Hetschel method has so far been employed, i.e. phosgenation of amines with further modications (Eq. (6)) [24]: RNH2 + COCl2 ! RNCO + HCl 6
The above reaction is pretty simple. Yet, the synthesis process based on it involves many steps in fact, it is troublesome and it has a bed environmental reputation all that because of extreme toxicity of phosgene, toxicity of amine feeds and toxicity of diisocyanate products themselves. In order to minimise the environmental impact of COCl2, extensive research has been directed toward the development of eective catalyst(s) for oxidative carbonylation (Eq. (7)): RNH2 + R0 OH + CO + 1/2O2 ! RNHCOOR0 + H2 O and reductive carbonylation (Eq. (8)): RNO2 + 3CO + R0 OH ! RNHCOOR0 + CO2 8 7
The synthesised carbamates would then be subjected to thermal decomposition to yield isocyanates (Eq. (9)) [25]: RNHCOOR0 ! RNCO + R0 OH 9
None the less, phosgene is still needed for the commercial production of diisocyanate monomers with the vital importance for the polyurethane technology. When analysing the changes which took place over the last decade in the diisocyanate production processes, a clear qualitative revaluation can be noticed. The group of regular products, like aliphatic diisocyanates (e.g. 1,6-diisocyanatohexane, formula (10)), OCN(CH2 )6 NCO 10
and aromatic diisocyanates: toluene-2,4-diisocyanate and toluene-2,6-diisocyanate (TDI), utilised as a mixture of isomers (formula (11)),
CH 3 NCO OCN CH3 NCO
11
NCO
2,4TDI (80 %)
2,6TDI (20%)
and 4,4 0 -methylenebis(phenyl isocyanate) (MDI) (formula (12)),
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OCN
CH2
NCO
12
or 1,5-naphtylene diisocyanate (NDI) (formula (13)), which is not so frequently used,

NCO
13
NCO
was joined by new alicyclic diisocyanates, which can be converted into polyurethane coatings more resistant to photo-degradation in direct sunlight service: isophorone diisocyanate [5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclo-hexane] (IPDI) (formula (14)),
14
and 4,4 0 -methylenebis(cyclohexyl isocyanate) (HMDI) (formula (15)): 15 Other diisocyanates, in particular 1,3-phenylene diisocyanate and 1,1-biphenylene diisocyanate, gained much less importance and they are employed in very specic applications only [26]. The fundamental problem to be considered when using diisocyanates is the need to provide adequate reactivity of their functional groups towards the compounds with unstable hydrogen atoms in their molecules. The isocyanate group, N@C@O, is generally very active due to its two cumulated double bonds. However, depending on its location within the chain (primary group, secondary group), on possible steric hindrance(s), and on the so-called substitution eect which is frequently the case in some diisocyanates or urethaneisocyanates, considerable dierences in reactivity can be observed. Such dierences can be important for commercial processes and they should be controlled by the use of suitable catalysts. Those problems made subjects of many theoretical analyses in the past [27]. A more detailed analysis will be presented below for reactivity of isocyanate groups in the most popular monomer: 2,4- and 2,6-TDI. 2.2. Polyols 2.2.1. Aliphatic linear polyethers The basic polyether polyols applicable for the production of linear PUs can be obtained by the addition reaction (following the anionic mechanism principle) of ethylene or propylene oxide to suitable glycols, produced beforehand in the water addition process to corresponding oxiranes in the catalytic presence of NaOH. What is especially worthy of notice here is block polyethers which go under the name of PLURONIC (formula (16)):
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H(O
CH2
CH2 ) n
(O
CH CH3
CH2 O)
(CH2 CH2 )n OH
16
and which oer only primary hydroxyl groups more reactive towards isocyanates. Similar performance is available from poly(tetramethylene oxide)glycol (formula (17)), which is produced by cationic polymerisation of tetrahydrofuran, and which is much more expensive: H(OCH2 CH2 CH2 CH2 )n OH 17
Polyether polyols are produced in Poland, their trade name is ROKOPOLs, and their molecular weights fall within a pretty wide range of 4003000 g/mol. The properties which are important from the viewpoint of application are: viscosity and water content; the latter should not exceed 0.05 wt%. Polyethers impart softness and exibility to polyurethanes. It would be advisable to make a secondary comment in this place: the grafting process of oxiranes on multi-functional polyols (glycerol or pentaerythritol) [28,29], on amines (triethanolamine), on hydrocarbons or phenol-formaldehyde resins, and on hydroxymethyl derivatives of compounds having imine group(s) in their structures (formula (18)):
N CH2 CH2 (O CH2 CH2 O)
n
18
(urea, melamine, uric acid or barbituric acid) can yield very interesting multi-functional polyethers applicable in the production of thermally stable, cross-linked foams [30,31]. The use of dihydroxyl derivatives of parabanic acid (formula (19)) can also be of some importance for the production of linear polyurethanes;
O C C O HO CH R CH2 N N O CH2 CH R OH
19
they can be obtained from the reaction of parabanic acid with formaldehyde, oxiranes or ethylene carbonate [32,33]. 2.2.2. Aromatic polyethers Within the group of aromatic polyethers which are important for the polyurethane processes, dianoles are worthy of notice. They are polyethers (e.g. Dianole 24) obtained in the reaction of 2,2-bis(4-hydroxyphenyl)propane (bisphenol-A) with oxiranes (formula (20)) [34,35]:
CH3 HO CH2 CH2 O
n1
C CH3
O CH2 CH2 OH
n2
20
or bisphenol-S polysulfone with oxiranes (formula (21)) [36]:

O HO CH2 CH2 O n1 S O O CH2 CH2 O H n2
21
925
Dianoles can be additionally subjected to esterication with glycolic acid, phosphoric acid or acrylic acid, which yields linear polyester polyols also applicable in the production of PUs [37,38]. 2.2.3. Aliphatic saturated polyesters The polycondensation process of dicarboxylic acids and glycols makes the most frequently used method for the synthesis of linear polyestrols. Polyadipates of ethylene glycol, diethylene glycol or propylene glycol (formula (22)) are usually utilised as linear polyesters in the polyurethane elastomers production processes. H[OCH2 CH2 OCO(CH2 )4 COOCH2 CH2 ]n OH 22
Since more and more attention is paid to the need of biodegradability (in part at least) of polyurethanes, polycaprolactone diol started gaining popularity as a polyol-type feed useful for the manufacture of such polymers. It is obtained by grafting e-caprolactone on glycol. The initial monomer, on the other hand, is obtained by oxidation of cyclohexanone (Eqs. (23) and (24)):
O C [O] C O O
23
C 2n O
+
O
HO
CH 2 CH 2 O
CH 2 CH 2 OH
24
O O n CH 2 CH 2 O CH 2 CH 2 O C (CH 2)5 O n H H O (CH 2)5 C
Polyols of that type oer lower viscosity gures than oligoesters derived from dicarboxylic acids and glycols. They are more expensive than traditional polyestrols, but product polyurethanes have superior mechanical properties. However, PUs obtained from polyesterdiols are less resistant to hydrolysis in relation to polyether polyurethanes [3941]. General attention is attracted recently by one more type of polyesterdiols applicable in the production of PU elastomers, i.e. aliphatic polycarbonates obtained from cyclic alkylene carbonates (Eq. (25)) [42,43]:
R n O O R = H, CH3 O R R R O
n-1
R OCH2CCH2 R OH
H OCH2CCH2OC
25
2.3. Difunctional chain extenders Diols make the group of difunctional chain extenders for urethaneisocyanate prepolymers, which is most widely employed in the production of PU elastomers. That group
926
comprises ethylene glycol, diethylene glycol, 1,4-butanediol and 1,6-hexanediol [44,45]. Diamines, like 1,2-ethylenediamine and 1,6-hexamethylene-diamine, can also be used as chain extenders, but in this case urethane chains are extended through urea groups. Aliphatic amines are used frequently to extend chains of urethane ionomers [46,47]. A solid position in the PU anionomers production processes was earned by the carboxylic-containing chain extender (formula (26)) [48]:
H2C H3C
OH
C COOH
26
H2C OH
2,2-bis(hydroxymethyl)propionic acid (DMPA)
There also is a group of some more specic and interesting extenders, like that shown by formula (27) [49]:
HO CH2 CH2
CH2
CH2 OH
C O
27
N N,N '-bis(2-hydroxyethyl)isonicotinamide
which is utilised in the production of PU cationomers for special outlets [40], or like Dianoles as already mentioned above these are applicable for the conversion of PU elastomers with a higher number of aromatic rings in the production of chemically resistant coatings [35,50] (formula (28)):
CH3 HO CH2 CH2 O C CH3 O CH2 CH2 OH
28
bis[4-(-hydroxyethoxy)]bisphenol A (Dianole-22)
Moreover, there is a pretty numerous group of low-molecular weight and difunctional diols and/or amines, which form rigid mesogens utilised in liquid crystal linear PUs (formulas (29)(31)) [5153]:
HO
CH2 CH2 O
CH2
CH2 OH
29
4,4'-bis(2-hydroxyethoxy)biphenyl (BHBP)
927
H2N
NH2
30
4,4'-diaminobiphenyle (DABP)
CO O CH2 CH2 OH
31
CO O CH2 CH2 OH
bis-(p-hydroxymethyl-phenyl)terephthalate
2.4. Catalysts The catalytic activity in the reaction of isocyanates and compounds with unstable hydrogen atom(s) (i.e. alcohols, amines, water, carboxylic acids, malonates, etc.) is shown by tertiary amines and organometallic compounds, and among the latter the most important compounds are those of Sn, Pb and Fe. The most popular amine catalyst is 1,4-diazabicyclo-[2.2.2]-octane (DABCO), and the most widely used tin catalysts are: dibutyltindilaurate (DBTDL) and dibutyltindioctanate. And just these two types of compounds make the basis for very specic catalytic systems, which have been developed and which oer a high selectivity with respect to polyol components with dierent molecular weights and with primary, secondary or tertiary hydroxyl groups, and also with respect to small amounts of water possibly present in polyol feeds (or added for some specic purpose). These catalysts are used in the liquid form in most cases, as solutions in glycol(s) or polyol(s) which are employed for the so-called polyol masterbatches. Catalytic salts of Bi, Fe, Ti, Co, Cd and Zn are used less frequently. Iron(II) acetoacetate, trialkylphosphines, and such compounds as N-methylmorpholine and piperidine, have also won some signicance. The problems of catalysis in the polyurethane technology were discussed in details in every monograph on PUs, presented so far [2,5456]. Moreover, there were many review papers published in that subject [5761]. It seems more important for the materials engineering to understand the basic elements of PU chemistry and the mechanism for step-growth polyaddition of diisocyanates and polyols. The role of catalysts and the consequent kinetic questions can be presented on that background. Those issues are important not only for the commercial production of linear polyurethanes by big producers, but they can also be critical for local processing in the automotive industry, in civil engineering, in repair or renovation of power supply systems, etc. 3. Reaction mechanisms occurring in the polyurethane production process 3.1. Reaction of isocyanates with hydroxyl compounds kinetics The growth in the PU manufacturing technology attracted the scientists who became eager to learn as much as they could about the mechanism(s) and kinetics of the reactions which combine to make the polyaddition process of diisocyanates and polyols. The knowledge on those issues turned out indispensable to control the changes in reactivity of
928
components through selection of suitable catalysts, auxiliary agents, polymerisation conditions and processing conditions. The urethanisation reaction of diisocyanates seems pretty simple but its mechanism is not simple. Complexity of that mechanism results from the structures of reacting substances, from the type(s) of catalyst(s) used, and also from the eect(s) of solvent(s) and viscosity of the reaction medium. Hence, one cannot go very far in generalisation. On the contrary, many processes have to be considered individually. Nevertheless, some general rules became well known [6275]. Activity of the isocyanate group, N@C@O, is very high due to the presence of two cumulated double bonds. At the rst stage of the carbamate-yielding reaction, the nucleophilic centre of the hydroxyl reagent is added to the electrophilic carbon atom in the carbonyl group of isocyanate, and the proton is simultaneously transferred to the nitrogen atom (scheme (32)):
R1 N C O+H O R2 R1 N H R1 NH C O C O O R2 O R2 R1 N H C O O R2
32
The analysis of kinetic research done for various substrates, with and without any catalysts, with and without any solvents, with solvents of various polarities, under equimolar conditions and with excess amount of one monomer, proved that the basic reaction, which produces urethanes, satises the second order kinetic equation (Eq. (33)): V dR1 NCO k R1 NCO R2 OH dt 33
where [R1NCO], momentary concentration of isocyanate component; [R2OH], momentary concentration of hydroxyl component; t, time of reaction; k, rate constant. The polyaddition reaction is a step-growth process and its individual stages are irreversible. Addition of further monomer molecules to the urethane oligomer structure is very fast, thus it is rather hard to isolate the initial products of that process, i.e. dimer oligourethanes, trimer oligourethanes, etc. Deviations from the second order kinetics may result from the auto-catalytic eect of groups OH and NHCOO, or from the eects of solvents. The auto-catalytic eect of hydroxyl groups on isocyanate groups can be illustrated as follows (scheme (34)):
R1 N C O R2
R1 N C O R2 O H
O H
R1
O + R2
k1 k2
34
+ R2
O H k3 R1 N H C O R2 O + R2 O H
929
Somewhat dierent mechanism should be suggested for the urethane auto-catalysis (scheme (35)):
k1' R1 N C O + R1 N H C O R2 R1 N H C N R1 O C O R2 O + R2
n
R1
N H
C N R1
O C O R2 O
n
k2'
35
N H C O R2 O
k3'
R1
N H
C O R2
O + R1
The auto-catalysis process forms an active complex in both cases, and that reacts then with hydroxyl groups and undergoes decomposition which yields urethane groups and hydroxyl compounds or urethane compounds, respectively. The rates of the reactions (34) and (35) can be described by the following kinetic equations (36) and (37) [62]: dR1 NCO k 1 k 3 R1 NCOR2 OH dt k 2 k 3 R2 OH 0 0 dR1 NCO k 1 k 3 R1 NCOR2 OHR1 NHCOOR2 dt k 02 k 03 R1 NHCOOR2
2
36 37
The values of k2 and k 02 for aromatic isocyanates are much higher than k3[R2OH] and k 03 R1 NHCOOR2 , hence these equations can be reduced to more simple forms (38)(41): dR1 NCO 2 k I R1 NCOR2 OH dt dR1 NCO k II R1 NCOR2 OHR1 NHCOOR2 dt where kI k1k3 k2 k0 k0 k II 1 0 3 k2 40 41 38 39
As can be seen from Eqs. (38) and (39), the rate of stoichiometric reaction of isocyanates and hydroxyl compounds, with no external catalysts but with the auto-catalytic eect, can be described formally by means of third order kinetic equations. The values of rate constants kI and kII are of the same order [62,76]. The auto-catalytic eect becomes apparent predominantly for the reactions which are carried out in solvents, and it increases in polar solvents, despite the association eect. For the processes operated with no solvents, the reaction follows the relation (33) [62,77]. Following advances of the polymerisation process, viscosity of the reaction medium increases and the reaction rate drops down since the diusion eects restrict
930
undisturbed access of reacting substances to active sites. That needs to be considered when designing a RIM process [76]. Moreover, proper interpretation of kinetic ndings requires catalytic activity gures for both external catalysts and auto-catalytic urethane groups. As a most general rule, one may assume that the rate of the polyaddition reaction, measured through disappearing free NCO groups, is dependent on the concentration of both acidic and alkaline catalysts. That results from the fact that the catalyst aects the rate of formation of active polar complexes as presented in schemes (32) and (34). The contribution from the catalysts to the rate of the reaction considered can be presented by the general equation (42) [78]: dNCO dOH dt dt 2 k OH NCO OH g k COOH COOH NCO OH g k C C NCO OH 42 where kOH, total rate constant; that is aected by the formation of a complex structure by the NCO and OH groups, by the reaction of that complex with diol, etc.; kCOOH, total rate constant; that is dependent on the formation of a complex structure by a proton and NCO, and on the reaction of that complex with diol; kC, total rate constant; that is inuenced by the formation of a complex structure by NCO and catalyst, and by the reaction of that complex with diol, etc.; g, eciency factor for the catalyst employed (0 6 g 6 1). 3.2. Eects of solvents on the kinetics of the reaction of isocyanates and polyols The issues of catalysis and kinetics for the reaction of diisocyanates and polyols in the presence of solvents attracted the interests of numerous researchers [23,69,7274]. The eorts were focused predominantly on nding kinetic parameters for the reactions of various mono- and diisocyanates with alcohols and diols in selected solvent systems which did not react with isocyanates, e.g. in chlorobenzene, THF or 1,4-dioxane (Table 1). The investigations carried out in a few solvents with dierent polarities, from e = 2.2 for decalin to e = 49.0 for dimethyl sulfoxide, made it possible to correlate the rate constants of that reaction and dielectric constants of the solvents employed. The Kirkwood equation (43) was used for that purpose [79]: e1 ln k ln k 0 A 43 2e1 where e, dielectric constant of a solvent; k, rate constant of the reaction studied; k0, rate constant for the reaction proceeding in a solvent with e = 1; A, constant value which is dependent on temperature, on Boltzmann constant, on dipole moment of a solvent used, and on Loschmidt number NL = 2.68 1019 cm3. The eect from polarity of solvent(s) on the kinetics of the reaction between diisocyanates and alcohols was assumed to result from the polar structure of the transient active complex formed. Having the above aspects in mind, it is interesting to learn the kinetics of the reaction between 2,4-TDI or 2,6-TDI and butanol in the presence of styrene. The reactions of those isomers with a mono-functional hydroxyl compound were assumed to make model reactions for a much more complex polyaddition process of TDI and difunctional polyol in styrene. The isocyanate prepolymer obtained in this process can be further converted to
P. Krol / Progress in Materials Science 52 (2007) 9151015 Table 1 Kinetic parameters for the reaction of phenyl isocyanate or TDI and hydroxyl compounds Isocyanate C6H5NCO Hydroxyl compound 1,4-Ethanediol 1,4-Butanediol 1,4-Hexanediol 1-Butanol 1-Hexanol Temperature (C) 35 35 50 35 50 45 40 60 80 60 80 100 23 35 45 60 80 60 80 100 40 60 80 60 80 100 60 80 100 23 Solvent 1,4-Dioxane 1,4-Dioxane Chlorobenzene 1,4-Dioxane Chlorobenzene Chlorobenzene Chlorobenzene kexp 104 (dm3 mol1 s1) 0.091 0.542 95.0 30.7 52.0 117 7.94 16.92 35.05 10.89 28.07 44.35 16.3 22.8 27.5 5.59 14.27 6.08 13.05 27.77 3.28 7.51 18.21 6.47 15.49 36.84 5.15 11.84 24.91 2.1 and 18.1 1.4 and 11.1b Ea (kJ mol1) 20 34
931
Reference [72] [72] [73] [72] [73] [73] [23]
1-Octanol
Chlorobenzene
32
[23]
Suberina
THF (catal. DBTL) Chlorobenzene Chlorobenzene
18.7
[69]
TDI
Ethanol 1-Hexanol
38 39
[23]
1-Octanol
Chlorobenzene
39
1-Decanol
Chlorobenzene
48
Oligo(oxypropylene-adipate) 2,4-TDI 2,6-TDI

a b
Cyclohexanone
40.7
[74]
Suberina
THF (catal. DBTL)
[69]
Suberin polyester-diol type macro-monomer with 1624 carbon atoms. The gures refer to the substitution eect and not reactivity of NCO groups in 2,6-TDI.
yield the polyurethane-unsaturated polyester or polyurethanepolystyrene IPNs, and it was for that reason essential to learn the kinetics of the polyaddition process in the styrene medium [80,81]. The kinetic parameters rate constants and activation energy values were found for the reaction of TDI with butanol in the presence of styrene (Table 2) [82]. When the liquid aliphatic hydrocarbons were introduced to the reaction system, the model reactions could be conducted under isothermal conditions. The measured values turned out generally consistent with those published earlier in literature reports (Table 1). Organisation of the process into two stages, with dierent stoichiometry of the urethanisation reactions, made it possible to establish the parameters for the reaction of NCO groups at 2- and 4- positions within TDI (kI, EaI and kII, EaII, respectively). The know fact was thus conrmed, which is still sometimes called in question, that the reactivity of the NCO group at position 4 in 2,4-TDI is 1.53 times higher than that at position 2, having even considered the kinetic eect from substitution in both TDI isomers. On the other hand, the additional
932
Table 2 Kinetic parameters for the reaction of TDI and butanol, taking place in solutions in aliphatic hydrocarbons with styrene added Type of solvent Reaction temperature (C) Stage I Pentane DMB Hexane 50% mixture (pentane + styrene) 50% mixture (DMB + styrene) 50% mixture (hexane + styrene) mixture: 69% pentane and 31% styrene 50% mixture (pentane + styrene) mixture: 38% pentane and 62% styrene 36.5 52 70.5 50 66 81 43.5 50 62 Stage II 38 51 70.5 52.5 64 83 48.5 52.5 73.5 ln kexp Stage I 7.95 7.24 6.83 7.79 7.50 6.23 7.86 7.79 6.68 Stage II 8.97 7.75 7.76 7.75 7.47 5.42 8.48 7.75 6.38 2.78 1.68 2.53 1.00 0.89 0.45 1.86 1.00 0.75 kI/kII Ea (kJ mol1) Stage I 29.1 Stage II 31.8
46.7
76.8
69.1
75.6
Concentration of process solution = 50 wt% [82].
component (styrene) introduced to the reaction system upset the reaction considerably, although it presented no diculties in nding formal kinetic parameters on the basis of the measured changes in concentration of free NCO groups by the generally employed method reaction of excess isocyanate with dibutylamine [83]. The presence of styrene was found, however, to reduce noticeably the reaction rate; that solvent could also be favourable for side reactions with the 2,6-TDI isomer, especially at the nal stage of the process, when that isomer was left unreacted in the system. The reaction temperature of our tests (below 83 C) and no external catalysts suggested that we faced other reactions than trimerisation and/or possibly formation of allophanate compounds by that diisocyanate. It is worth mentioning that the investigations as mentioned above make the grounds for the process-related issues connected with the production of new polymeric materials, like IPNs, for which both styrene (considered to be an inert solvent) and aromatic diisocyanate (reacting with a specic polyol) are of great importance. 4. General kinetic model of the diisocyanates and polyols polyaddition process 4.1. Kinetic scheme of the polyaddition process, inclusive of substitution eects in diisocyanates and urethaneisocyanate oligomers The complex polyaddition process of diisocyanates and polyols, as presented above by means of the seemingly simple reaction (2), can be shown in more details as a system of sequential-parallel irreversible reactions which yield longer and longer chains of urethane oligomers and polymers. Assuming that the studied process is based solely on the nucleophilic addition of the OH group to NCO, one can suggest a relatively simple kinetic scheme for the polymerisation process, based on a theoretically innite system (44) of sequential-parallel reactions [23]: A B ! A1 B1 A1 B1 A ! A2 B1 A1 B1 B ! A1 B2 A1 B1 A1 B1 ! A2 B2
44
933
In that scheme, A stands for the difunctional hydroxyl monomer, B stands for diisocyanate, while AnBm stands for the oligourethane structure, which can be diisocyanate urethane AnBn+1, urethane diol An+1Bn or oligourethane AnBn with the terminal group NCO on one chain end and the OH group on the other. For the needs of kinetic analysis, it is also necessary to dierentiate the oligomer structures AnBm from the viewpoint of reactivity of their functional cap groups. One can assume, for the needs of simplication, that all the OH groups in the monomer (D) and in the urethanehydroxyl oligomers (d) are primary, secondary or tertiary groups, and hence their reactivity specications are the same. In case, however, of 2,4-TDI and urethaneisocyanate oligomers derived from that monomers, it is necessary to dierentiate NCO groups from the viewpoint of substitution at the benzene ring. It will be convenient to designate those groups in the monomer with block letters E and F, and the analogous groups in oligomers with small letters e and f, respectively. The group E at the position 4 within 2,4-TDI is more reactive. In case of oligourethanes derived from 2,6-TDI, the substitution eect should additionally be considered which characterises reactivity of the second NCO group after the rst group has been converted to the urethane structure NHCOO. The substitution eect is certainly also met in 2,4-TDI derivatives, but in this case it overlaps the changes in reactivity produced by chemical non-equivalence of substituent groups. And because of usually lower reactivity of groups in oligomers just due to the substitution eect these groups have been represented by small letters e and f. For the needs of clarity, the group OH in urethanehydroxyl oligomers has also been codied as d despite the fact that usually there is no formal reason to dierentiate reactivity specications for the OH groups in monomers (D) and in oligomers (d). The chemical structures of diols, diisocyanates, urethaneisocyanate prepolymers and urethanehydroxyl oligomers, which are present in the presented kinetic model, and which are essential for further considerations, have been shown below as (45)(49):
CH3 NCO (F) R2 = HO R2 OH monomer DD CH2 CH2
45
NCO (E) monomer EF

CH3 NCO O NH
CH3 NH
O C O R2 OH
46
OH NCO dimer ed
C O R2 dimer fd
CH3 NH
O C O R2 O
O C NH
CH3
47
NCO trimer ee NCO
934
CH3 NCO O NH C O
O NH C O R2 O
CH3 NCO O R2 trimer ff O C NH

O C NH CH3
48
CH3
49
NCO NCO trimer ef
The above coding system makes it possible to distinguish individual reactions in the scheme (44) and to assign their specic rate constants kmn, which produces a more complex kinetic scheme (50) [23]: A B ! d A1 B1 f A B ! d A1 B1
d d d d d d d d d k De k DF e k DE
A1 B1 e A ! d A1 B1 Ad A1 B1 B ! e BA1 B1 A1 B1 B ! e BA1 B1
k dE f k dE e k dF e
A1 B1 e B ! f BA1 B1 f A1 B1 B ! BA1 B1
f f k df f k dF e f f
50
A1 B1 d A1 B1 ! d A2 B2
k de
A1 B1 e d A1 B1 e ! d A2 B2 e A1 B1 d A1 B1 ! d A2 B2 A1 B1 d A1 B1 ! d A2 B2
e f k df e f k de f e
itd: In order to reduce the number of reacting substances, these have been organised into suitable fractions. Two types of fractions have been arranged: fractions of even orders F2, F4, F6, . . . , F2n, comprising two types of oligomers d(AiBi)e and d(AiBi)f; and fractions of odd orders F1, F3, F5, . . . , F(2n 1), composed of four types of oligomers: d(AiBiA)d, e (BAiBi)e, e(BAiBi)f and f(BAiBi)f. These can be found in Fig. 1. [F1] refers to the concentrations of monomers [A] and [B], while [F2] refers to the concentrations of dimers, etc., as illustrated by the exemplary equations (51):
935
7000 6000 5000 4000 __ Mn 3000 2000 1000 0 0 5000 10000

t [s]15000
20000 25000
0.0030 0.0025 0.0020 0.0015 -1 ] -1 0.0010 3 ol s m m 0.0005 [d k1 0.0000
Fig. 1. Graphical presentation of model relations for average molecular weight Mn of PUR versus time, for dened values of the rate constant k1 in the step-growth polyaddition process of TDI and 1,4-butanediole (r = 1, p2 = 1.5) [89].
F1 A B F2 d A1 B1 d A1 B1 F3 e A1 B2 e A1 B2 f A1 B2 d A2 B1 F4 A2 B2 A2 B2 itd: The kinetic scheme for the step-growth polyaddition process of for example 2,4-TDI and 1,4-butanediole, when written down in accordance with that convention, will be composed of 32 types of reactions as presented in Table 3 [23]. 4.2. Assumptions for the kinetic model based on Florys theory The mathematical model for the studied polyaddition process, based on the kinetic scheme (50), is formally a system of dierential equations which describe the changes in concentrations of reacting substances over time, for a batch reactor with constant volume and with perfect agitation of reacting substances. The reaction rates for all isocyanate urethenisation reactions can be presented by the quadratic kinetic equation (33), wherein the suitable rate constants kmn for the reactions specied in Table 3 should be used in place of the reaction rate constant k [23,78]. Assuming the Florys theory [86], according to which reactivities of active sites (in polyurethane functional groups of polymer) are not dependent on the size of the chains but on their chemical structures, one can utilise equation (52) to dene precisely the substitution eect p1 which is specic, e.g. for 2,4-TDI or 2,6-TDI, the same for both isocyanate groups: k ED k FD p1 k eD k fD 52
d e d f e f f d e f
51
936
Table 3 General kinetic scheme for step-growth polyaddition process involving 2,4-TDI and 1,4-butanediole [23,85] No. for reaction type 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 Isocyanate substrate EF EF EF EF EF EF EF EF Ed Fd Ec Ef Ef Ff Ed Ed Fd Ee Ef Ef Ff Ed Fd Ee Ef Ef Ff Fd Ee Ef Ef Ff Hydroxyl substrate DD DD Ed ed fd fd dd dd DD DD DD DD DD DD Ed Fd ed ed ed ed ed dd fd fd fd fd fd dd dd dd dd dd Denotation for rate constant 2kED 2kFD kEd kFd kEd kFd 2kEd 2kFd 2keD 2kfD 4keD 2keD 2kfD 4kfD 2ked ked kfd 2ked ked kfd 2kfd 2ked 2kfd 2ked ked kfd 2kfd 2kfd 4ked 2ked 2kfd 4kfd Product fd ed ef ee ef fd ed dd dd ed fd ed fd ed fd ed ee ef ee ef dd fd ef ef dd ed fd ed fd
For 2,4-TDI, it is necessary to introduce another parameter p2 to represent dierences in NCO groups at the positions 2 and 4 on the ring in monomers and polymers (Eq. (53)): k ED k Ed k eD k ed p2 k FD k Fd k fD k fD 53
Based on the kinetic scheme (50), the mathematic model was formulated for the polyaddition process considered. The model is a system of ordinary linear dierential equations which describes changes in concentrations of monomers, dimers, trimers and tetramers, i.e. fractions F1, F2, . . ., gradually formed and reacting in the polymerisation process of diisocyanate and polyol. The number of such equations is limited in practice to about 10, and the number of components covered by the discussed system does not exceed a dozen or so [78]. Apart from factors p1 and p2, the model has 8 more kinetic parameters, i.e. reaction rate constants as shown in Table 1 (54): k ED ; k FD ; k Ed ; k Fd ; k eD ; k fD ; k ed ; k fd 54
937
After additional simplications which result from the assumed additivity condition for activation energy of urethanisation of NCO groups in 2,4-TDI, the number of essential parameters in the model is reduced to 3 principal ones (55): k ED ; p1 and p2 55
In case of most isocyanate monomers, the isocyanate groups are chemically equivalent (2,6-TDI, MDI, NDI and HDI) (p2 % 1) [87], or the ratio of their reactivities is known, e.g. in 2,4-TDI (p2 1.5) [38]. The number of parameters in the model for the analysed reaction system is thus further reduced to the most important 2 items (56): k ED and p1 56
The values for those parameters were found [23,85] for the model reaction system: 2,4-TDI and 1,4-butanediol, solution in chlorobenzeneTHF, at 101 C (2:1) and 86 C (1:1), for the initially equimolar concentrations of monomers A and B [F1]0 = 0.77 mol/dm3 (57): k ED 6:51 104 dm3 mol1 s1 k ED 17:2 104 dm3 mol1 s1 and and p1 1:55 86 C p1 1:62 101 C 57
4.3. Modelling possibilities for chemical compositions of reaction mixtures This chapter presents the original method for computer simulation of the course of the step-growth polyaddition process; that method has been implemented and veried in the laboratory practice. As it will be presented below, the calculations make it possible to mathematically forecast the average molecular weight of the linear PU formed at a certain process stage, conversion of monomer (TDI or polyol) which is used in a deciency (in relation to its equimolar amount) for a given reaction, and optimum reaction time which is necessary to convert said monomer. The parameters are calculated versus reaction time for the process parameters which have been set up. Those calculations have been carried out with the use of our own software which has been developed on the basis of the kinetic model for the step-growth polyaddition process for theoretical grounds please refer to Section 4.2 and to [88]. The following information were introduced as the entry data: initial concentration of monomer A [mol/dm3], initial molar ratio of monomers B and A (r) [dimensionless quantity] (Eq. (58)), NCO0 B0 OH0 A0
58
reaction rate constant (kED) [dm3 mol1 s1], constant representing kinetic eect of substitution (p1), molecular weights of parent substances A and B [g/mol], step for numerical integration of model dierential equations [85] as assumed for the classical Eulers method (h) [s].
938
The ndings of the simulations were obtained in the form of two-dimensional diagrams of changes of the following quantities versus reaction time: 1. Concentrations of monomer, dimer, trimer, and further fractions, expressed by the following Eqs. (59): F1t A B F2t A1 B1 F3t A1 B2 A2 B1 etc., usually up to fraction F10, specied as mole fraction or mass fraction, 2. Conversion levels, e.g. for OH groups, in the reaction occurring under excess of diisocyanate (r > 1.0), expressed by Eq. (60): at OH0 OHt OH0 60 59
or NCO groups under excess of polyol (r < 1.0), 3. Number average molecular weight for linear PU (Eq. (61)): Pn i1 M i ci t M n t Pn i1 ci t
61
The obtained results could be presented in various congurations and so it was possible to draw conclusions about the impact of the polymerisation process parameters (time, temperature, ratio of monomers) on the structure of polyurethane produced (polymerisation degree, distribution of molecular weights, concentrations of unreacted monomers). Before and during the analysis, one should always be aware of the limitations existing in the model: the model in particular fails to make any allowance for the side reactions entered by isocyanate groups biuretisation, dimerisation or trimerisation. That software was utilised inter alia to simulate the step-growth polyaddition process which was carried out in some selected reaction systems composed of: TDI, 1,4-butanediol or polyoxyethylene glycols; POG 200 (Mn = 200 g/mol), POG 600 and POG 1000. Five steps were analysed for each polyaddition process according to the model based on the kinetic scheme (50) (Table 4) [89]. The key question for the numerical analysis of the process was to calculate, with the assumptions made, the suitable time over which the substrates charged to the reactor (A and B monomers, or oligourethanes AnBn depending on the process stage) should be contacted at constant temperature with excess of initial raw materials (mixture of 2,4-TDI and 2,6-TDI, or selected compound A). The calculations have shown that the optimum reaction time increases usually at the successive stages IV for a given monomer A, and with the increasing molecular weights of hydroxyl substrates: 1,4-butanegiol, POG 200, 600 and 1000. That fact should not be explained by the declining reactivity of the terminal functional groups in urethane macro-monomers, which appear at successive polymerisation stages (since that factor has not been considered in the model, and additionally the Florys theory does not link the polymers reactivity and its molecular weight), but rather by declining reaction rates due to decreasing molecular concentrations of reacting substances when the size of their molecules increase as presented in Table 4, column 6.
Table 4 Consecutive reactions of 2,4- and 2,6-TDI (M = 174 g/mol) and polyoxyethylene glycols, considered in the studied process of step-growth polyaddition Stage of polyaddition I-BD I-200 I-600 I-1000 II-BD II-200 II-600 II-1000 III-BD III-200 III-600 III-1000 IV-BD IV-200 IV-600 IV-1000 V-BD V-200 V-600 V-1000 Type of polyol regent BD POG 200 POG 600 POG1000 BD POG 200 POG 600 POG 1000 BD POG 200 POG 600 POG1000 BD POG 200 POG 600 POG1000 BD POG 200 POG 600 POG1000 Basic reaction in polyaddition stage A + 2B ! A1B2 r Molecular weight of decient substrate (g/mol) 90 200 600 1000 438 548 948 1348 618 648 2148 3348 967 1297 2497 3697 1147 1697 3697 5697 Initial concentration of the hydroxyl substrate (mol/dm3) 1.53 1.34 0.93 0.71 6.01 3.56 2.04 0.90 0.91 0.73 0.53 0.29 3.65 2.29 1.37 0.62 0.65 0.50 0.35 0.19 Calculated reaction time (s) 2400 3600 3600 7200 3600 7200 10,800 21,600 3600 5400 7200 10,800 3600 7200 18,000 21,600 3600 5400 14,400 18,000 Calculated average molecular weight of PU (g/mol) 262.2 298.9 432.2 565.5 266.1 449.4 1116.0 1782a 438.2 548.3 948.3 1348.0 440.9 698.2 2125.0 2559a 613.1 541.9 2109 2131
4.0 4.0 4.0 4.0 0.25 0.25 0.25 0.25 4.0 4.0 4.0 4.0 0.25 0.25 0.33 0.66 6.0 5.0 3.0 2.0
A1B2 + 2A ! A3B2
A3B2 + 2B ! A3B4
A3B4 + 2A ! A5B4
A5B4 + 2B ! A5B6
The following constant values were adopted for the simulation calculations: k1 = 104 dm3 mol1 s1 (T = 56 C), p2 = 1.5, h = 5 s [88]. a Progressive increase of the molecular weight was observed to the end of the simulated process.
939
940
The reaction time is of great weight but when the reaction is carried out over the time which is longer than optimum, not only the expected growth of PU molecules is not achieved, which is apparent in diagrams presented in Fig. 1, but that can turn out even disadvantageous. Although the chain propagation reactions, which in advanced processes always proceed at a deciency of one monomer, formally do not have to stop as soon as that raw material has been completely converted, but the rate of the process dramatically drops down then. This is because the feedstock which is left unconverted in the reactor reacts solely with oligomers (hydroxyl or isocyanate ones) and the molar concentrations of the latter go down when the values of their Mn increase. If it is TDI to be used in excess (stages I, III and V), its considerable amounts remain available in the system after the reaction is completed ref. to Fig. 2, changes in concentration of fraction F1 and they can undergo undesirable side reactions. Those reactions have not been considered in the model, but they are commonly known to take place even in non-catalysed systems, in particular at higher temperatures. The above mentioned issue is linked to the degree of conversion a(t) (Eq. (60)), which represents conversion of the decient substrate under the conditions simulated for the reaction considered. The ndings from those calculations have been presented in Fig. 3. The software makes it also possible to analyse changes in concentrations of individual fractions [Fn] of monomers, dimers, trimers, etc., in the course of the process (scheme (50)). Those concentrations were analysed by the GPC method under actual process conditions, while they were subjected to continual monitoring during simulation [85]. As it was expected, the concentration of each fraction (except for F1) passes through a peak value and it then gradually decreases. The time for the maximum value is probably the most convenient moment to identify those components in the mixture. The peaks of successive fractions become more and more broadened, and the concentrations of PU com-
12
10 8 F1 [mol/dm ]
3
6 4 2 0 2000 4000 t [s ] 2 6000 8000 0 1

r
5 4 3
Fig. 2. Graphical presentation of model relations for the concentration of monomers (fraction F1) versus time, for dened values of the index r in the step-growth polyaddition process of TDI and 1,4-butanediole (k1 = 0.0005 dm3 mol1 s1, p2 = 1.5) [89].
941
1.0
0.8
0.6
0.4 0.2 0.0030 0.0025 0.0020 0.0015 1 -1 ] 0.0010 3 ol s m 0.0005 dm [ k1 0.0000 0 0.0 2000 4000 t [s] 6000 8000
Fig. 3. Graphical presentation of model relations for the conversion degree a of monomer versus time, for dened values of the rate constant k1 in the step-growth polyaddition process of TDI and 1,4-butanediole (r = 1, p2 = 1.5) [89].
ponents become lower and lower. As has been shown, such a reaction system becomes so much complicated over time from the viewpoint of its chemical composition that it is very hard to analytically identify all the components by the GPC method. Which is most valuable, however, the system is composed solely of the compounds with NCO or OH cap groups at both ends (depending on the process stage) and the system as a whole is therefore capable of reacting further and selectively [90]. In order to illustrate that fact, Fig. 4 presents the examples of calculated changes in concentrations of dimer fraction [F2] versus time for the reactions carried out at dierent initial molar ratios of substrates r = 14 (Eq. (58)). The above analysis covered the isothermal process at 86 C, for which the earlier studies had established the second order reaction rate constant as kED = 5 104 dm3 mol1 s1. If it is assumed that the process additionally involves the use of for example the DABCO catalyst, the basic urethanisation reaction can be attributed the rate constant kED which is 810 times higher [75]. In that case, any increased rate of the process will result not only in faster conversion of the monomer but in much higher molecular weight of PU as well, which can be observed in Fig. 1. The relative reactivity factor p1, which simulates the substitution eect in aromatic diisocyanates, should also be considered. The calculations as discussed above have been done for the value of p1 = 1.5 assumed constant for each case [85]. To make the analysis complete, calculations have been done also for dierent values of p1, assuming that some researchers nd the substitution eect to be much higher, like k2 = 400/33 for 2,6-TDI, and as much as 320/110 for MDI [91], although some researchers claim the substitution eect to be negligible for the latter diisocyanate (p1 = 1.0 0.2) [87]. The results obtained from those calculations have been illustrated in Fig. 5. As can be seen, the substitution eect p1 which is increased twice only would slow down the polyaddition process considerably and would yield PUs with much higher molecular weights for
942
0.8
0.6 F2 [mol/dm ]
3
0.4
0.2
0.0 0 2000 4000 t [s] 2 6000 8000 0 1

r
5 4 3
Fig. 4. Graphical presentation of model relations for the concentration of dimers (fraction F2) versus time, for dened values of the index r in the step-growth polyaddition process of 2,6-TDI and 1,4-butanediole (k1 = 0.0005 dm3 mol1 s1, p2 = 1.5) [89].
2400
2000 1600 1200 800 400 0 0 5000 10000

t [s 15000 ]
__ Mn
2.5 2.0 1.5 1.0 20000 25000 0.0 0.5

k2
Fig. 5. Graphical presentation of model relations for average molecular weight Mn [g/mol] of urethane oligomers versus time, for dened values of the parameter p2 in the step-growth polyaddition process of TDI and 1,4butanediole (r = 1, k1 = 0.0005 dm3 mol1 s1) [89].
comparable amounts of time. That would become even more apparent if a higher value was assumed for p1, e.g. p1 % 11 as specied in [91]. The most valuable results obtained from calculations have been presented in Figs. 68. They illustrate gradual increase in the average molecular weights of linear PUs produced successively at stages IV in the processes based on POG 200, 600 and 1000. Those reac-

700 600 500
Mn [g/mol]
943
400 300 200 100 0 500 1000 1500 2000 2500 1 3 2 4

s] t[
No. 1 (r = 4,00) No. 2 (r = 0,25) No. 3 (r = 4,00) No. 4 (r = 0,25) No. 5 (r = 5,00)
ddit olya
ion s
tage
No.
Fig. 6. Proles for changes in molecular weights of PUR in the step-growth polyaddition process (b) of TDI and POG 200 (k1 = 0.0005 dm3 mol1 s1, p2 = 1,5) [89].
2000
1600
Mn [g/mol]
1200
800
400 0 3
t [s ]
5 4
ta ns ge No .
5000 1
2
ly Po
ad
dit
io
Fig. 7. Proles for changes in molecular weights of PU in the step-growth polyaddition process (c) of TDI and POG 600 (k1 = 0.0005 dm3 mol1 s1, p2 = 1.5) [89].
tions were carried out with excessive amounts of one monomer or the other, alternately, which is reected by the values specied for the molar ratio r. The above simulations made it possible to calculate the optimised reaction time after which linear polyurethanes were produced in the system with possibly maximum Mn values. The ndings were presented in Table 4, columns 8 and 9. The presented calculations made it possible to optimise the reaction conditions time and temperature for given initial substances in a real process practised in the bench scale
944
2500
2000
Mn [g/mol]
1500
1000
500 0 5000
t [s ]
5 4 3 2 10000 1
Po d lya dit ion g sta eN o.
Fig. 8. Proles for changes of molecular weights of PU in the step-growth polyaddition process (d) TDI and POG 1000 (k1 = 0.0005 dm3 mol1 s1, p2 = 1.5) [89].
experiments [92]. Moreover, the kinetic parameters available in reports and specic for the kinetic eect of substitution in aromatic diisocyanates rate constant kED and ratio p1 could be subjected to critical review. 5. Principal reactions utilised in the polyurethane technology Addition of diisocyanate to a difunctional hydroxyl compound (2) makes the basic reaction which yields linear polyurethanes. Other reactions, specic for isocyanates, also bring signicant contributions to the polyurethane goods manufacturing processes, especially to those processes which utilise linear polyurethanes at their initial processes and produce foamed materials, elastomers and coatings. Whether the consequences of those reactions become apparent or not, it is decided by both the structure of the monomers used, and by the conditions adopted for the polyaddition process: temperature, time type and amount of catalyst (if any), presence of inhibitors which are employed to stabilise isocyanate prepolymers, auxiliary agents added (if any), initial molar ratio of monomers and method of feeding (dosing) them. It is important to promote the reactions desired for the given process and to minimise at the same time the side reactions. In the foamed polyurethane manufacturing process, for example, the urethane chain growth reaction is important in which urea groups extend the chains to produce the matrix for the foam. Equally important is the reaction of free isocyanate groups which foams the polyurethane material with in situ evolved CO2 (Eqs. (62)): RNCO H2 O ! RNH2 CO2 RNCO RNH2 ! RNHCONHR 62
In order to avoid that reaction, the polymerisation process should be carried out under inert gas blanketing, with the use of nitrogen or argon in most cases.
945
Moreover, the isocyanate groups with their electrophilicnucleophilic specications can enter various reactions which are more or less required, depending on specic polyurethane processes, and they can react with all electron-donor and electron-acceptor groups [2,54,93]. Isocyanates can undergo dimerisation at the temperature just above 43 C and yield yellow-coloured uretidione structures (63), while dissociation of the dimer can be expected only above 175 C. That reaction is responsible to a high degree for unwanted yellowing of coatings produced from TDI- and MDI-based aromatic polyurethanes (formula (63)):
OCN H3C N C O O C N CH3 NCO
63
Alkaline conditions, on the other hand, promote trimerisation to isocyanurates. That reaction is irreversible and the resultant isocyanurate ring is stable up to the temperature of 200 C. Hence, that structure is desirable in polyurethaneisocyanurate foams with improved thermal stability (formula (64)):
NCO H3C O C N C O N N C O NCO CH3
64
OCN CH3
Polymerisation of diisocyanates (65) and production of polyamide-1 is much less probable since the alkaline medium and low temperatures (20 to 100 C) are required, and that combination is not employed in the PU goods production processes:
O n R1 N C O ~N R1 C~
n
65
The reaction between isocyanate groups in the presence of trialkylphosphine oxides can release CO2 and form carbodiimide structures (Eq. (66)): 2R1 N@C@O ! R1 N@C@NR1 + CO2 66 The presence of urethane groups in the alkaline reaction mixture is also favourable for the formation of allophanate compounds (Eq. (67)):
O O
~ NH C O ~ + ~ NCO
~N
C O~
120 C
~ NH C
67
946
That reaction in undesirable in case when for example prepolymer with free NCO groups has to be stored for some time. Cross-linking with the use of allophanate bonds is utilised on the other hand in the production of thermoplastic polyurethane elastomers. Inhibitors are used in order to restrict side reactions and thus improve stability of prepolymers. These are usually Lewis acid compounds or other base-bonding materials. The anti-catalytic performance is also oered by metallic catalyst chelating compounds. Benzoyl chloride and p-nitrobenzoyl chloride are the most eective inhibitors. They prevent any polymerisation reaction of NCO-capped isocyanates and urethane prepolymers with urethanes, amines and urea. At the same time, they catalyse the reaction with OH groups and water. Stability of prepolymers is also improved by polyphosphoric acid [94]. New reactions of isocyanates have been revealed recently and they have been utilised in the production of polyurethane-based powder coatings [9497]. The latest options utilise the reactions of internal masking of diisocyanates by means of uretidione, biuret and allophanate bonds for that purpose [98109]. There are reactions of special value these will mask polyisocyanates with low toxicity and high content of reactive functional groups by means of e-caprolactam, benzyl alcohol, oximes, and some heterocyclic compounds, like pyrazole, triazole and imidazole. Those types of polyisocyanates are synthesised in general by obtaining the suitable tri-functional or tetra-functional reactive isocyanate prepolymer in the reaction of diisocyanate with tri-functional or tetra-functional compounds [110] (e.g. trimethylolpropane or pentaerythritol) or in their trimerisation reaction [111]. Which matters a lot in the production of powder coatings is the dimerisation reaction, but that technology has some drawbacks progress of the competitive reaction which yields isocyanurate structures needs to be controlled, and considerable amounts of unconverted diisocyanates need to be removed from the reaction mixture. That, however, can be successfully accomplished by nding high-selectivity catalysts [97]. It should be stressed that dimerisation of aromatic diisocyanates makes a much easier process, but application of the product in powder coatings is limited due to its inferior weathering resistance. Aliphatic and cyclo-aliphatic diisocyanates are of greater importance [110]. Yet, only IPDI could so far oer satisfactory yield when subjected to dimerisation (99% of dimer in relation to isocyanurate structures), owing to the dierence in reactivities of isocyanate groups. When other generally employed diisocyanates (HDI and HMDI) are subjected to dimerisation, chemical equivalence of both their isocyanate groups results in the formation of considerable amounts of isocyanurate structures (2550%). Internal masking by means of biuret or allophanate bonds is easier to do and its yield is high. Those reactions are reversible at lower temperatures (120 C) than dimerisation is (180 C), and they can make competitive options for relatively dicult and long dimerisation processes. 6. Manufacturing methods for polyurethane elastomers A signicant impact on the properties of linear polyurethanes, which is somewhat underestimated, comes from the molecular weight and its distribution. And these factors are in turn aected by a number of process parameters and by the issues connected with the process equipment and organisation of process operations in time. The critical part of the PU production processes alike in any step-growth polymerisation is the feeding operation of the isocyanate and polyol components. The volumes of feeds should be closely monitored to reach the required degree of polymerisation. In order to obtain linear PUs with possibly high-molecular weights, it is advantageous to run the process with
947
the equimolar ratio of functional groups. In case of two-stage processes, that recommendation refers to the last stage of chain extension. That is accomplished in practice by the use of precise metering pumps. There are theoretical grounds for that. As provided for by the Carothers equation (68), which describes the relation between the number-average degree Pn of non-stoichiometric step-growth polyaddition, conversion a of functional groups, and initial ratio r of functional groups, if the polymer with the maximum under given conditions molecular weight (i.e. degree of polymerisation Pn) is to be produced, complete conversion is required for the decient monomer: Pn 1r 1 r 2ra 68
On the other hand, huge excess of one of monomers (r > 2) which is the case in the production of isocyanate prepolymers assures complete conversion of functional groups in the other reacting substance (polyol). At the same time, however, formation of products with higher molecular weights is limited, hence usually Pn < 3 in such cases. The non-stoichiometric polyaddition or polycondensation processes usually yield polymers with high polydispersity resulting inter alia from side reactions. The question of relation between polydispersity of molecular weight in polyurethane DP M w =M n and the initial molar ratio of monomers is practically more complex. For example, the research done by Sanchez-Adsuar et al. [6] has shown the degree of polydispersity to go down from DP = 6.0 to DP = 3.8 when the ratio r increases from 1 to 2, and then to go up back to DP = 7.8 for r = 3. The non-stoichiometric polyaddition is utilised in PU processes for the production of urethaneisocyanate prepolymers, and more seldom for the production of urethanehydroxyl or urethaneamine prepolymers. The sequence and rate of adding components are also important for the production of polyurethane intermediates. When manufacturing prepolymers, the decient monomer is usually added to the monomer which is used in excess. If those components were added in reverse order, prepolymers would be produced initially and then as the equimolar ratio is approached high-molecular weight products would be obtained with high polydispersity. When the monomers have more than two functional groups, polymers will be produced from the very beginning, with much more complex structures, and with a considerable degree of spatial cross-linking, instead of linear PUs. The polyaddition processes of diisocyanates and polyols are carried out in solvents or directly as the bulk process depending on the type of technology and expected performance properties of the product. It is hence so very important to learn the kinetics of the polyaddition process in the presence of a solvent which frequently seems to be inert. The process in bulk is specic for the RIM method. The bulk process is used predominantly to produce foamed materials, elastomers, and also coatings and adhesives which can be dissolved if necessary at the nal stage of the process to be applied as solutions, e.g. on fabrics for industrial use [112]. 6.1. Single-stage and prepolymer-based methods The methods utilised for the production of PUs can be arranged in two general groups: single-stage methods and multi-stage (prepolymer-based) methods. In the former case, all the raw materials are charged simultaneously and dierent rates of dierent reactions are compensated for by the use of adequate catalysts. The whole heat of reaction is evolved
948
right away which increases the temperature of the reaction mixture considerably. That method is simple, yet its applicability is limited as the properties of the produced goods are inferior to PUs obtained from prepolymer-based methods. In the latter case, prepolymer is obtained at the rst stage with reactive isocyanate or hydroxyl cap groups. Depending on the type of prepolymer produced (isocyanate type or hydroxyl type) and on the assumed value of M n , the required amounts of reacting substances are selected. The chain expands at the further stage when the prepolymer reacts with the compounds which contain two reactive groups at least. Depending on functional groups of the extender and its amount (i.e. ratio of groups r = NCO:OH), the linear polymer can be produced or the product is obtained which is cross-linked by urethane or allophanate bonds. When the prepolymer material contains double bonds, its cross-linking process can follow the radical polymerisation model which can be controlled by radiation, by the use of sulfur, peroxides or diazo compounds [113]. Cross-linking of polyurethanes has also been reported by the controlled radical polymerisation (CRP) method in the atom transfer radical polymerisation (ATRP) system with the use of urethane macro-initiators [114116]. The polymer product shaping process involves the casting, rolling or RIM method. The use of special feeding equipment, provided with a few heads each supplying the feed in a dierent colour, produces multi-colour goods. Linear PUs and those cross-linked with allophanate bonds perform like thermoplastic elastomers [68]. They will undergo thermal softening at the temperatures over the dissociation point for the allophanate bonds (120 C) and they can be processed by methods applicable for thermoplastics (e.g. extrusion or injection moulding). Hence, one can produce various unit goods, bres and/or foils in this way. The use of various raw materials, at various amounts, and the ability to control the location within the polymer chain where some elements should be built-in, all that gives a chance to produce tailored PUs with strongly varied properties. Adding to commonly used feeds, various other compounds can be used to impart specic features to polyurethanes. Incorporation of mesogenic rigid segments makes it possible to obtain PU elastomers performing like liquid crystals [117]. The NCO group, when inserted instead of the hydroxyl group, makes the prepolymer t for further polyaddition, while the substitution of one hydroxyl group by the amino group and the other hydroxyl group by the chloroformyl group makes it t for polycondensation. PUs obtained in this way were characterised by high glass transition temperatures Tg,h = 118 C and high degree of crystallinity (scheme (69) [118]:
H 2N H O O O HO H O H O C Cl O C NH H O polycondesation
OH OCN
O H O polyaddition OH
69
949
Extension of PU prepolymers with uorescein makes them glossy [119], and the use of phenolphthalein oers the chance for further modications of free carboxyl group, e.g. to produce ionomers [120]. Introduction of the tricyanocyclopropane substituent to the hydroxyl component imparts the piezoelectric properties to polyurethanes [121], and ferrocene structures when built-in into soft segments are responsible for the reducing-oxidising properties [122]. The use of N-acyldiisocyanates will produce poly(N-acylurethanes) [123]. The two-stage method, depending on the relative amount of one of the monomers used, makes it possible to obtain prepolymers with both isocyanate and hydroxyl terminal groups, and additionally to control their molecular weights. On the other hand, however, the use of huge excess of one of monomers as discussed earlier will put considerable limitations to molecular weights and monodispersity of prepolymers. Additionally, unconverted excessive amounts of diisocyanate are objectionable because of its toxicity and negative impact on other properties of the products. The need thus arises to remove unconverted monomers and the vacuum distillation method is employed for that purpose [124]. Less severe distillation conditions can be provided when thin lm evaporators are used [125,126]. That method reduces the content of unconverted monomer down to below 0.1 wt%. Extraction of monomers with solvents (e.g. heptane and acetonitrile) can reduce the content of unreacted TDI down to 0.3 wt% [127,128]. The extraction method can also use compressed and dried CO2 which makes it possible to completely remove HDI from the prepolymer material [129]. A method has also been developed for removal of free diisocyanates to the level of 0.40.2 wt% with the use of adsorption columns packed with Xtype molecular sieves which contain Na2O:Al2O3:SiO2 [130]. Diisocyanates can also be recovered from prepolymers by the ltration method the monomer needs to be reacted for that purpose with benzyl alcohol to yield solid carbamates [131]. 6.2. Multi-stage polyaddition process with recovery of unreacted monomers Within the multi-stage processes, the PUT method is worth mentioning which was developed by Martin et al. [3]. The prepolymer with NCO terminal groups was synthesised in that method from z polyhexamethylene glycol (PHMO) and MDI at the molar ratio of 1:2. The process involved no solvents and it was carried out at 70 C under nitrogen blanketing. Glycol was added to the pre-dened amount of MDI during 10 min, and the process conditions were maintained for 2 h more. That prepolymer was then reacted with rigid segments which had been synthesised especially for that purpose, with known chain lengths and MWD. The synthesis of rigid segments was based on reacting suitable amounts of MDI with 1,4-butanediol (BD) (0.84 mol MDI: 6.7 mol BD). MDI was dissolved in DMF and it was added to the BD solution at 50 C with continuous mixing, and then heating was continued over 2 h. After the reaction mixture was cooled down to room temperature, the product precipitated in the form of white crystals these were ltrated, washed with methanol and then washed with water to remove residual DMF. The trimer BDMDIBD and heptamer BDMDIBDMDIBDMDIBD were found to make the basic products of that reaction. The GPC revealed that despite the adopted excessive volumes of BD the mixture contained at least two more products with higher molecular weights. The authors did not specify, however, any information on polydispersity of that mixture. The obtained product was dissolved in DMF again and it was added to the prepolymer material, which had been produced earlier, at the molar ratio of 1:1.
950
After mixing the components for 2 min, the mixture was placed in a mould at 100 C and it was blown with a strong ow of nitrogen to expel the solvent. Another method for the synthesis of rigid segments from TDI and BD was adopted by Furukawa et al. [132]. They obtained the trimer BDTDIBD by adding dropwise the suspension of BD (0.34 mol) in benzene, at 60 C and under nitrogen blanketing, to the solution of TDI (0.09 mol) in the same solvent. After complete conversion of TDI, the reaction product was extracted with hot water and then subjected to re-crystallisation. The obtained product (0.2 mol) was reacted with TDI (0.1 mol) to produce the heptamer (BDTDIBDTDIBDTDIBD). The obtained trimer made the principal product of the reaction, while the heptamer was obtained together with 3-, 5-, 9- and 11-mer. Thus obtained intermediates made rigid segments of elastomers which were reacted with poly(ethyleneadipate). Shilov et al. [133] synthesised rigid segments separately in the reaction of MDI with BD, and soft segments separately in the reaction of PTMG with the pyromellitic anhydride, at the molar ratio of 2:1 in each case. The obtained isocyanate prepolymer and hydroxyl prepolymer were reacted at the next stage with each other at the ratio of 1:1 to produce the linear PU. The possibility of extending with diol and isocyanate, alternately, and the use of a trifunctional isocyanate, is a method employed for the synthesis of polyurethane dendrimers [134]. The step-growth method gives the chance to control the order in the segmented structure of the PU chain and it is for that reason utilised for the production of elastomers and micro-cellular foams with improved mechanical strength, exibility and hardness. The multi-stage method for the synthesis of linear PUs was described in [92]. Earlier, the successive stages of that process were analysed with the use of computer simulation methods (Section 4.3). In accordance with the scheme (50), the synthesis of urethaneisocyanate prepolymers AnBn+1 and urethanehydroxyl oligomers An+1Bn was carried out alternately, and these were reacted at further stages with the diol monomer (A) [polyoxyethylene glycols (POG) with M n 200, 300, 400, 600 and 1000 g/mol or polycaprolactone diol (PCD) with M n 530 and 1250] and the mixture of 2,4-TDI and 2,6-TDI (B), respectively. The reactions were carried out in bulk in a glass reactor, under nitrogen blanketing. Benzoyl chloride was used (0.3 wt% with respect to TDI) as a viscosity control agent; moreover, its use made it possible to expand the stability period of synthesised prepolymers AnBn+1 and hence the prepolymers could be employed as parent substances in subsequent reactions. The polyaddition process was always initiated by a reaction which proceeded at a considerable excess of diisocyanate (B). In order to make the complete conversion possible for the parent substances A or B which were in short supply, each reaction as can be observed in diagram (50) was carried out at 100% excess of the other reacting substance, i.e. BD, POG, PCD or TDI. The feeds were introduced under possibly mild conditions to avoid any uncontrolled conversion of NCO groups which were still present in the system to allophanates, or their cyclisation to isocyanurates. No external catalyst was employed in the experiments. A calculated amount of hydroxyl-terminated or isocyanate-terminated oligomer prepared at an earlier stage was introduced drop by drop to TDI or to appropriate glycol, respectively. It was always the decient component that was introduced to the component which was present in excess. The time of introduction was adjusted to about 30 min. The reacting mixture was maintained at 65 C. The temper-
P. Krol / Progress in Materials Science 52 (2007) 9151015 Table 5 Specications for the reactions which yield urethane oligomers [142] Symbol of oligomer I-BDa I-BDb I-200a I-200b I-300a I-300b I-400a I-400b I-600a I-600b I-1000a I-1000b I-530a I-530b I-1250a I-1250b II-BDa II-BDb II-200a II-200b II-300a II-300b II-400a II-400b II-600a II-600b II-1000a II-1000b II-530a II-530b II-1250a II-1250b III-BDa III-BDb III-200a III-200b III-300a III-300b III-400a III-400b III-600a III-600b III-1000a III-1000b III-530a III-530b III-1250a III-1250b Polyaddition stage no. I Basic reaction in polyaddition stage A + 3B ! A1B2 + B Polyol component BD BD POG 200 POG 200 POG 300 POG 300 POG 400 POG 400 POG 600 POG 600 POG 1000 POG 1000 PCD 530 PCD 530 PCD 1250 PCD 1250 BD BD POG 200 POG 200 POG 300 POG 300 POG 400 POG 400 POG 600 POG 600 POG 1000 POG 1000 PCD 530 PCD 530 PCD 1250 PCD 1250 BD BD POG 200 POG 200 POG 300 POG 300 POG 400 POG 400 POG 600 POG 600 POG 1000 POG 1000 PCD 530 PCD 530 PCD 1250 PCD 1250
951
Extraction solvent system for excess monomer Hexane/ethyl Hexane/ethyl Hexane/ethyl Hexane/ethyl Hexane/ethyl Hexane/ethyl Hexane/ethyl Hexane/ethyl acetate (2:1) acetate (2:1) acetate (1.5:1) acetate (1.5:1) acetate (1:1) acetate (1:1) acetate (1:1) acetate (1:1)
II
A1B2 + 3A ! A3B2 + A
Water Toluene Toluene Toluene Toluenexylene CCl4 Toluenexylene CCl4 Like at stage I
III
A3B2 + 3B ! A3B4 + B
(continued on next page)
952 Table 5 (continued) Symbol of oligomer IV-BDa IV-BDb IV-200a IV-200b IV-300a IV-300b IV-400a IV-400b IV-600a IV-600b IV-1000a IV-1000b IV-530a IV-530b IV-1250a IV-1250b V-BDa V-BDb V-200a V-200b V-300a V-300b V-400a V-400b V-600a V-600b V-1000a V-1000b V-530a V-530b V-1250a V-1250b
Polyaddition stage no. IV
Basic reaction in polyaddition stage A3B4 + 3A ! A5B4 + A
Polyol component BD BD POG 200 POG 200 POG 300 POG 300 POG 400 POG 400 POG 600 POG 600 POG 1000 POG 1000 PCD 530 PCD 530 PCD 1250 PCD 1250 BD BD POG 200 POG 200 POG 300 POG 300 POG 400 POG 400 POG 600 POG 600 POG 1000 POG 1000 PCD 530 PCD 530 PCD 1250 PCD 1250
Extraction solvent system for excess monomer Like at stage II
A5B4 + 3B ! A5B6 + B
Like at stage I
ature was maintained at that level for another 2 h after the predened volume of the decient component had been added. It was very important for that method that the polyurethane mixture had to be puried carefully, i.e. unreacted diisocyanate and polyol monomers had to be removed therefrom. That can be accomplished by conservative evaporation in vacuum evaporators, which is not so frequently employed in practice, or by means of selective extraction. Extraction was employed to remove excess unconverted monomer after every stage and thus the puried intermediate AnBm could be employed as a parent substance for another polyaddition stage. The principal reactions for every stage IV are presented in Table 5. The letter a denotes the samples taken directly from the reactor, while the letter b denotes the products after extracting out the excess of TDI or diol. On the basis of the assumed reaction stoichiometry and experimentally determined content of free NCO groups, we could calculate the compositions of initial mixtures, i.e. weight fractions for substrates (AnBn+1 and B at odd stages 1, 3, 5, as well as An+1Bn and A at even stages 2 and 4 of the processes) and for the reaction products. In case of
953
substrates products before extraction products after extraction

90 80 70 60 50 40 30
A B A1B2 A2B3 A3B2 A4B3 A3B4 A4B5 A5B6 A5B4 A6B5 A7B6 A6B7 A7B8 A8B9
20 10 0
Stage I
S5
Stage II
S9
Stage III
S13
Stage IV
S17
Stage V
Fig. 9. Chemical compositions for raw materials and products of successive reactions of BD and TDI [142].
even stages 2 and 4, the course of reaction and hence the expected chemical compositions of the formed urethanehydroxyl oligomers were conrmed indirectly by comparing the theoretical and experimental losses in weights of samples after excess monomer A had been extracted out. Exemplary compositions of mixtures at successive stages of the reaction between BD and TDI were presented diagrammatically in Fig. 9 [92]. 7. Non-isocyanate methods for the synthesis of N-substituted linear polyurethanes Which is interesting, although with no practical use so far, is the production of PUs in the cationic polymerisation, in the ring opening process of cyclic urethanes. Polymerisation of seven-membered rings takes place at the temperature which is only slightly above the monomer melting point. Six-membered rings would polymerise at 100 C, while the ve-membered structures do not polymerise at all that comes from the positive contribution of the entropy component DS to the free enthalpy DG = DH TDS of the polymerisation reaction of cyclic compounds, at least six-membered. The value of the
Amount of component [%]
954
enthalpy component for such reactions is zero (DH % 0) in practice. The dominant reaction at higher temperatures is polymer degradation (DG > 0) with cyclisation (Eq. (70)):
O O O NH N H O
70
This method is applicable in the production of multi-block urethane copolymers, e.g. with poly(tetrahydrofurane), with the use of such initiators like methyl triuoromethylsulfonate or triuoromethylsulfonic anhydride [135,136]. There are other methods, the so-called isocyanate-free methods for the production of linear PUs, which were developed pretty long ago. They are based on the interphase condensation of diamines and bischloroformates (Eq. (71)): nH2 NR0 NH2 + nClCOOROOCCl ! (NHR0 NHCOORCOO)n + 2nHCl 71
or on the reaction of urea derivatives with carbonates. There is no commercial application for them [137,138], although they are interesting from certain view points: this is the only way for the production of e.g. N-substituted polyurethanes, wherein for example it is impossible to create hydrogen bonds with the involvement of urethane groups. It is on the basis of inter alia this type of polyurethanes that the eect of those bonds on thermal stability of linear polyurethane structures could be studied [139]. Another method can turn out commercially interesting to some extent, which utilises urea as the source of the OCONHR segment. The linear or cross-linked PUs can be produced in this method by reacting urea and oligodiols and then condensing the obtained carbamate intermediates with formaldehyde [55]. 8. Determination of molecular weights of linear polyurethanes by gel-permeation chromatography (GPC) and mass spectrometry (MS) methods Having in mind the essential eect of molecular weight on strength of obtained linear polyurethanes, as mentioned above, it seems advisable to present the potential way(s) of controlling the progress of the step-growth polyaddition process from that point of view. The same process was subjected to theoretical analysis earlier, in Section 4.3, and the computer simulation method was utilised which had been developed for that purpose. The multi-stage model process for polyaddition of 2,4-TDI, 2,6-TDI and 1,4-butanediol was carried out under experimental conditions, and the obtained concentration data for fractions F1-F10, collected with the use of the GPC method, were then used to verify the adopted kinetic model (50) and to nd the kinetic parameters kED and p1 [85]. Further studies were based on earlier model calculations to conduct much more complex processes with the use of polyols having much higher molecular weights [92,140142]. Following the idea of scheme (50), PUs obtained at successive stages of the polyaddition process should be initially mixtures of monomers and oligomers, and after extraction they should be mixtures of predominantly oligourethanes. So, it is necessary to identify individual components. That problem was solved by analysing individual samples with the use of size exclusion chromatography (GPC) and mass spectrometry (ESI and
P. Krol / Progress in Materials Science 52 (2007) 9151015 Table 6 Interpretation for GPC chromatograms of monomers and urethane prepolymers [142] Symbol of oligomer Mn as per MWD curves 96.9 177.7 459.6 748.9 350.6 617.6 884.5 1146.1 1390.2 1633.7 182.1 267.6 761.0 862.3 1036.1 1310.9 1570.1 1817.7 178.2 378.7 894.1 1148.1 1419.6 1665.4 1925.0 2161.6 2464.6 2807.3 162.5 727.5 995.6 1190.7 1418.7 1705.1 1932.0 2190.1 2435.1 2731.0 3062.2 3455.7 105.0 117.8 152.9 186.3 Compound Theoretical molecular weight (g/mol) 90 174.17 502.34 766.51 354.17 618.34 882.51 1146.68 1410.85 1675.02 174.17 238.17 766.51 824.51 1030.68 1294.85 1559.02 1823.19 354.17 882.51 1146.68 1410.85 1675.02 1939.19 2203.36 2467.53 2731.70 174.17 766.51 1030.68 1294.85 1559.02 1823.19 2087.36 2145.36 2351.53 2615.70 2879.87 3144.04 106 (n = 2) 150 (n = 3) 194 (n = 4) Amount of component as calculated by standarisation of GPC chromatograms (wt%) 100 8.03 87.49 4.47 6.92 65.96 9.22 13.34 2.57 1.99 4.12 4.86 7.93 4.49 53.09 9.54 9.12 6.85 6.03 0.80 6.43 33.95 8.62 9.33 7.72 8.95 11.43 6.71 1.78 0.92 1.84 4.58 39.47 9.46 9.84 11.48 4.41 3.02 2.62 2.15 4.89 46.54 23.63 14.95 77.18 22.82 1.16 79.16 20.84 Amount of component as calculated from reaction mass balance (wt%)
955
M w =M n
BD I-BDb
A B A1B2 + 2CH3OHa A2B3 + 2CH3OH A2B1 A3B2 A4B3 A5B4 A6B5 A7B6 B B + 2CH3OH A2B3 + 2CH3OH A3B3 + CH3OH A3B4 + 2CH3OH A4B5 + 2CH3OH A5B6 + 2CH3OH A6B7 + 2CH3OH A2B1 A4B3 A5B4 A6B5 A7B6 A8B7 A9B8 A10B9 A11B10 B A2B3 + 2CH3OH A3B4 + 2CH3OH A4B5 + 2CH3OH A5B6 + 2CH3OH A6B7 + 2CH3OH A7B8 + 2CH3OH A8B8 + CH3OH A8B9 + 2CH3OH A9B10 + 2CH3OH A10B11 + 2CH3OH A11B12 + 2CH3OH A A A
1.00 1.05
II-BDb
III-BDb
1.30
27.00 17.42 55.60 1.62
IV-BDb
27.91 17.39 54.28
V-BDb
1.28
26.80 15.98 48.28 8.93
POG200
1.07
(continued on next page)
956 Table 6 (continued) Symbol of oligomer Mn as per MWD curves
Compound
Theoretical molecular weight (g/mol) 238 (n = 5) 282 (n = 6) 174.17 238.17 562.34 (n1 = 3) 886.51 (n1,2 = 3) 562.17 (n1,2 = 4) 886.34 (n1 = 3, n2,3 = 4) 1298.51 (n14 = 4) 1666.68 (n15 = 4) 2078.85 (n15 = 4, n6 = 5) 2535.02 (n14 = 4, n57 = 5) 3079.19 (n1 = 4, n28 = 5) 238.17 606.34 (n1 = 4) 974.51 (n1,2 = 4) 1342.68 (n13 = 4) 1754.85 (n13 = 4, n4 = 5) 2123.02 (n14 = 4, n5 = 5) 2667.19 (n1 = 4, n26 = 5) 3497.53 (n17 = 5)
Amount of component as calculated by standarisation of GPC chromatograms (wt%) 7.46 2.53 20.00 4.33 65.65 10.02 0.94 5.65 24.83
Amount of component as calculated from reaction mass balance (wt%)
M w =M n
214.7 230.1 I-200b 170.5 260.6 529.0 889.0 II-200b 359.3 513.3 901.0
A A B B + 2CH3OH A1B2 + 2CH3OH A2B3 + 2CH3OH
1.31 63.51 36.49 1.36
A2B1 A3B2
67.75
1305.1 1673.0 2088.8
A4B3 A5B4 A6B5
16.65 21.66 16.25
32.25
2520.8
A7B6
12.44
3072.9
A8B7
1.58
III-200b
187.8 595.1 962.5 1361.7 1752.8
B + 2CH3OH A1B2 + 2CH3OH A2B3 + 2CH3OH A3B4 + 2CH3OH A4B5 + 2CH3OH
1.00 2.52 4.58 5.47 28.06 36.46 16.04
1.43
2121.3
A5B6 + 2CH3OH
27.15
47.50
2668.4
A6B7 + 2CH3OH
20.64
3519.1
A7B8 + 2CH3OH
10.58
P. Krol / Progress in Materials Science 52 (2007) 9151015 Table 6 (continued) Symbol of oligomer Mn as per MWD curves 105.9 482.6 846.6 Compound Theoretical molecular weight (g/mol) 106 (n = 2) 474.17 (n1,2 = 3) 886.34 (n1 = 3, n2,3 = 4) 1166.51 (n13 = 3, n4 = 4) 1578.68 (n1,2 = 3, n35 = 4) 2034.85 (n16 = 4) 2403.02 (n17 = 4) 2947.19 (n14 = 4, n58 = 5) 3875.70 (n111 = 4) 5282.38 (n18 = 4, n914 = 5) 238.17 606.34 (n1 = 4) 1062.51 (n1,2 = 4) 2167.02 (n13 = 4, n4,5 = 5) 2383.19 (n16 = 4) 2751.36 (n17 = 4) 3183.53 (n18 = 4) 4376.04 (n19 = 4, n1012 = 5) 5804.72 (n114 = 4, n15 = 5) 7233.40 (n119 = 4) Amount of component as calculated by standarisation of GPC chromatograms (wt%) 1.26 1.64 2.05 Amount of component as calculated from reaction mass balance (wt%)
957
M w =M n
IV-200b
A A2B1 A3B2
1.50
1157.3
A4B3
1.94
1587.0
A5B4
14.13
38.36
2029.3 2400.1 2979.1
A6B5 A7B6 A8B7
10.03 17.56 20.25
15.98 45.66
3860.4 5276.8
A11B10 A14B13
19.24 11.89
V-200b
326.5 629.10 1058.0 2177.9
B + 2CH3OH A1B2 + 2CH3OH A2B3 + 2CH3OH A5B6 + 2CH3OH
0.36 1.77 2.14 11.15 28.90
1.29
A6B7 A7B8 3175.6 4369.2 A8B9 + 2CH3OH A11B12 + 2CH3OH
11.67 32.61 15.89 21.78 26.82
5814.6
A15B16 + 2CH3OH
20.44
7230.1
A19B20 + 2CH3OH
26.47 (continued on next page)
958 Table 6 (continued) Symbol of oligomer Mn as per MWD curves 1414.5
Compound
Theoretical molecular weight (g/mol) 1383 (n = 11) 2004.34 (n1 = 14) 3288.51 (n1,2 = 11) 1611 (n = 13) 2484.17 (n1,2 = 9) 3396.17 (n1,2 = 13) 4497.11 (n13 = 11) 5712.51 (n13 = 10, n4 = 11) 4617.68 (n1,2 = 10, n3 = 11 6630,85 (n1,2 = 11, n3,4 = 12) 7960.02 (n15 = 11) 3510.17 (n1 = 13 n2 = 14) 4611.34 (n1,2 = 11 n3 = 12) 5826.51 (n1,2 = 10, n3,4 = 11) 7155.68 (n14 = 10, n5 = 11) 8712.85 (n14 = 10, n5,6 = 11) 10726.02 (n17 = 11) 3174.51 (n1 = 10, n2 = 11)
Amount of component as calculated by standarisation of GPC chromatograms (wt%) 100
Amount of component as calculated from reaction mass balance (wt%)
M w =M n
PCD 1250
1.20
I-1250b
2049.4
A1B2 + 2CH3OH A2B3
100
95.14 4.86
1.73
II-1250b
1639.7 2452.8 3382.6 4440.4 5714.4
A A2B1 A2B1 A3B2 A4B3
9.25 11.79 16.73 33.55 28.66 96.52 3.48
1.26
III-1250b
4685.1
A3B4 + 2CH3OH
41.71
95.29
1.51
6601.2
A4B5 + 2CH3OH
58.29
3.37
A5B6
1.34
IV-1250b
3582.9
A2B1
5.99
1.11
4675.0
A3B2
9.56
5883.3
A4B3
14.37
7225.0
A5B4
24.93
96.60
8716.8
A6B5
45.14
3.12
A7B6 V-1250b 3173.3 A2B3 + 2CH3OH
0.28 4.56 1.17
P. Krol / Progress in Materials Science 52 (2007) 9151015 Table 6 (continued) Symbol of oligomer Mn as per MWD curves 4047.9 Compound Theoretical molecular weight (g/mol) 4047.68 (n1 = 8, n2,3 = 9) 6288,85 (n1 = 10, n24 = 11) 8302.02 (n1,2 = 11, n35 = 12) 9517.19 (n16 = 11) 11074.36 (n17 = 11) 12631.53 (n18 = 11) Amount of component as calculated by standarisation of GPC chromatograms (wt%) 9.31 Amount of component as calculated from reaction mass balance (wt%)
959
M w =M n
A3B4 + 2CH3OH
6296.4
A4B5 + 2CH3OH
16.06
8308.3
A5B6 + 2CH3OH
34.12
79.66
9552.2
A6B7 + 2CH3OH A7B8 A8B9
35.99
2.56 0.23 17.56
a Designations: (1) ni (i = 214) theoretically calculated polymerisation degree in POG or PCD. (2) AnBn+1 + 2CH3OH provides the information that the saved le corresponds to the isocyanate prepolymer AnBn+1 which has been blocked on both sides with methanol (when samples were being prepared for analysis).
MALDI-ToF) methods in which mild excitation techniques were employed to take records of basic molecular ions. It was possible from GPC chromatograms which were recorded with the use of use detectors: RI, LS and DV, to obtain a reasonably precise function
Fig. 10. MWD curves for oligomers (IV) BDb (according to Table 5) [142].
960
of molecular weight distribution (MWD) for individual samples of studied oligomers and to make their quantitative evaluation (Table 6). It is obvious that the basic reason for polydispersity of every urethane oligomer sample is primarily polydispersity of the hydroxyl component itself. All diols, except for
Fig. 11. MWD curves for oligomers (IV) 200b (according to Table 5) [142].
Fig. 12. MWD curves for oligomers (IV) 1250b (according to Table 5) [142].
P. Krol / Progress in Materials Science 52 (2007) 9151015 Table 7 Interpretation for mass spectra of urethane oligomers [142]
Designations for oligomers as per Table 1 I-BDb Type of MS method MALDI No. of g. Band location (M/z) 525 675 790 378 642 792 907 1171 261 525 551 790 1054 1203 1319 1583 1848 361 551 906 1171 1320 1435 262 376 414 525 551 995 1201 1583 1848 1938 2112 2641 409.1 365.1 11 12 689.2 365.1 969.3 1013.4 542 954 1279 1647 Relative intensity (%) 100 5.71 2.86 22.22 100 5.19 2.22 1.11 46.15 18.27 34.61 20.19 100 8.65 6.73 7.70 1.92 47.28 29.09 18.17 100 9.10 7.28 97.83 84.79 100 35.87 73.92 11.96 14.14 32.60 4.35 2.17 3.27 3.27 100 88.00 100 100 97.00 100 48.25 100 30.07 20.98 Probable structure of molecular ion A1B2 + Na+ + 2CH3OH A3B2 + Na+ + CH3OH A2B3 + Na+ + 2CH3OH A2B1 + Na+ A3B2 + Na+ A3B3 + H+ A4B3 + Na+ A5B4 + Na+ B + Na+ + 2CH3OH A1B2 + Na+ + 2CH3OH A2B2 + Na+ A2B3 + Na+ + 2CH3OH A3B4 + Na+ + 2CH3OH A4B4 + 2CH3OH A4B5 + Na+ + 2CH3OH A5B6 + Na+ + 2CH3OH A6B7 + Na+ + 2CH3OH A2B1 + H+ A2B2 + Na+ A4B3 + Na+ A5B4 + Na+ A5B5 + H+ A6B5 + Na+ B + Na+ + 2CH3OH B2 + Na+ B2 + H+ + 2CH3OH A1B2 + Na+ + 2CH3OH A2B2 + Na+ A3B4 + H+ + CH3OH A4B4 + H+ + 2CH3OH A5B6 + Na+ + 2CH3OH A6B7 + Na+ + 2CH3OH A7B7 + Na+ + 2CH3OH A7B8 + Na+ + 2CH3OH A9B10 + Na+ + 2CH3OH A + K+ A + K+ A1B2 + Na+ A + K+ A3B2 + K+ A3B2 + K+ A2B1 + Na+ A3B2 + Na+ A4B3 + Na+ A5B4 + Na+ Calculated molecular weight (g/mol) 523.34 673.34 789.51 377.17 641.34 793.51 906.51 1170.68 261.17 523.34 551.34 789.51 1053.68 1204.68 1317.85 1582.02 1846.19 355.17 551.34 906.51 1170.68 1321.85 1433.85 261.17 371.34 413.34 523.34 551.34 999.68 1205.68 1582.02 1846.19 1936.19 2110.36 2638.70 409 (n = 8) 365 (n = 7) 692.34 (n1 = 6)
961
II-BDb
MALDI
III-BDb
MALDI
IV-BDb
MALDI
V-BDb
MALDI
POG 200 I-200b II-200b
ESI ESI ESI
365 (n = 7) 969.34 (n13 = 4) 1013.34 (n1,2 = 4, n3 = 5) 541.17 (n1 = 3, n2 = 4) 953.34 (n13 = 4) 1277.51 (n1 = 3, n24 = 4) 1645.68 (n1 = 3, n25 = 4) (continued on next page)
MALDI
962 Table 7 (continued)
Designations Type of No. Band for oligomers MS of location as per Table 1 method g. (M/z) 2060 2428 III-200b ESI MALDI 689.2 610 935 1259 1628 1996 2409 365.1 645.2 969 586 955 1279 1692 2060 2385 2797 3077 3490 3814 689.2 733.2 1129 1260 1454 1630 1998 2411 586 815 1894 3201 995 1252 1553 1155 3884 4503 5241 994 1201 1527
Relative intensity (%) 7.69 3.50 100 100 48.91 92.39 31.52 20.65 7.61 100 38 35 39.00 36.00 36.00 100 52.00 43.00 22.00 17.21 10.4 7.17 94 100 100 86.57 91.04 95.52 91.79 39.55 100 100 3.01 2.37 100 45.00 40.00 100 0.95 0.63 0.48 55.56 100 19.44
Probable structure of molecular ion A6B5 + Na+ A7B6 + Na+ A1B2 + Na+ A1B2 + Na+ A2B3 + Na+ A3B4 + Na+ A4B5 + Na+ A5B6 + Na+ A6B7 + Na+ A + K+ A2B1 + K+ A3B2 + K+ A2B1 + Na+ A3B2 + Na+ A4B3 + Na+ A5B4 + Na+ A6B5 + Na+ A7B6 + Na+ A8B7 + Na+ A9B8 + Na+ A10B9 + Na+ A11B10 + Na+ A1B2 + Na+ A1B2 + Na+ A2B3 + Na+ + 2CH3OH A3B4 + Na+ A3B4 + H+ A4B5 + Na+ A5B6 + Na+ A6B7 + Na+ A + Na+ A + Na A2B1 + Na+ A3B2 + Na+
+
Calculated molecular weight (g/mol) 2057.85 (n16 = 4) 2426.02 (n17 = 4) 692.34 (n1 = 6) 609.34 (n1 = 5) 933.51 (n1,2 = 4) 1257.68 (n1 = 3, n2,3 = 4) 1625.85 (n1 = 3, n24 = 4) 1994.02 (n1 = 3, n25 = 4) 2406.19 (n16 = 4) 365 (n = 7) 645.17 (n1 = 4, n2 = 5) 969.34 (n13 = 4) 585.17 (n1,2 = 4) 953.34 (n13 = 4) 1277.51 (n1 = 3, n24 = 4) 1689.68 (n15 = 4) 2057.85 (n16 = 4) 2382.02 (n1 = 3, n27 = 4) 2794.19 (n18 = 4) 3074.36 (n1,2 = 3, n39 = 4) 3486.53 (n1 = 3, n210 = 4) 3810.70 (n1,2 = 3, n311 = 4) 692.34 (n1 = 6) 736.34 (n1 = 7) 1129.51 1257.68 1455.68 1625.85 1994.02 2406.19 (n1 = 5, n2 = 6) (n1 = 3, n2,3 = 4) (n1 = 5, n2 = 6) (n1 = 3, n24 = 4) (n1 = 3, n25 = 4) (n16 = 4)
IV-200b
ESI
MALDI
V-200b
ESI MALDI
PCD 1250 II-1250b
MALDI MALDI
585 (n = 4) 815 (n = 6) 1891.17 (n1 = 6, n2 = 7) 3198.34 (n1,2 = 7, n3 = 8)
III-1250b
MALDI
A1B2 + Na+ + 2CH3OH 997.17 (n1 = 4) A1B2 + H+ 1253.34 (n1 = 7) 1555.51 (n1 = 3, n2 = 4) A2B3 + Na+ A + Na+ A3B2 + Na+ A4B3 + Na+ A5B4 + Na+ 1155 (n = 9) 3881.34 (n1,2 = 9, n3 = 10) 4503.51 (n1 = 7, n24 = 8) 5239.68 (n15 = 7)
IV-1250b
MALDI
V-1250b
MALDI
A1B2 + Na+ + 2CH3OH 997.17 (n1 = 4) A1B2 + H+ + 2CH3OH 1203.34 (n1 = 6) 1533.51 (n1 = 3, n2 = 4) A2B3 + H+
a Designations: (1) ni polymerisation degree in POG or PCD.
963
1,4-butanediol, were inhomogeneous materials as regards their chemical compositions. Hence, adequate polymerisation degrees ni were required to be attributed to every component (i.e. to every peak) in chromatograms of POG or PCD. Then, in order to be able to compare homogeneity features of oligourethanes produced at successive polyaddition stages, the Peak Fit v4. software was employed to calculate the corresponding MWD curves. The exemplary charts were presented in Figs. 1012 [142]. The adopted procedure made it possible to observe step-by-step the growth of molecular weights of oligomers produced at every step of polymerisation. The best chromatographic separation was obtained for samples taken from the reactor just after steps 1 and 2, when the chemical composition of the mixture analysed was reasonably simple. Good separation was then harder and harder to achieve as the mean molecular weights of products increased. The obtained MWD curves especially for stage 5 and stage 6 became similar to those described in reports for high-molecular weight PUs synthesised for example of ethylene glycol polyadipate, TDI or MDI, and then expanded with ethylene glycol [143]. One dominant oligourethane is usually observed in the polymer mixtures after the rst two stages; its structure results from adopted stoichiometry (Table 5). The chemical compositions of the products obtained from further stages become much more complex and the adopted stoichiometry is decisive more for the types of terminal functional groups rather than for reaction selectivity. In parallel to the most welcome oligomer, there are always a few other products present and their shares happen to be comparable to that of the required product. Some small amounts of high-molecular weight products appear as early as at the initial two steps. For example, step 1 will yield A1B2 but also isocyanate oligourethanes with higher molecular weights (A2B3 and A3B4) will be produced. Unconverted monomers can also be observed in some samples. Further polymerisation steps produce compounds with higher molecular weights, as expected, but they also yield lower oligomers, probably by the reaction of monomers introduced with monomers which have not been completely removed from previously synthesised products. The recorded chromatograms made the basis for the calculations of number-average M n and weight average M w molecular weights as well as polydispersity degrees PD M w =M n for the products formed. The values for the latter fall within 1.052.37 and they tend to be even closer to the scope of 1.11.3. No distinct increase in the scatter of molecular weights could be observed along the sequence of polyaddition stages that is advantageous for the process oered. The values of PD > 1.3 are specic for oligourethanes in which some amounts of monomers can be found after they have not been extracted out completely, and in particular for isocyanate prepolymers in which some small amounts of TDI are present. The ESI and MALDI-ToF mass spectrometry methods were employed to unambiguously identify individual compounds within the analysed samples which had been found present on the basis of SEC analyses. The bands were visible in recorded MS spectra which could be attributed to the suggested molecular ions of oligomers, i.e. their sizes and structures, with the atomic weights of Na+, K+ or H+ cations added, as results from the adopted excitation method. Majority of positive ions present in ESI spectra contain K which has been introduced as KI, and some minor part of them contain Na. MALDIToF spectra principally take records of adducts of oligomers and Na+ or H+ cations, and also possibly of K+ (about 15%) [144,145]. Additionally, isocyanate products reacted with methanol employed to dissolve samples which is also apparent in the ndings.
964
The recorded spectra reveal generally a high number of M/z signals with much diversied intensities; after a detailed analysis one can make signal-product pairs for majority of expected adducts. The calculated theoretically molecular weights of polyols and produced urethane oligomers match with the locations of their corresponding signals in MS spectra. Every spectrum is made up of a specic sequence of signals arranged at the intervals of M/z = 44 from each other, which corresponds to the structural unit of CH2CH2O for POG, or at the intervals of M/z = 114 (i.e. CO(CH2)5O) for PCD (Table 7). The ESI spectra can take records of MWD only up to the value of M/z = 1200. Hence, it is impossible to fully identify the components of the samples studied (Figs. 13 and 14) [138,146]. The MALDI-ToF technique is capable of analysing a much broader scope of M/z. Just for illustration, Figs. 15 and 16 present exemplary spectra for oligomers obtained from two stages of reactions of TDI and POG 300, while the detailed interpretation of spectra for all the synthesised oligomers can be found in Table 7. The employed MS methods complement the chemical compositions of oligomers as found by GPC and make them reliable. Said compositions are much more complex than one could expect from the balance calculations and from kinetic modelling, still the general compatibility with the model has been kept. In the MS spectra recorded, signals can be seen which represent for example oligourethanes created from POG or PCD molecules with various polymerisation degrees ni. When individual molecular ions are precisely recorded with the use of MALDI-ToF technique, the compounds can be identied which could not be isolated with the GPC method due to poor separation of individual components, even with the use of three chromatographic columns connected in parallel. Some MS spectra reveal the presence of oligomers with the compositions close to expectations, which seemed to be missing in GPC, while some other spectra demonstrate many more
100
689,2
733,3
80
Relative abundance
645,2
60
777,4
40
657,2
701,2
745,2 601,2
20
505,1 557,1
821,4
865,3 881,4
925,4
500
600
700
800
900
M/z
Fig. 13. ESI spectrum for oligourethane I-200b (according to Table 5) [142].
965
high-molecular weight products which have been recorded in chromatograms in the form of so-called tails.
100
925,3
969,3
1013,4
1057,4
80
Relative abundance
1101,4
60
881,3
40
837,2
1145,4
1189,4
20
1233,4 1277,5
800
900
1000
1100
1200
1300
M/z
Fig. 14. ESI spectrum for oligourethane II-200b (according to Table 5) [142].
Fig. 15. MALDI-TOF spectrum for oligourethane I-300b (according to Table 5) [142].
966
Fig. 16. MALDI-TOF spectrum for oligourethane V-300b (according to Table 5) [142].
9. Polyurethane ionomers 9.1. Anionomers Polyurethane anionomers include the group of linear polyurethanes or those with lower density of cross-linking PU which have very small numbers of acidic functional groups, e.g. COO or HSO , in their chains [147]. In general, the structure of a PU anionomer 3 chain, alike that of any PU elastomer (2), is composed of blocks and it comprises both rigid urethane segments (derived from diisocyanates and diamines) and exible polyether or polyester segments (formulas (72)(74)):
R1 NH CO O R O OC COONH R1 NH CO NH R3 NH OC NH R1 NH CO
72 where R1, aromatic, alicyclic or aliphatic radical derived from diisocyanate employed in the synthesis; R2, aliphatic chain derived from polyol, e.g. oligo-oxypropylene glycol:
O CH2 CH CH3 O n
73
R3, aliphatic radical, e.g. (CH2)6 from diamine employed to extend the isocyanate prepolymer chain, built-in into the chain through applicable urea structures. The COO groups, which make principal elements of PU anionomers, are located in the element R and they are derived in most cases from some additional substrates, e.g. dihydroxyacids:
967
O CH2 CH2 C
CH2 CH2 O
COOH
74
but they can also be introduced in other locations within the PU chain resulting from chemical modications of that chain [148]. Yet, the actual structure of a PU chain can be much more complex and it is dependent not only on the type of employed raw materials but also on the conditions adopted for the polyaddition process, e.g. which feedstocks were charged earlier and which were charged later, stoichiometry of reaction, process temperature and time, as well as possible presence and amount of the polyaddition catalyst used. The process conditions are responsible for the fact that PU macro-molecules can comprise also biuret groups, allophanate ones, carbodiimide or azaheterocyclic isocyanurate structures, or oxazolidone ones. Majority of additionally created structures are polar structures. That adds to the nature of carboxyl, urethane and ether or ester groups which are typically present in anionomers. Hence, polarity of resultant PUs becomes considerable and those materials oer better solubility in water (as compared to insoluble non-ionic polyurethanes) and in polar organic solvents, e.g. in N,N-dimethylacetamide, dimethylformamide and acetonitrile dimethylsulfoxide. When a PU anionomer is not completely water-soluble, it is usually capable of forming aqueous emulsions or dispersions, and it can form specic polymer gels in the presence of organic solvents [149]. That should be accounted for by enhanced polar interactions of the dipoledipole or dipole-induced type, and by ionic interactions in the polymersolvent and polymerpolymer system. Moreover, a higher tendency to form hydrogen bonds as compared to non-ionic PUs brings its contribution, too. One can expect that such strong interactions between polar functional groups in PU anionomers will notably aect the supermolecular structure, arrangement of phases and separation of exible and rigid segments present in PUs. And these issues, in turn, are decisive for the electrical properties: improved conductivity and higher dielectric constant of those materials. The surface energy of the anionomers considered can be modied by introducing functional groups and structural segments with hydrophobic performance (non-polar hydrogen groups and low-polarity ether groups) and hydrophilic performance (polar acid groups, amine groups and ammonium groups) [150]. PU elastomers which have some features of ionomers were found to oer improved thermal stability and improved mechanical properties, and even higher potential for thermodynamic miscibility with non-polar polymers, e.g. poly(p-phenylene vinylene), or with polar ones, e.g. poly(styrene-acrylic acid) [151,152]. For the above reasons, polyurethane ionomers draw attention of numerous researchers from the 1980s [148,153,154]. The systems were synthesised which contained carboxyl and sulfo groups [155159], and with carbon or uorocarbon [160,161] trunk chains. The recent literature reports conrm continual interest in that group of polymers, applicable for example as waterborne and environmentally friendly lacquers and adhesives wherein no additional emulsiers are required [162164]. They are even more interesting since the intermediates used for their manufacture urethaneisocyanate prepolymers are not water compatible and they need to be accurately reacted with polyols in the aqueous medium rst. urethaneisocyanate anionomers, on the other hand, demonstrate the ability to react selectively in the aqueous medium with diamines, e.g. with 1,6-hexamethylenediamine (HMDA). That process extends the PU chain but no hydrolysis of isocyanate and no release of CO2 takes place, which is the case when foamed plastics are produced in situ [165,166]. In case of classic linear PUs containing strongly hydrophilic urethane and
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hydroxyl groups, it is also possible to produce emulsions but additional surfactants are required to make those emulsions stable, and the dispergation process becomes eective only after high shear rates are employed [167]. Polyurethane anionomers in the form of aqueous dispersions have been employed for example as the so-called temporary binders which made it possible to mould the oxide-type ceramic materials into products [168]. The polyurethane ionomers are produced by prepolymer-based methods in multi-stage processes. At the rst stage, the urethaneisocyanate prepolymer is prepared from a selected pair: diisocyanate and polyol. At further steps, it is reacted with 2,2-bis-(hydroxymethyl)propionic acid (DMPA), and nally its COO groups are neutralised with triethylamine, and the prepolymer chain is extended in the aqueous dispersion medium with 1,6hexamethylenediamine. What is critical for the adopted synthesis method is the need to provide adequate molar ratios for the introduced reacting substances at successive reaction stages. Stage I Synthesis of isocyanate prepolymer (AB2) (Eq. (75)) HOAOH 2OCNBNCO ! OCNBNHCOOAOCONHBNCO A B ! AB2 75 where A segment derived from polyol structure (16, 17 or 24), B segment derived from diisocyanate structure. Stage II Synthesis of urethaneisocyanate anionomer and its ammonium salt. Urethaneisocyanate anionomer which contained COOH groups was synthesised with the use of DMPA (X) (26) as a chain extender for the AB2 prepolymer (Eq. (76)): 2AB + X ! BABYBAB 76
where X = DMPA (formula (26)), and Y = segment derived from built-in DMPA. Afterwards, the urethaneisocyanate macro-anionomer (with the carboxyl groups in its structure) is subjected to the reaction (structural fragment Y) with triethylamine, which yields the triethylammonium cation. That reaction can be represented by Eq. (77):
BABYBAB + N(C2H5)3 COOH BABYBAB COO (-) [NH(C2H5)3](+)
77
The macro-anionomer produced in that way was capable of forming aqueous dispersions. Under these conditions the free NCO groups of this macro-anionomer react much slower with the carboxylate groups than with water and NH2 groups coming from HMDA which is put in during the Stage III. Therefore additional creation of the possible amide cross-links with some part of COO groups which are present in the segments coming from DMPA can be neglected. Stage III Extension of urethane macro-anionomer in the reaction with 1,6hexamethylenediamine. The macro-molecules of isocyanate anionomers which were not converted at stage III must be extended at the next stage by means of HMDA. The reaction is carried out in aqueous dispersion, taking advantage of higher reactivity of isocyanate groups with amino groups that isocyanate groups and water (Eq. (78)):

n BABYBAB + n H2N (CH2)6 NH2 [NH (CH2)6 NH BAHBYBHA] NH
n
969
COO (-) [NH(C2H5)3](+)
COO (-) [NH(C2H5)3](+)
78
Finally, the introduced solvents have to be expelled, and water is evaporated under mild conditions from the aqueous dispersion which have been applied to the perfectly smooth and chemically inert surface, e.g. Teon, to produce the polymer lm [167]. 9.2. Cationomers Variety of chemical structures, which is specic for polyurethanes, and which became available due to diversity of raw materials and synthesis methods developed so far, makes also the feature of cationomers. Those materials have the prospects ahead of them which are not any less interesting than those for anionomers, i.e. they can be utilised as waterborne lm-forming emulsions [169,170], coatings which make glass bres water-repellent [171], materials for electronics (for example, a photosensitive PU coating with built-in stilbene-based chromophores was obtained [172]) or bactericidal coatings with structural pyrimidynyl groups [173]. However, the interest attracted by PU cationomers is much inferior in relation to analogous anionomers. Strongly polar cationic groups incorporated into rigid segments of linear PUs improve considerably polarity and intermolecular forces within those segments, which contributes to increased phase separation, higher glass transition temperature and melting point of rigid segments, and improved mechanical strength of that polymeric material. Alike for anionomers, the increasing content of ionic groups in PU chains improves the hydrophilic performance, mechanical strength and exibility of PU cationomers, while their unit elongation increases even by several hundred percent. Moreover, the spectrum of mechanical relaxation of the polymers is wider which is favourable for better their fatigue life [174]. As a result, the relatively high concentration of ionic groups converts the (usually) hydrophobic PUs into highly hydrophilic materials which are soluble in typical organic solvents like methanol or acetone, and which form homogeneous solutions, emulsions or dispersions with water [170]. Adding to hydrogen bonds, which are formed within the urethane-, ether- or ester groups, there is a possibility of ionic interactions between NHR cations (intentionally introduced 3 to the chains) and higher-mobility negative counter-ions in acid radicals. The energy of ionic bonds, wherein quaternary ammonium salts are involved, is considerable and it is not much dependent on the anion type. In is inter alia for that reason that PU cationomers oer superior adhesion to polar surfaces [170,171]. Irrespective of that, some protons in NH groups can form additional hydrogen bonds with anions of ionic groups. Such quasi-cross-linking quaternary ammonium bonds in PU ionomers remain stable up to the temperature of about 150 C. The polymer can ow above that limit the bonds break out then but they are restored after the material is cooled down. High stresses have the similar eect which can be accounted for by high residual elongation of that ionically cross-linked polyurethane. The properties of cationomer-based coatings are also controlled by the size of dispersion particles [170]. A more spectacular example of the application of cationomer-based elastomer coatings as specic radiation sensors is provided in [175]. A polyurethane cationomer was synthesised in the reaction of MDI, poly(oxyethylene)adipate, 1,4-butanediole and Nmethyldiethanoloamine (N-MDA), with the N-stilbene chromophore built-in into the chain. Those cationomers were characterised by considerable UV absorption (kA = 313332 nm) which in turn under specic conditions was followed by secondary uorescence (violet-blue light with the wavelength of 420470 nm).
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PU cationomers are produced chiey in the reaction of isocyanate-capped prepolymers and low-molecular weight tertiary amines which contain hydroxyl groups in their structures. The suitable ion is obtained when amine is neutralised with acid (acetic acid or formic acid in most cases), or when ammonium salt is formed in the reaction with dimethyl sulfate, alkyl chlorides, benzyl chloride or even with another polymer which contains chlorine atoms, in accordance with scheme (79):
CH3 OCN NCO + HOCH2CH2NCH2CH2OH CH3 OCONH OCONH NHCOOCH2CH2N CH2 CH2 CH3 + NHCOOCH2CH2N CH2 CH2 ClR RCl
79
This type of cationomer was synthesised in the process composed of a few steps. Initially, a classic urethaneisocyanate prepolymer was produced in the reaction of 2,4-TDI and 2,6-TDI with poly(oxytetramethylene) glycol (PTMO). That prepolymer was extended with the use of a compound with the tertiary nitrogen atom in its structure: dihydroxyl derivative of N,N 0 -bis(2-hydroxyethyl)isonicotinoamide (BHEIN), 2,3-dihydroxypyridine (DHP), 3,5-pyridine dimethylol (PDM) or N-MDA, in order to obtain a cationic centre. That material was further reacted with the previously obtained hydroxyl-capped prepolymer produced in the reaction of said diisocyanate and PTMO and 2-bromoethanol. The cross-linked polyurethanes, which additionally contained Br-neutralised alkylammonium cations, resulted from that procedure [176]. The use of various tertiary amines and alkyl chlorides or aryl chlorides gives the additional chance to modify polarity of polyurethane cationomers. Irrespective of that, the route remains open for structural modications which is typical for PUs, i.e. the use of various polyols and diisocyanates. If the substrates contain more than two functional groups, the additional choice becomes available to create branched and cross-linked structures. The useful cationomers contain 0.11.2% of NHR groups [55]. 3 The most important property of polyurethane cationomers is their ability to form stable aqueous dispersions, with acidic reaction, with no use of any emulsiers. The general structure of a polyurethane cationomer looks like in diagram (80):
80
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The prepolymer AB2 (scheme (75)) as produced initially, is then passed to the next stage of the cationomer synthesis process, i.e. it is reacted with a suitable dihydroxylamine (Eq. (81)) [177]: nAB2 + nZ ! (ZBAB)n 81
where Z = (HOCH2CH2)2 > NR, R = CH3, (CH2)3CH3, C(CH3)3, C6H5, which introduces tertiary N-alkyl groups into the polyurethane chain. Stage 3 yielded the polyurethane cationomer after reacting the NR groups with the use of HCOOH (Eq. (82)):
...AB O CH2 CH2 N CH2 CH2 O BA... + HCOOH R R= CH3 or C4H9 ...AB O CH2 CH2 NH+ CH2 CH2 O B ... COOR
82 Another process stage, alike for anionomers, is extension of so obtained prepolymers with the use of HMDA (Eq. (83)):
AB O CH2 CH2 NH+ CH2 CH2 O B NCO + n H2N (CH2)6 NH2 COOR AB O CH2 CH2 NH+ CH2 CH2 O B NH CO NH (CH2)6 NH CO NH B O CH2 NH CH2 CH2 O BA COOCOOR R
+
83 This reaction can be run in aqueous dispersion, too. After organic solvents have been expelled from the product dispersion, and after evaporation of water, the polymeric lm is produced [177], just alike for anionomers.
10. Examples of copolymers with linear polyurethanes 10.1. Acrylic-polyurethane copolymers The specialist literature has so far reported numerous examples of the synthesis and application of even more complex polymer systems which make use of linear polyurethane structures. Which is noteworthy is in particular poly(urethane-acrylate) copolymers due to their ability to form waterborne dispersions which can be utilised in the production of environmentally friendly polyurethane lacquers and special binding materials applicable for example in the ceramics processes. The powdered materials like corundum (Al2O3) or zirconium oxide (ZrO2) can be blended with polyurethaneacrylate binders and then moulded in the one-axis pressing operation, and the obtained so-called green ceramics can be subjected to preliminary machining. The corrosion-resistant parts of machinery or chemical equipment can thus be brought very close to their nal dimensions. After the ring process, only minor nal adjustments are needed for which very hard and expensive diamond tools are required [178,179]. In another example, the
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ceramic-polymeric slurry can be processed in the tape casting process to yield thin ceramic foils for electronics [180,181]. Mastering the synthesis of such polymer systems is not easy since the reaction stoichiometry needs to be precisely controlled at every successive stage of the process. And even then, we may not declare having learned the manufacturing process for the polymeric binder which oers the nal ceramics with repeatable performance properties. The considerable variety of chemical structures in oligomers to be converted into the nal urethaneacrylate copolymer will impact the potential for the formation of stable aqueous systems, miscibility of such systems, and chemical anity of the polymer for the surface of the ceramic materials. Moreover, phase structures of the systems obtained are equally important as their chemical structures. The former will be aected not only by the chemical structure of the urethaneacrylate ionomer itself, but also by the conditions adopted for the preparation of the polymer-ceramic slurry (with the use of Al2O3 or ZrO2), and by the conditions adopted for the cross-linking process (at the drying step) as well. When the micro-structure of the block PU polymer itself is analysed, considerable phase heterogeneity of that material is observed [182]. So, after additional acrylate segments have been introduced as internal plasticiser elements, the system becomes even more complicated. That can be advantageous on one hand since further possibilities are available to make the polymer structure compatible with the ceramic material surface. On the other hand, however, the manufacturing process becomes more dicult: the need to control the chemical structure of the polymer chain is additionally boosted by the need to control supermolecular structures at the ceramic product moulding stage(s). When water-repellent alkyl structures are incorporated into the PU macro-molecules, it becomes possible for example to precipitate polyurethane particles from organic solutions. The particles will not agglutinate and after the drying operation they can be employed as environmentally attractive powder coatings [183]. Moreover, poly(urethane-acrylic) dispersions which have the characteristic of IPN systems nd their outlets as tight protective coatings [184,185]. The IPN systems are characterised by interpenetration of linear macro-molecules or independent spatial networks of minimum two polymer types, which have been synthesised according to dierent mechanisms, e.g. acrylic polymers obtained in the free-radical polymerisation process and polyurethanes obtained in the polyaddition reaction of diisocyanates and polyols. In case of compositions, in which the linear structure is oered by one polymer only, e.g. poly(butyl acrylate), the system is called semi-IPN. Basically, the chains of both polymers should not be xed together by any covalent bond but they should be only tangled by the actions of hydrogen bridges and dispersion forces [30]. This is the case when acrylic monomers contain no active hydrogen atoms and when they cannot react with the isocyanate prepolymer. Those monomers are subjected to polymerisation in aqueous emulsion, in the presence of a dissolved initiator, e.g. hydrogen peroxide, and the dispersion of the polyurethane ionomer (produced separately beforehand) is also present in the system as the emulsier that function is sometimes supported by the external surface active agent [185188]. Irrespective of that method, the networks created by both polymers can be xed together when an unsaturated compound with the OH group in its molecule (e.g. 2-hydroxyethyl acrylate HEA) is used as one of raw materials in the synthesis of polyurethanes, i.e. extension compound for isocyanate prepolymer chains.
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The poly(urethane-acrylic) macro-anionomer product was synthesised in a four-staged step-growth polymerisation process, followed by free-radical copolymerisation in aqueous emulsion [168]. The chemical basis for that process is termination of linear urethaneisocyanate chains (Eq. (75)) by means of HEA (Eq. (84)): OCNRNCO + 2HOCH2 CH2 OOCCH@CH2 ! H2 C@CHCOOCH2 CH2 OOCNHRNHCOOCH2 CH2 OOCCH@CH2 84 where B represents a complex structure of polyurethane anionomer as shown in (75) or (76). The urethaneacrylate macro-anionomer produced in that way is capable of forming aqueous dispersions and it can be subjected to emulsion copolymerisation at further stages with typical acrylates (methyl acrylate and butyl acrylate) in the free-radical copolymerisation process, yielding the poly(urethane-acrylic) macro-anionomer, i.e. the nal product of this synthesis. The hydrophobichydrophilic performance of copolymers is controlled both by the surface activity of individual segments and by the chemical structure of the hydrophobic block. The latter can be modied by the use of various macro-initiators in the controlled radical polymerisation (CRP) of vinyl monomers. If a suitable urethane oligomer is used as the macroiniferter, the process will yield urethanemethacrylate ionic dispersions with less hydrophobic or more hydrophobic nature, wherein said polyurethane will make the hydrophilic site, while the hydrophobic performance of the copolymer will be controlled by the number of vinyl segments attached to the macro-monomer core and by their length. The most important issue is to select the suitable macroiniferter and to make it react in the aqueous medium with the hydrophobic monomer. The chain propagation reaction, following the radical mechanism, should produce the macro-molecule with the possibly compact structure. The research done in recent years have demonstrated the possibility of synthesising that kind of comb-like or star-like copolymers in the controlled/living techniques of radical polymerisation (ATRP) which can produce polymers with narrow poly-dispersity of molecular weight [115]. A living polymer can be formed in the reaction system by minimising the irreversible chain termination reactions, so that the chain propagation reaction comes to prominence. The suitable oligourethane I thus needs to be synthesised rst, which as the macroinifert must be capable of forming the stable radical I at the same time. That urethane oligomer, after addition of vinyl chain radicals, will develop the modied hydrophobic performance, depending on the type of monomer and length of produced chains. The side chains should contain ionic groups, e.g. derived from metacrylic acid, if the obtained copolymer is planned to be well water-dispersible. The urethane oligomer was used as the macroinifert in [114]; it was synthesised in the reaction of isocyanate prepolymer produced of MDI, PTMO and aromatic chain extender: 1,2-tetraphenylethane-2-diol. The aromatic structure of that compound made the resonant stabilisation possible in the created urethane macro-radical. The scheme for the reaction which yields the polyurethaneacrylate dispersion with the use of the urethane macroinifert is as below (scheme (85)):
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HO
OH + 2 OCN
CH2
NCO
60 oC
OCN TPED 30 oC DBTDL
NCO
85
MA 75 oC
PU-PMA Block Copolymers
i) DMF ii) H2O
Block Copolymeric Anionomer i) DMF ii) H2O
Block Copolymeric Dispersion
Dispersions of Block Copolymeric Anionomers
10.2. Polysiloxanepolyurethane copolymers It is necessary to dene precisely at the beginning of this chapter that the group of polysiloxanepolyurethane copolymers (PU-PDMS) can incorporate the high-molecular weight systems wherein the linear chains, or less frequently branched chains, are built of urethane segments which have been derived from diisocyanates and polyols (2), and most generally which are built of polysiloxane segments (formula (86)):
R3 R1 Si R4 O R3 Si O R4 n R3 Si R4 R2
86
wherein the radicals R3 and R4 can represent alkyl groups (methyl groups in most cases), while the radicals R1 and R2 represent alkylhydroxyl groups. With such a denition, the formula (86) shows the structure of a classic poly(dimethylsiloxane) (PDMS) chain. It is also possible to form the PU-PDMS structure directly in the reaction of diisocyanate and polysiloxanediole (formula (87)):
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H R
O N C H n O
O Si O C N R O
87
with siloxanediole usually synthesised by hydrolysis of suitable chloroalkylsilane. In both cases we introduce polyol-type siloxane segments to polyurethane chains. Those copolymers can be synthesised in a single-stage process and in a two-stage process as well [189193]. In the cases which have been so far described in literature reports, the siloxane segments present in the polyurethanepolysiloxane copolymers have dierent structures and the methods employed to incorporate them into the copolymer chains are dierent. For that reason, a,x-polydimethylsiloxanediole [191,194,195,197206] and a,x-polydimethylsiloxanediamines [192,196,207,209] (structure (84)) can be distinguished out within that group; they substitute some part of exible polyether segments, while the substituents R1 and R2 in this case stand for OH and NH2 groups. It is also possible to use PDMS with two hydroxyl groups at the same end of the chain (structure (88)) [197]:
CH3 R1 Si CH3 O CH3 Si O CH3 n CH3 Si CH3 C3 H6 R2 OH OH
88
or to use the branched ethyl-propylamine polydimethyl siloxane (formula (89)):

CH3 CH3 O Si O n CH3 CH2 NH CH2 NH2
2
CH3 Si O CH3 m
3
89
which can yield urea-type oligomers when combined with diisocyanates. This can be used in aqueous emulsion and employed as the polyurethane chain extender [210]. The isocyanateurethane or urea prepolymer can also be terminated with the mono-functional 3-amine-propyltriethoxysilane. The linear PU-PDMS so obtained can be subjected to cross-linking by hydrolysis of ethoxylate groups (structure (90)) [189]:
C2H5 H O H N CH2 CH2 CH2 O C N R1 N C O H O Si O C2H5 O C2H 5
90
The polysiloxane compounds employed until now in the synthesis of poly(urethanesiloxanes) replaced some part of exible polyurethane segments. The use of PU-PDMS
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copolymers based solely on polysiloxane exible segments is considered in a small number of newest reports [190,196,208]. The process is described, for example, for the production of that type of copolymers in micro-emulsions [211]. The obtained latex formulations oered a very low value of free surface energy cS = 26.328.9 mJ m2. It was explicitly found in other research programmes that PU-PDMS products obtained in the prepolymer method, i.e. by building-in polydimethyl siloxane segments to the polyurethane chain at the prepolymer synthesis stage, followed by chain extension by means of 1,4-butanediole, oered superior strength properties to their structural analogues synthesised in the one-stage method [212]. Descriptions can also be found for physical mixtures of polydimethyl siloxanes which formally do not contain any groups capable of reacting with polyurethane components [213]. It was conrmed for such polymer blends obtained in the co-extrusion method that polysiloxanes tend to migrate to the surface after some time which conrms thermodynamic immiscibility of PU and PDMS components in practice. However, even a small content (1.52%) of polydimethyl siloxanes in the mixture with thermoplastic polyurethane improves the tensile strength of the latter even by 40%, and its abrasion resistance by 25% [212]. The hybrid coatings known in the literature under the name of ceramers make an interesting example for the systems composed directly of isocyanates and polysiloxanes. They are produced, e.g. by reacting tetraethylorthosilikate modied by 3-amine-propyltrietoxysilane with isocyanurate obtained by trimerisation of HDI [206,214216] (structure (91)):
(CH2)6 NCO O N O
91
N OCN (H2C)6 O N (CH2)6 NH O C NH (CH2)3 Si (OCH 2CH3)3
Stanciu at al. [194,195] synthesised a PU-PDMS system wherein soft segments were represented by polydimethyl siloxane and by ethylene glycol polyadipate at the same time. The produced isocyanate prepolymer was then extended with the use of 1,4-butanediole. The PU-PDMS systems, in which soft segments had the structures of polyesters and a,xpolydimethylsiloxanodioles, were found to oer more advantageous strength properties. Additionally, the increasing length of the PDMS chain was accompanying by improving exibility and thermal stability of the produced rubber plastics. Unfortunately, tangent of the mechanical loss angle (tan d)max was increasing at the same time, which makes the evidence that those materials are less prone to reversible and dynamically changing deformations [194]. The PDMS-derived exible segment acts like the internal plasticiser for rigid poly(ester-urethane) segments which is reected by lowering the softening point by about 7 C [217]. The mechanical and thermal performance of PU-PDMS copolymers is additionally aected by the potential presence of crystalline structures which can possibly be met in linear polyurethanes synthesised from the aromatic symmetrical diisocyanate (MDI) and the aliphatic one (HDI). Those reasons were found to be responsible for better thermal stability of copolymers containing PDMS soft segments built-in into HDI-derived urethane hard segments, even in relation to analogous systems produced of aromatic MDI [218]. PU-PDMS formulations with additional poly(ethyleneadipate) are characterised by the two-phase micro-structure, in which hard urethaneurea segments form dispersion in the
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continuous or semi-continuous soft phase of elastomer [195]. PDMS elements, when introduced to PUs, create thermodynamically immiscible systems and contribute to the microphase separation of rigid and exible segments. They are also responsible for some separation within the soft phase which results from dierent values of the solubility parameter for the components which otherwise form a macroscopically homogeneous phase [219]. It is hence clear that any increase in the molecular weight of the exible PDMS segments to be built in would induce disturbances in the original order, which would be manifested by the decrease in crystallinity, which can be observed experimentally. The studies of the copolymer with high levels of mono- and di-functional PDMS components, with the use of the transmission electron microscope (TEM), conrmed the presence of lamellar structures arranged at random in the continuous polyurethane matrix [195]. Incorporation of polydimethylsiloxane with secondary amino groups at both ends (structure (92)) [192] into the polyurethane chain makes another interesting method for the synthesis of PU-PDMS systems:
CH3 NH CH2 CH CH2 CH3 CH3 Si O CH3 n CH3 Si CH3 CH2 CH CH3 CH2 NH CH3
92
Such PU-PDMS copolymers, owing to the tend of the siloxane segments to migrate to the surface, oer improved thermal stability under oxidizing conditions. That is because the oxidation process covers the surface of copolymer with the additional protective layer of PDMS homo-polymer. There are also numerous possibilities of building in PDMS segments into PU ionomers [189,190,197,198,210,220224]. The polymer coatings obtained from environmentally friendly waterborne PU-PDMS systems, wherein polydimethyl-siloxanes make the only exible segments, show the required hardness, their resistance to organic solvents and water is similar to that of typical PUs, and their adhesion to steel is good [190]. The interesting structure was found in the ionomer obtained from the two-stage synthesis of polyurethane and PDMS with two hydroxyl groups located at the same side of its chain (86) [197]. Polyurethane formed the core chain of the produced polymer, to which various lengths (n = 30, 63, 213) of side polydimethylsiloxane chains were attached. As compared to PU ionomers synthesised with the use of classic a,x-polydimethylsiloxanediol, the obtained coating oered the lower value for the maximum wetting angle (in accordance with expectations) which was comparable to that of non-polar silicone rubber. The adequately synthesised polyurethane elastomers and polysiloxanes are characterised by considerable resistance to biodegradation, and they are known for their physiological inertness, hence they make the interesting materials for the production of medical implants [191,205]. For example, adhesion of blood platelets was tested to PU-PDMS copolymers grafted with poly(oxyethylene) glycol, where various chain extenders were used, and where bonds were formed through allophanate groups or ester groups [205]. The advantageously lower adhesion, i.e. also prevention of blood cell aggregation, was aected by degree of phase separation and hydrophilic performance of the copolymer surface. Applications of linear PU-PDMS copolymers in electronics seem promising, e.g. as polymer electrolytes [225227]. Another class, which goes beyond the scope of this work,
978
is made by cross-linked polyurethanepolysiloxane systems applicable as coating materials and structural materials; they are similar to typical hardening plastics [190,199 202,223,15,228]. That type materials, produced with the use of a,x-polydimethylsiloxanediol, are employed e.g. as coating materials analogous to moisture-hardened classic urethaneisocyanate prepolymers [190]. Those coatings oer excellent mechanical properties: tensile strength reaching as high as 17 MPa, unit elongation over 700%, and hardness of even 70 Sh A, good water resistance and thermal stability which is close to that of homo-polysiloxanes. 11. Micro-phase separation in polyurethane elastomers. Glass transition temperatures. Analysis of phase structures by DSC, SAXS and AFM methods As it was already mentioned, the specic structural feature of high-molecular weight linear PUs, and in particular elastomers, is their segmented structure. The PU chain is composed of hard segments and soft segment arranged alternately [229,230]. The hard segments are most frequently made of non-polar hydrocarbon structures derived from diisocyanates, urethane oligomers obtained from diisocyanates and low-molecular weight hydroxyl chain extenders, or urea oligomers produced with the use of diisocyanates and water or amino chain extenders. The exible segments, on the other hand, are composed of oxyethylene groups or oxypropylene groups, in particular oxytetramethylene polyester polyols or polyesters which make linear polyurethane even more exible. The structure of the segmented PU can be schematically presented as below (scheme (93)):
93
The structure of a PU macro-molecule results from the spatial arrangement of polymer chains in the condensed phase, i.e. after the polymerisation process and possibly after cross-linking with the use of allophanate groups or biuret groups. Linear PUs obtained from MDI and 1,4-butanediol form a zigzag chain in which benzene rings of MDI are arranged at the right angle against each other [231]. On the other hand, the PU chains synthesised of 2,4-TDI and 2,6-TDI are arranged in one plane because of the coplanar arrangement of both TDI-derived benzene rings and urethane groups attached to those rings [232]. Considerable structural diversication of PU chains gives rise to strong interactions both within individual macro-molecules and between dierent macro-molecules. The hard segments can interact with each other e.g. through hydrogen bonds or through dispersion
979
inuences of polar urethane groups, which contributes to agglomeration of those groups and formation of a compact rigid phase. That phase is hardly miscible with the soft phase which has been formed with the use of much less polar soft segments. If the hard phase and soft phase within a linear PU become completely immiscible, two separate phase transition points can be frequently observed as two clearly dierent glassy temperatures for soft segments (Tg1) and for hard segments (Tg2). That is specic just for linear and segmented PU elastomers. In some cases, additional crystalline phases can form within each of those phases. Melting points for hard segments (Tm2) or for soft segments (Tm1) can also be observed then. The interactions through hydrogen bonds can also create separate hard domains within the soft phase or separate soft domains within the hard phase. That certainly produces a multi-phase system in which usually the continuous soft phase makes the matrix. The matrix is penetrated through by some part of the hard phase or by the whole of it. Alternatively, the hard phase can be dispersed in the matrix. There are cases in which a given macro-molecule of the linear PU goes through a few or even through a dozen or so hard domains and/or soft domains. That is typical for semi-crystalline micellar structures [233]. It is specic that the polar urethane groups, which join the hard segments and soft segments together, are grouped at the domain interphase in most cases. Separation of microphases is not precise, however, and some hard segments are dispersed within the domains of soft segments and the intermediate phase is thus formed, as illustrated in [234] (scheme (94)):
interphase Faza po rednia
Faza twarda hard phase
94
Faza mi kka soft phase
The degree of phase separation in PUs is controlled by numerous factors: chemical structure of PU chains, polarity of their structural fragments, sizes of hard segments and soft segments, molecular weights and molecular weight distribution in linear PUs, method employed to shape the nal PU product (foil, bre) and process parameters adopted for that method (temperature, melt cooling rate, solvent evaporation rate, possible presence or absence of mechanical stresses). From the theoretical viewpoint, phase separation can be controlled by the thermodynamic factors which result from dierences in structures of hard segments and soft segments, and by kinetic factors which for example promote separation of aliphatic segments due to their higher mobility and thus lower viscosity of the reaction mixture which is just polymerising.
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The studies by Kang and Stoer [235] showed thermodynamic factors to be the most decisive. PUs with structural segments derived from aliphatic diisocyanates had lower separation degrees than their equivalent PUs obtained from aromatic diisocyanates. Those researchers observed no impacts from kinetic factors. Such impacts were observed by Chu et all. [236] who analysed the phase structures of PUs which contained soft segments derived from poly(oxypropylene glycol) with ethylene oxide molecules built-in at chain ends, and much more hydrophobic and less mobile soft segments derived from PTMO. The eect of M n for soft segments within 10002000 g/mol turned out to be essential in those considerations [236]. The micro-phase separation is generally more prominent in polyetherurethanes due to stronger interactions between ester groups and urethane groups than between ether groups and urethane groups [237]. Also, a higher degree of separation can be observed with linear PUs which have been extended with low-molecular weight compounds, e.g. dianoles (20), containing aromatic rings with symmetrically located substituents. The chances are higher then that the arrangement of polymer chains can be favourable for phase separation as early as at the polymer material solidication stage. On the other hand, the rotation hindering elements, like voluminous substituents at the benzene ring (e.g. Br atoms), contribute to improved miscibility of phases. Miscibility is also improved by increased polarity of structural fragments within macro-molecules [238]. The level of phase separation in PU elastomers usually increases with the increase in the cross-linking density [16], although something completely opposite was observed by Yu et al. [239]. Also, the increasing length of the extender chain enhances the trend for phase separation [240]. The segmented structure, which is much more clearly outlined in PUs synthesised in the prepolymer-based method, is favourable for phase separation, which in turn aects the physical and mechanical properties of the produced PU materials, e.g. their hardness and modulus of elasticity, abrasion resistance and scratch resistance, vibration dampening and noise attenuation capacity [92]. The obtained phase structure makes the linear polyurethanes behave like elastomers, i.e. oer negative glass transition temperatures (Tg1) resulting from the presence of soft segments, high ultimate elongation (over 500%) and considerable exibility at low temperatures. That was found, e.g. on the basis of DSC thermograms of linear polyurethanes obtained in the multi-stage polyaddition method described in Section 6.2, which were nally subjected to cross-linking with the use of triethanolamine (TEA) or Desmodure RE (D-RE). Two glass transition points (Tg1 = 19 C, Tg2 = 57 C) can be observed in the thermogram of PU synthesised from the urethaneisocyanate oligomer 1b1000 (Table 5) and nally extended with TEA (Fig. 17), which conrms clearly the micro-phase separation process. On the other hand, the DSC curve for the polyurethane synthesised from the urethanehydroxyl oligomer and extended with D-RE (Fig. 18) shows generally one glass transition point only at Tg1 = 42 C, but the endothermic peak is also seen at Tm = 35.5 C that represents melting of the crystalline phase. The detailed interpretations for DSC thermograms of polyurethanes produced in the multi-stage polyaddition process can be found in [233]. That study made it possible to evaluate qualitatively the phase structures of polyurethane elastomers synthesised in various methods from the same pool of feedstocks. Also, the eects were analysed which come from chemical structures present in the studied PUs ether groups and ester groups which are decisive for the structure of the soft phase in
981
Fig. 17. DSC curve for PU obtained from the oligomer 1b1000 (according to Table 5) and triethanolamine [141].
Fig. 18. DSC curve for PU obtained from the oligomer 2b1000 (according to Table 5) and Desmodure RE [141].
urethanes obtained from 2,4-TDI, 2,6-TDI and cross-linking compounds: D-RE or TEA. Two glassy temperatures were observed for the studied PUs which are typical for elastomers: the rst one for glass transition of soft segments appeared at Tg,s = 65 to 44 C, and the second one could be observed at Tg,h = 41 to 35 C which represented relaxation of hard segments in PUs. Three or even four phases could be distinguished in all
982
synthesised PUs: hard crystalline phase composed of TDI segments and the cross-linking compound; intermediate phase i.e. mixture of TDI-derived hard blocks, cross-linking agent and oligomerol-derived soft blocks; soft phase composed of polyol-type soft segments; and also crystalline phase composed of soft blocks was observed in some samples. The examples of DSC thermograms for selected PUs, listed also in Table 5, were shown in Fig. 19 [233]. The thorough analysis revealed that the crystalline phase was dispersed in the continuous phase in every case. It was also found out that phase separation in PUs obtained from POG was generally much better than that for PUs which contained PCD in their structures. The increasing value of M n for oligodiol did not have any signicant eect on the structure of the hard phase, it slightly reduced separation of soft phase, and it improved purity of that phase and its potential for crystallisation at the same time. With the increasing length of the linear urethane chain, which is decisively controlled by the prepolymer method, somewhat lower separation and purity of the soft phase is observed, and in some samples also inferior order in the hard phase and increased amounts of the intermediate phase. The presence of aromatic structures (derived from D-RE) in the hard phase promotes the orderly arrangement of that phase and reduces separation of the soft phase at the same time. Two chain extenders were tested: TEA and D-RE, and better crystallinity of the hard phase advantageous also for the mechanical properties was available when hydroxyl oligomers were extended with triisocyanate. Based on the specic heat and melting enthalpy values as measured at the phase transition points, Tg and Tm, respectively, it turned out possible to plot phase diagrams for those polyurethanes, i.e. to obtain the general image of their phase structures (Fig. 20) [233]. The soft segments are usually arranged at random, hence the properties of the phase formed by them are isotropic. The hard segments are arranged nearly perpendicular to
Heat flow [W/g] Endo Exo
PU-II-200 (2) PU-II-300 (2) PU-II-400 (2) PU-II-600 (2) PU-II-1000 (2) PU-II-530 (2) PU-II-1250 (2) 0.5 W
-50
50
100
o
150
200
250
Temperature [ C]
Fig. 19. DSC thermograms of PU obtained by the prepolymer method (2) at the stage II, with the use of dierent glycols (according to Table 5) extended by Desmodure RE [233].
983
Fig. 20. Phase diagram of PU obtained by the prepolymer method (2) at the stage V, extended by triethanoloamine (according to Table 5) [233].
the longitudinal centre line of hard domains hard domains are thus locally anisotropic and they aect correspondingly the physicalmechanical properties of PUs [92]. The studies of phase changes in PU ionomers with the DSC method also revealed substantial dierences within the low-temperature and high-temperature glass transitions of exible polyether segments and hard segments with more diversied urethane structures and urea structures. It is most probably for that reason that denitely more complex proles for DSC thermograms were observed within positive glass transition temperatures for the PU anionomer synthesised from MDI, polyoxypropylene glycol (Mn = 450 g/mol), and 2,2-bis(hydroxymethyl)propionic acid (DMPA), neutralised with triethylamine (TEA) and extended by means of 1,6-hexamethylenediamine (HMDA) (1.95 wt% COO) (sample no. 2), and for the analogical PU anionomer obtained from 4,4 0 -methylenebis(cyclohexyl isocyanate) (HMDI), (1.91 wt% COO) (sample no. 3) (Fig. 21) [234]. In accordance with expectations Tg1 < 60 C corresponds to glass transition of soft ether segments, while Tg2 represents the glass transition point of the hard urethane segment and it is aected both by the type of diisocyanate and by the ionic reactant. As is shown by the data in Table 8, the type of diisocyanate can have completely dierent eects on Tg2 in anionomers and in cationomers, which proves the signicance of ionic segments for the formation of the hard phase in the polyurethane ionomer. That can be accounted for by the dierences in intermolecular interactions in both types of ionomers [241,242]. Not in all cases the DSC method makes it possible to infer unmistakably about the polymer phase structure, especially when the chemical structure is complex and thus the supermolecular structures can be expected to be very complex, too. In order to illustrate such a case, Fig. 22 provides the DSC thermogram for the polyurethaneacrylate copolymer obtained with the use of 2-hydroxyethyl acrylate, as mentioned in Section 10.1 [168]. That thermogram shows that the analysed copolymer comprises the soft phase with the glass transition temperature Tg1 = 62 C, i.e. exible polyol segments, which is conrmed also by earlier ndings [243]. The glass transition point within the positive range
984
-0.0
Tg =- 67.39 C
2 3
-0.2
Tg =- 61.37 C
-0.3
Tg = 27.42 C
2
-0.4
Tg = 71.83 C
2
-60
-40
-20
20
40
60
80
100
120
140
160
Fig. 21. DSC thermograms for polyurethane anionomers obtained from MDI (curve no. 2) and HMDI (curve no. 3) (according to Table 8) [241].
Table 8 Glass transition temperature of hard segments in the waterborne polyurethane ionomers obtained from polyoxypropylene glycol of Mn = 450 g/mol, various diisocyanates and ionic regents, extended in aqueous medium with HMDA [241,242] Type of diisocyanate TDI MDI HMDI TDI MDI HMDI Type of ionic reagent DMPA Type of ionomer Anionomer Tg2 (C) 12 27 72 30 16 3
N-MDA
Cationomer
of temperatures, Tg2 = 2.14 C, probably conrms low miscibility of polyol-type exible segments with rigid urethane segments, which in PU elastomers usually form the hard phase with Tg2 > 50 C that phase has not been shown in this thermogram. That can be explained by the plasticizing eect exhibited by methyl and butyl acrylates on the hard phase in PU. A wide endo peak within 60110 C is also noteworthy; it indicates some orderly arrangement which is more clearly seen in the hard phase of that copolymer. The presence of orderly structures within the hard phase was also conrmed by X-ray diffraction observed for coating samples obtained from that copolymer. A maximum for the scattering vector q = 0.035 A1 is clearly seen in the SAXS pattern (Fig. 23), which made it possible to calculate the linear parameter of orderly arranged aggregates forming the internal structure of the hard domain under consideration as d = 179 A. The similar SAXS prole was obtained for the PU elastomer in which the hard
985
0.0
-0.1
Tg = -62.37 C
-0.2
Q [mW/mg]
-0.3
Tg = 2.14 C
-0.4
-0.5
-0.6
-60
-40
-20
20
40
60
80
100
120
140
Temperature [oC]
Fig. 22. DSC thermogram of urethaneacrylic copolymer [168].
segments had been produced of model urethanes obtained from 1,4-butanediole and piperazine. Flexible segments in that PU had been derived from poly(tetramethylene oxide). The recorded value of d = 106 A was assumed to correspond to the interdomain spacing between the structures of rigid segments within the hard domain [183]. The interdomain structures turned out much more complex in case of the analysed copolymer which was evidenced by the second and more attened maximum for q = 0.054 A1 (d = 116 A) (Fig. 23). That can be explained by the presence of additional interdomain spacing, resulting from the presence of other hard segments derived from acrylates. The analysis of SAXS patterns with similar proles for ionomers based on copolymers of styrene and acrylic acid suggests that the rst maximum (q = 0.1 A1) represents the bigger ionic aggregates, wherein the clusters have the diameters within 50100 A, while the second 1) appears only for the acrylate content above 11.7 mol% and for maximum (q = 0.3 A acrylates with the Cs+ counter ion built-in, i.e. for the presence of smaller structures (so-called multiplets) with the diameter below 40 A [244]. The slightly smaller interdomain spacing in the considered polyurethaneacrylate copolymer can thus result from the presence of hard acrylate segments. The WAXS pattern (Fig. 24) conrms the above conclusions. Two peaks can be seen outlined in that gure the rst is very wide and it appears at the lower value of the angle 2H. It speaks for the presence of the area with inferior order and more loose packing. Another peak is clearly sharper and it appears at the higher
986

2000
1600
Intensity [imp/min]
1200
800
400 0.02 0.04 0.06

-1
0.08
q [ ]
Fig. 23. SAXS spectrum of FP urethaneacrylic copolymer [168].
500 450 400 350 Intensity of scattering 300 250 200 150 100 50 0 0 10 20 30 2 40 50 60 70
Fig. 24. WAXS spectrum of FP urethaneacrylic copolymer [168].
987
value of the angle 2H it conrms the presence of the more orderly phase with higher packing [168]. Fig. 25 provides the comparison of SAXS patterns for the polyurethane anionomers synthesised from various diisocyanates [241]. In the face of the complex interdomain structure of the analysed polyurethaneacrylate copolymer (as proved by means of the DSC and SAXS methods), it was advisable to continue analysing the size and shape of the hard domains and their dispersion within the copolymer matrix, in the form of a thin lm (coating). The atomic force microscopy (AFM) method was found applicable in visualisation of the surface micro-structure of the cross-linked coating [168]. That technique is useful to observe the changes in exibility of the polymer surface when the polymer is subjected for example to cross-linking, which on one hand advantageously improves strength of that material and on the other hand it makes the PU chains more rigid at the same time, i.e. the material becomes less exible. Those properties result from the specic morphology of polyurethane elastomers which can be studied by means of transmission electron microscopy (TEM), and recently also the AFM and Raman micro-spectroscopy methods have been employed [182,245]. The AFM method, which records the interactions between the measuring tip and the sample, oers the precise visualisation of the structures, i.e. makes it possible to obtain the image with hard and soft domains visible, with various shapes and sizes, and with the specic arrangement over the sample surface. Those images show the mechanical nature (coarseness and friction factor) and/or physicalchemical nature (wettability, polarity) of the surface, depending on the adopted detection technique. The AFM method has so far been utilised inter alia to analyse supermolecular structures in segmented PUs [182], to
10000
1000
4 1 3 5
Intensity
100
10
1 0.00 0.01 0.10 1.00
q
Fig. 25. SAXS spectra for polyurethane anionomers no. 15 [241]: (1) anionomer obtained from TDI, (2) MDI, (3) NMDI, (4) IPDI, HDI.
988
study the surface structures in sparingly degradable PUs applicable in the production of medical implants [246,247], and to analyse such structures in thin lms of PU ionomers [248]. The possible applications for visualisation of phase structures in polyurethane anionomers with the use of the AFM technique have been presented in [168,249]. Before the examples of AFM micrographs are presented which show the phase morphology in the urethaneacrylate copolymer as considered above, it is necessary to submit the short description of the measurement method at least. The cover layer to be studied was obtained by careful evaporation of water from the copolymer dispersion at 120 C during 2 h. Evaporation of water was conrmed by comparing the sample weight before and after evaporation (the evaporation operation took 1 h). After one more hour of drying, the sample weighing operation was repeated. The atomic force microscope (Nanoscope III, Digital Instrument, USA) was employed to study the supercial structures of the coating obtained from the copolymer. The scans were taken at ambient temperature, in air, and in contact mode (CM) conditions, i.e. at direct contact between the sample surface and the tip. The pyramidal Si3N4 tip employed in the CM system has a spring constant of 0.06 N/m (NanoprobeTM). Each scan was presented in the following data formats: topographic image (height, h), two-dimensional or three-dimensional (3d), phase image (phase, p), which represents the phase lag for probe vibrations at the boundary between two media due to friction of the probe tip on the sample surface (friction, f) or axial deection z of the probe tip after it hits any surface irregularity (deection, d). Figs. 26 and 27 show three-dimensional AFM images for topography of urethane acrylic copolymer surface samples of 30 30 lm and 10 10 lm, respectively, while the corresponding two-dimensional images have been shown in Figs. 28 and 29. They demonstrate a strongly diversied topography within even respectively small surface fragments of the analysed samples. The light-coloured places represent hard domains which are grouped into compact areas having the size of from 0.5 to 2.0 lm. Sometimes, however, they are dispersed all over the matrix which is formed by the soft domains. Miscibility
Fig. 26. Three-dimensional AFM image of a 30 30 lm surface area of urethaneacrylic copolymer sample [168].
989
Fig. 27. Three-dimensional AFM image of a 10 10 lm surface area of urethaneacrylic copolymer sample [168].
Fig. 28. Two-dimensional AFM image of a 30 30 lm surface area of urethaneacrylic copolymer sample [168].
Fig. 29. Two-dimensional AFM image of a 10 10 lm surface area urethaneacrylic copolymer sample [168].
990
of hard and soft segments forming both types of domains is apparently limited and that limitation is more clearly seen at the interphase. The dierences in height (h) (light-coloured and dark places) reach as high as 2500 nm. The most light-coloured details of topography in the obtained AFM image represent the particles with the diameter of about 100 nm (Fig. 27). These can be attributed to linear dimensions of individual hard domains formed (light-coloured agglomerations against the dark background) or soft domains formed (dark-coloured against the light or grey background). Fig. 30 provides the 10 10 lm AFM image scan of the analysed surface. Those images result from the changes in physical properties, e.g. mechanical features or surface friction, experienced when the sample is analysed with the use of the AFM method. Single inclusions or whole agglomerates of hard domains are visible on the background of dark-coloured or grey polymer matrix formed by soft segments. The analysis of the phase image (Fig. 30) suggests that the domains which produce sharply outlined heights in the topo-
Fig. 30. AFM phase image (friction) of a 10 10 lm surface area of FP sample. Section analysis of structures observed in AFM image of urethaneacrylic copolymer sample [168].
991
graphic picture (Figs. 27 and 29) are not composed as one might expect from h-type images (3d or 2d) solely of hard segments. Hard segments are also to some extent dispersed within the matrix of the copolymer. That AFM image is clearly dierent from a typical image for a segmented PU elastomer as observed with that technique, in which domains of hard segments and domains of soft segments can be clearly observed [182,183]. We face a better dispersed structure in the urethaneacrylate copolymer which probably results from the presence of 2-hydroxyethyl, methyl and butyl acrylates, and from the presence of ionic groups. The former components exert the softening eects while the later bring their contribution both into stiening the structures through ionic bonds and hydrogen bonds, and into softening the structures at the same time through water repellent alkyl groups of built-in acrylates and additionally triethylamine counter-ions. Inclusions or even agglomerates of hard segments can be seen in some limited areas. In just those areas probably there existed the possibility of better orientation what was manifested in the form of diraction maximum in the SAXS curve (Fig. 23). The AFM image (Fig. 30) generally shows that the structure of urethaneacrylic copolymer has been composed of a relatively homogeneous matrix, into which shapeless hard domains have been included in the form w single islands. The mass fraction of that reasonably well-developed hard phase can be evaluated at 2530%, hence the balance 813% of hard segments must be dispersed in the soft phase. There are strongly non-uniform and tumour-like structures in the AFM image (Fig. 30) which have been built-in into the matrix. In order to be able to investigate that image more closely, the section along the line AA 0 was analysed. The width of that excrescence was indicated by markers. The AFM analyser recorded considerable uctuations in supercial properties along that line what makes the evidence for actual diversication of the surface. That can result from immiscible hard domains and soft domains located close to each other and overlapping with each other [168].
12. Intermolecular interactions. Hydrogen bonding. Free surface energy The van der Waals intermolecular interactions with the dispersion nature [(induced) dipoledipole type] and with the inductive nature, and also those involving the hydrogen bonds, have the signicant ordering impacts on the supermolecular structures of linear polyurethanes. The urethane and ester groups, because of their stable dipole moments, are characterised by relatively high cohesion energy values (36.5 and 12.1 kJ/mol) as compared to the ether group (4.2 kJ/mol) and methylene group (2.85 kJ/mol). The cohesion energy of the aromatic ring amounts to 16.9 kJ/mol [55,250,237]. The urethane, ester and ether groups do not only aect the polymer cohesion energy but they are also active in the formation of hydrogen bonds. Under the solid-state conditions, at room temperature, nearly all NH groups in PUs are involved in those bonds. The NH group in the urethane structure is always a proton donor, while the acceptor function can be provided by the oxygen atom within the urethane C@O group, or within the ester group in case of polyesterurethanes, or by the ether oxygen atom in case of polyether urethanes [251]. If urea groups are present in the polymer chains, additional types of hydrogen bonds can be formed. The presence of hydrogen bonds in PUs was conrmed by IR spectroscopy [252259]. The bands representing the carbonyl groups (17301740 cm1) and imine groups
992
(34453450 cm1) are shifted towards lower frequencies in IR spectra and they can be observed at 17031710 cm1 and 33403260 cm1, respectively. Based on the observed shifts, the molecular orbital methods were employed to calculate the optimum molecular geometry as well as energy and length values for those bonds [257259]. The energy and length of the hydrogen bond between the imine group hydrogen atom and the urethane carbonyl group is dependent on the type of the structure (structures (95)). The most stable are those bonds formed by the ciscis (structure 95a) and transtrans (structure 95b) conformers because of the possible double interactions between oxygen and hydrogen. The bond energy in the structure 95a is 46.5 kJ/mol, and the bond length is 1.87 A. The bond . Only one hydrogen bond is possible in the struclengths in the structure 95b are 1.96 A tures 95c and 95d, hence it is weaker (its energy is 18.4 kJ/mol and its length is 2.13 A).
O C N O ... H H ... O N O C O (a) cis - cis
N C
H ... O C N O
O ... H
(b) trans - trans
N C O O ... H N C O (c) trans - trans O

H O C N O O ... H
O C N
95
(d) cis - trans
N O C O
H ... O
N O C O
H ... O
C O
(e)
(f)
Apart from hydrogen bonds, also the bonds between the urethane group and the ether oxygen atom can be formed in polyetherurethanes (formula 95e), and the additional bonds between the ester groups can be formed in polyesterurethanes (formula 95f). The binding energy between the imine group and the ether group atom is equal to 23.6 kJ/mol, and the bond length is 1.96 A. The bond with the ester group is more stable (its energy is 25.9 kJ/mol and its length is 2.0 A). The hydrogen bond between the imine group and the ether group atom is thus by one half weaker than the strongest bonds between two urethane groups, and the binding energy with the ester group is higher only by 2.3 kJ/mol. The earlier calculations have shown that the binding energy values for the
993
urethaneurethane bond and the urethaneester group bond are comparable, while the bond between the imine group and the ether oxygen atom is weaker than they are by about 6 times [55]. The calculations by Blackwell et al. [231] have shown that the urethane-tourethane hydrogen bond is linear, the angle of deviation from linearity is 22.0 6, and the bond length is 2.98 0.05 A. The hydrogen bonds undergo weakening at the temperature above 75 C [260]. The bonds of 95e undergo rearrangement then to form the urethaneurethane bonds, and they become dissociated at the temperature above 130 C. A high number of hydrogen bonds and polar groups in PUs puts considerable limitations to chain translation and for that reason those polymers can oer high strength, high Youngs modulus and low creeping at operating temperature. In case of polyurethane ionomers, the intermolecular interactions are additionally boosted by electrostatic interactions between ionic fragments present in chains, as discussed in chapter 9. The structural factors and intermolecular eects in PU ionomers also inuence the surface hydrophobichydrophilic performance of those materials, which can be characterised by means of the free surface energy cS of the plastic, and that can be shown by the following formula [261]: cS cLW cAB S S 96
where cLW denotes the polar component, which is aected predominantly by dispersion S interactions resulting from the chemical structure of hard urethanepolyether segments or urea segments and soft polyol segments (polyether or polyester ones), and from possible interactions between them through hydrogen bonds; cAB describes the Lewis acidLewis S base interactions which are controlled by the PU ionic centre and by the nature of counter ion involved, and in case of the aqueous dispersion of the ionomer also by pH of the medium [262]. The use of additional non-polar PDMS segments to the PU ionomer should reduce considerably the value of the surface free energy of so produced copolymers. Yet, there are few reports available on that subject only. Those some few which are available refer to the possible modications of surface properties of PU-PDMS systems from the viewpoint of changes in the hydrophobic performance of the plastic surface and potential applicability for medical implants [263]. The properties of PU surfaces were found to be very important when those polymers are to be employed as waterborne binders for oxide-based ceramic powders (Al2O3 and ZrO2), as discussed earlier, which are then subjected to green machining [150,168]. The surface properties are important also for the preparation of the aqueous ceramic-polymer slurry which is then converted to thin ceramic coatings in the tape casting or doctor blade processes: In order to modify the free surface energy of PU ionomers dispersed in water, anionomeric isocyanate prepolymers were extended with the use of diamines with diversied hydrophilic performance [150]. The surface energy values cL for the obtained dispersions were analysed through measurements of wetting angles H between those liquids and the standard surface of poly(tetrauoroethylene) with the known surface energy value cS = 20 mJ m2. The surface energy values cL for those liquids were then calculated from the van-Oss-Good and Neumann physical models [263]. The dispersion component cLW and the acidbase component cAB L L
994
were found to be signicantly inuenced by the structures of polyol-type and urethanetype segments which control the dispersion and polar interactions. The types of ionicgroup containing segments impacts much more the value of cLW than the value of cAB , L L which makes a rather surprising conclusion [150]. That question should be explained in more details by further research, and it should be veried how far the free surface energy of PU could be modied by adding ionic segments to its structure. Since the method employed to measure the wetting angle H is very sensitive, numerous factors have to be controlled which aect the surface energy to obtain reliable ndings: temperature, shape and size of drops of analysed liquids, rate of solvent evaporation from the liquid drops applied on the substrate, coarseness of substrate as well as numerous structural factors which are decisive for the polymer surface energy (molecular weight, polydispersity of chemical composition and polydispersity of molecular weight GPC method is applicable for that analysis) [261]. As one can expect, further research of the energy state of the surface will create new tools to control and adjust chemical and biological resistance of polymer materials, certainly inclusive of linear polyurethanes. Linear PUs were shown to give the opportunities for introducing far-reaching structural changes to the polymer and thus to aect the structure of its surface. The properly tailored structural changes are capable of improving the surface resistance of plastics which is very important if polymers are to be employed as biomedical materials [264]. Those changes can also improve biodegradability of polymers which is important for safe utilisation of plastic wastes after the product service period, e.g. spent foamed polyurethane [265]. Moreover, the hydrophobic performance of the plastic surface can enhance miscibility of polymer systems which are in general thermodynamically immiscible, e.g. polyolens and polyamides, or it can improve adhesion of polymers to inorganic llers, e.g. to glass bre or carbon bre, which makes a prerequisite in the production of polymer composite materials. Irrespective of the questions as above, new outlets for the polyurethane plastics, for example in electronics (selective and electrically conducting membranes [266]), in medicine (implants of blood vessels [164] and temporary membranes which help to restore operation of body organs which have been impaired in accidents [267]), in civil engineering (environmentally friendly coatings of waterborne lacquers [268] or polymer composite materials which involve polyolens and polyurethanes [269], etc., induce demand for precise information on the structures of external molecular layers and the surface properties resulting therefrom. A more methodical approach to that issue is required nowadays, in particular since the studies of polyurethane surface properties presented in reports have been done as contributory research only, to supplement the general investigation of specic materials intended for particular purposes, e.g. for medical implants (Pelletane polyurethane), for which the thrombocyte-toxic properties of blood-contacting organic materials are essential [263]. From the viewpoint of energy values, polyurethanepolysiloxane copolymers which are attractive for a number of such applications should be considered as medium-energy materials, cS = 3050 mJ m2. That value is dened by the specic arrangement of linear or branched structural polyurethane units and linear polysiloxane units into copolymer chains. Their chemical and physical interactions in so produced copolymers result in new properties, i.e. combination of positive features of polar PU elastomers, with mechanical strength over 10 MPa, and less mechanically resistant (0.10.5 MPa) hydrophobic polysiloxanes which are more thermally stable (200250 C) and which have cS = 3045 mJ m2 [264].
995
13. Thermal properties of linear polyurethanes When the eects are considered of chemical structures and phase structures of linear polyurethanes on their properties which are important from the viewpoint of materials technology, it is necessary to pay attention to thermal properties of those plastics. The previous chapter addressed the block structure of linear polyurethanes and its consequences for the phase transitions (recorded by DSC method) within glass transition temperatures of soft and hard segments, and for melting temperatures of crystalline structures formed within those phases. The eects of those parameters are also essential for thermal stability of PU plastics. What is especially important in this respect is the initial degradation temperature which is dependent on thermal stability of the weakest point(s) within the polyurethane macro-molecule urethane bonds and ester bonds. The initial decomposition point for the urethane bond (which is most representative for PUs) formed in the reaction of MDI and poly(ethyleneadipate) is 227 C [270]. Much higher decomposition temperature, i.e. 319 C, was recorded in this case as the minimum in the DTG prole for poly(esterurethane) produced from TDI and polyesters derived from adipic acid, ethyl glycol and neopentyl glycol, and trimethylolpropane [271]. Decomposition of urethane bonds in PUs obtained from MDI, polyester of adipic and phthalic acids, and ethylene glycol, begins at 240 C, it reaches its maximum rate at 337356 C, ester bonds which involve an aliphatic acid undergo destruction at 344 C, while those which involve an aromatic acid at 386400 C [251]. Decomposition of PUs obtained from TDI and castor oil or hydroxylated polybutadiene was observed to start as early as at 200 C and to run through three steps, with polybutadiene derived PUs being more stable [272]. Thermal decomposition of segmented PUs is a multi-stage process and its complexity is dependent on the presence of rigid segments [273]. The rst degradation stage is fast but its rate decreases for the higher contents of soft segments. The rate constants for the rstorder decomposition reaction of PUs obtained from MDI, poly(ethyleneadipate) and 4,4 0 -dihydroxydiphenylmethane reach (60429) 106 s1 at 300 C, depending on the content of soft segments. The growing contents of hard segments in PUs make those materials more susceptible to degradation. That behaviour suggests that degradation is initiated predominantly within hard segments. The controlling factor is high concentration of urethane groups obtained with the use of phenol derivatives which oer much inferior thermal stability. It was just for that reason that isocyanate prepolymers were blocked with phenols at the early stages of development of polyurethane stoving coatings [55]. After the rst stage of decomposition, i.e. when the weakest bonds in the polymer have been used up, the second and third stages are much more slow. At 300 C, the rate constants for the second stage fall within (16.744.7) 106 s1, depending on the content of soft segments, while for the third stage they amount to (17.810.3) 106 s1. More stable urethane groups connected to aliphatic radicals undergo decomposition during degradation stage 2. The most stable structures ester groups present in soft segments are damaged at the stage 3. The higher the content of soft segment in a polymer is, the more stable the polymer is at elevated temperatures and the lower the initial rate of its degradation is. That rule, however, is not always satised. Increased rate of degradation was also observed at the nal stage, i.e. for the lowest content of hard segments [274]. The principal process which takes place during degradation is depolymerisation, i.e. decomposition of PU to yield its parent substances: diisocyanate and polyols. The degradation products obtained from hard segments would be further converted to produce a
996
stable residue. The presence of aromatic rings in hard segments usually has the stabilising eect and it reduces the volume of volatile degradation products released. For example, 4,4 0 -dihydroxydiphenylmethane mentioned above, if released after decomposition of urethane groups, will evaporate from the reaction medium, while residual diisocyanate will undergo secondary reactions and it will produce more stable urea and isocyanurate structures [273]. If soft polyol chains contain other aromatic structures derived for example from phthalate esters, the molecule becomes more rigid, the intermolecular forces become stronger, Tg and Tm become higher, and thus the degradation rate drops down [274]. Thermal stability of polyurethane elastomers is also aected by the chain extender employed, by density of allophanate cross-linking, and also by the type of other cross-linking bonds in case of cellular elastomers. That type PUs can be linked together to form the spatial network with the involvement of various functional groups, like urethane, biuret or allophanate groups, or by means of covalent bonds between carbon atoms in neighbouring chains. The published reports on the eects of cross-linking density and types of crosslinking bonds of thermal stability of PUs are not much precise, though. Some researchers have notices better thermal stability for higher cross-linking densities, while others have never observed such correlations [271,275]. The impact from the type of the chain extender is also hard to establish explicitly, the more so as the increasing molecular weight of the extender changes the share of hard segments. Which is, however, beyond any dispute is that PUs with no cross-linking oer superior thermal stability to those cross-linked [271]. The presence of a side functional group in the chain extender molecule reduces the potential for the formation of urethaneurethane hydrogen bonds which makes it difcult for hard segments to agglomerate, i.e. their phase separation becomes hindered. When hard segments and soft segments are intermixed, interactions are shielded in the vicinity of the oxidable C@O groups in polyester segments. Cross-linking bonds have the opposite eect they make it hard to oxidise the ester group. Decomposition of PUs obtained in the prepolymer method takes place much easier than decomposition of their analogues with the similar compositions which have been synthesised in a single-stage method. Two minimum points for decomposition reactions can frequently be observed in the DTG patterns of those PUs these are specic for hard segments and soft segments. The activation energy for the rst stage of the decomposition process of PU obtained from the single-stage method is 77101 kJ/mol, depending on the composition of the polymer, while the second stage requires the energy of 111 316 kJ/mol. As compared to the product obtained from the prepolymer method, the activation energy values for those stages are 4486 and 80130 kJ/mol, respectively [18]. In order to illustrate the eects of the single-stage method and prepolymer method employed in the production of elastomers, and the molecular weights of linear polyurethanes cross-linked with TEA or D-RE, obtained as presented in Section 6.2 (Table 5) in the multi-stage polyaddition process with removal of unreacted monomers, DTA, TG and DTG thermograms of a few polyurethanes were presented in Figs. 31 and 32 [92,233]. These demonstrate complexity of the thermal degradation process of elastomers: the process comprises a few stages. The initial loss of 13% of the sample weight at 60 70 C results most probably from the physical desorption of the volatile organic substances, i.e. those derived usually from the raw materials employed, like for example low-molecular weight adducts of alkylene oxides which in most cases are present in polyols. The loss in weight observed within 180350 C, on the other hand, is caused by oxidative degradation which is represented by a small exothermic eect in the DTA curve. TG
997
Temperature difference, T [ C]
ENDO
EGZO
Mass decrement rate
Temperature [ C]
PU-I-200 (2) PU-I-300 (2) PU-I-400 (2) PU-I-600 (2) PU-I-1000 (2) PU-I-1250 (2)
Temperature [oC]
Fig. 31. DTA, TG and DTG thermograms of PU obtained at the rst stage with the use of dierent glycols, extended by Desmodur RE (according to Table 5) [233].
998
Temperature difference, T [C]
ENDO
EGZO
Mass decrement rate
Temperature [ C]
PU-I-300 (1) PU-I-300 (2) PU-II-300 (1) PU-II-300 (2) PU-III-300 (1) PU-III-300 (2) PU-IV-300 (1) PU-IV-300 (2) PU-V-300 (1) PU-V-300 (2)
Temperature [oC]
Fig. 32. DTA, TG and DTG thermograms of PU obtained in one-step method (1) or prepolymer method at stages IV (2) with the use of polyoxyethylene glycol with M n 300 g=mol (according to Table 5) extended by Desmodure RE or triethanolamine [233].
999
measurements for some PUs show even a small rise of weight within that temperature range which most probably results from the addition of oxygen [276]. Degradation becomes fast at temperatures above 300 C. The irregular shapes of thermograms (presence of a few overlapping peaks) speak for a few reactions taking place simultaneously at the range where the TG curve shows the weight loss. The DTG curve (Figs. 31 and 32) presents two peaks: at 300360 C (I) and at 370440 C (II). They are sharply outlined in case of PUs obtained from lower molecular weight polyols. In case of PUs derived from POG 200 and PCD 530 (Table 5), the peak (I) is more intense. When the molecular weight of polyol increases, intensity of peak (I) drops down and peak (II) increases at the same time, which proves two dierent destruction reactions causing a clear weight loss. In case of PUs synthesised from POG 600, POG 1000 and PCD 1250, only one peak, peak (II) can be observed. DTA thermograms show that both the reactions considered are endothermic. The temperature maximum for reaction (I) is observed within 300 360 C and this can be destruction of urethane groups. Reaction (II) with its maximum within 370440 C is most probably the disruption reaction of ether bonds and ester bonds in polyether urethanes and in polyester urethanes, respectively. When the polyol chain length increases, the thermal eect of endo processes within 300360 C declines at the same time, while that within 370440 C grows up. That can be correlated to the increasing share of ether-type bonds and/or ester-type bonds with simultaneous reduction in the number of urethane groups. The small exo peak which appears in the DTA prole above 450 C, and which is accompanied by a small weight increase in TG patterns, suggests the oxidation reaction of low-molecular weight solid products. The degradation process becomes completed in practice at the temperatures above 700 C, and the sample weight approaches zero then. Those ndings suggest the general improvement in thermal stability of ether bonds and ester bonds when the polyol chain length grows. Long and exible chains of polyols as presented in Section 11 form exible domains and their sizes expand to follow the growing polyol chain length. A higher content of that material is also observed in the intermediate phase. As can be seen, bigger exible domains advantageously aect thermal stability of ether bonds. Thermal stability of urethane groups is usually improved by the growing length of oligodiol chains. Thermal stability of ether bonds and ester bonds is also aected by the length of urethane segments that length is dependent on the structure of oligourethane and the stage of its synthesis. When the length increases as it was shown the content of exible segments in polymer increases, too, but the degree of phase separation decreases at the same time which lowers the share of soft phase. The temperature of thermal resistance slightly declines in such cases. The DSC investigations revealed that the share of soft phase gradually increased in the samples denoted as PU-I-200 (2) and PU-III-200 (2) as well as PU-I-600 (2) and PU-III-600 (2), which was reected by the observable increase in the decomposition temperature of ether bonds. That relation cannot be observed, however, in polyester urethanes [142,233]. The above eects are supplemented by the decline in thermal stability of urethane bonds when the length of the urethane segment increases, which can be observed each time. That decline is most probably caused by impairment in the orderly arrangement of supermolecular structures within the hard segments. PUs obtained from the single-stage method undergo degradation generally at lower temperatures than their equivalent polymers produced from the same feeds but in the prepolymer method (Fig. 32). Better separation of hard segments and soft segments was found in the latter, too [233].
1000
PUs, which have been cross-linked with Desmodure RE, are more thermally stable (temperature for the 5% weight loss (T5%) is 30 C) than their equivalent PUs, which have been hardened with the use of TEA (T5% = 160 C) that is exactly as one could expect. Both Desmodure RE and TEA produce a stable structure of hard segments which contains aromatic groups derived from 4,4 0 ,400 -triphenylmethane triisocyanate or from 2,4-TDI and/or 2,6-TDI. However, the tri-cyclic structure of Desmodure RE generates stronger stabilisation of the urethane group and better stiening of the structures of hard segments than TDI isomers together with TEA. If the distance between the polyol-derived fragments and cross-linking agents in PU is too high, there is no eect of the latter on thermal stability of ether bonds and ester bonds. The experimental ndings conrm the general rule that polyesterurethanes and more thermally stable than polyetherurethanes: ester bonds undergo decomposition at 390440 C, while decomposition of ether bonds takes place as early as at 360420 C [92,142,233]. Thermal stability of polyurethane materials becomes important in practice when those materials are to be employed in thermal insulation, i.e. for polyurethane foams produced from linear polyurethanes. Such foamed polyurethane insulation materials should not be used for regular service at the temperatures over 90 C. One can overcame this drawback by the use of isocyanurate foams or ureamelamine foams, which however can be employed at operating temperatures up to 120 C only [2]. Not only thermal stability itself is important for the application of PU ionomers in polymeric binders for powdered ceramic materials; the nature of degradation is equally important [150,168,277]. Thermal stability of polymeric binders is always much below that of ceramic materials. When the moulded green ceramic products go to baking, polyurethane undergoes complete decomposition to yield gaseous products: CO2, CO, H2O, nitrogen oxides and possibly HCN. TG analysis makes it possible to nd the rate of thermal degradation. That rate is important for the baking process. In order to illustrate the degradation prole, Fig. 33 provides DTA, TG and DTG thermograms of binders which involved PU anionomer obtained from aromatic diisocyanate (MDI) and cycloaromatic diisocyanate (HMDI). The proles presented in Fig. 33 show that the initial temperature is similar for both anionomers and it is close to about 150 C, while further parts of their decomposition processes are organised basically in two stages: (a) A relatively slow stage, up to the temperature of about 300 C, when about 25% of the binder material undergo decomposition. The alicyclic anionomer is more thermally stable which corresponds to higher rigidity of its structure as found by the DSC method. The aliphatic structural elements derived from poly(oxypropylene)glycol and the chain extender molecules are most probably the rst units which suer from destruction at this stage. The hydrocarbon cyclic structure remains intact and it will be damaged at the observable extent at the second stage. (b) A much faster stage up to 560660 C, during which the polymer is completely decomposed and its ring structures damaged. The aromatic anionomers are more stable structures and the temperature of 660 C is required for its nal decomposition, while alicyclic anionomers undergo decomposition much earlier, at 560 C only [277]. The eect of chemical composition of polyurethane anionomers obtained from various diisocyanates on their thermal stability and the relation between that stability and the
1001
DTG
DTA
20
100
200
300
400
500
o
600
700
800
Temperature [ C]
TG
100
75
Loss of the mass [%]
50
25
0 20 100 200 300 400 500 o Temperature [ C] 600 700 800
HMDI MDI
Fig. 33. DTA, TG and DTG thermograms of PU anionomer binders for powdered ceramic materials obtained from aromatic (MDI) and cycloaliphatic (HMDI) diisocyanates [277].
1002
presence of supermolecular structures was analysed in [241]. The information on thermal stability of PU anionomers was derived from thermogravimetric analysis (TG, DTG) and
DTG
DTA
20
100 200
300 400
500
o
600
700
800
Temperature [ C]
TG
0
25
Loss of the mass
50
75
100 20 100 200 300 400 500 600 700 800
Temperature [oC]
Fig. 34. TG, DTG and DTA thermograms for polyurethane PU anionomer obtained from TDI [241].
1003
%
0
TG
1 25 2 3
Loss of the mass
4 50
75
100 20 100 200 300 400 500 600 700 800
Temperature [oC]
Fig. 35. TG thermograms for polyurethane anionomers no. 14 [241]: (1) PU anionomer obtained from the reaction of 2,4- and 2,6-TDI, polyoxypropylene glycol (Mn = 450 g/mol) (Mn = 450) and 2,2-bis(hydroxymethyl)propionic acid (DMPA), neutralised with triethylamine (TEA) and extended by means of 1,6hexamethylenediamine (HMDA), (2) PU anionomer obtained in the same way from MDI, (3) PU anionomer obtained from HMDI, (4) PU anionomer obtained from IPDI.
from the DTA curves which were recorded at the same time (Figs. 34 and 35). The relative mass loss at the stage 1, which takes place within T DTA1max 310360 C, amounted to from 30% for the relatively most stable anionomer no. 2 up to 68% for anionomer no. 1. That mass loss most probably resulted from decomposition of less stable ether structures of rigid segments and from partial decomposition of urethane structures, created for example with the participation of less reactive NCO groups of diisocyanates used in the synthesis process. Exactly within that temperature range, the minimum value of the DTG peak is located which represents the highest rate of mass loss from samples. At the stage 2, on the other hand, which is characterised by the value of T DTA2max 527588 C, the analysed anionomers undergo complete decomposition in practice, so that Dm/m0 = 97100%. The comparative analysis of the obtained data (Fig. 35) shows that the anionomer no. 2 is the most stable material. It was synthesised from aromatic symmetrical diisocyanate MDI and its decomposition at the stage 2 T DTA2max 541 C reached 88%. So, the nal degradation took place at that stage and it covered even the most stable aromatic structures. 14. Modern trends in applications for linear polyurethanes The principal issues for the materials technology, i.e. applications for linear polyurethanes, were already presented in previous sections when the structural questions and physicalchemical interactions within those polymers were discussed. That approach seems the most clear since it provides the correlation between the structural factors and
1004
the properties resulting therefrom. The most important properties from the viewpoint of materials technology are: static and dynamic mechanical properties, acoustic, optical and electrical properties, as well as corrosion resistance, chemical performance and biological performance of PU plastics. This section, however, is going to present the synthetic review of the latest trends in applications for the materials based on linear PUs. Special attention has been paid to elastomers, ecologic lacquers, adhesives and binders, biomedical materials and modern materials for electronics. 14.1. Elastomers Linear polyurethanes make important intermediate products in the manufacture of elastomeric structural materials and for a wide range of protective coatings. Applicability in those elds is usually controlled by numerous and dierent physicalchemical properties and by the specic performance properties resulting from the former. The static and dynamic mechanical properties seem to play the most essential role here. The fundamental static properties for isotropic materials are dened by three basic mechanical moduli, which represent the tensile strength or bending strength of polymers (Youngs modulus E), shear strength (Kirchos modulus G) and compression strength (Helmholtz modulus K), and by the corresponding strains: unit elongation and percentage permanent elongation, deection, deformation angle and changes in product geometry, as well as by the accompanying Poisson ratio m = 0.30.5. The static properties also involve hardness and abrasion resistance. Further, dynamic mechanical properties, like: creep compliance under steady stress conditions, impact resistance and fatigue strength under periodically changing stress conditions, are also important for applicability of PU elastomers. In case of foamed polyurethanes, the acoustic performance, i.e. acoustic velocity and sound reduction factor, need to be considered, either. Those properties are characterised by the so-called complex dynamic moduli (E*, G* and K*), mechanical loss tangent (tg d) and logarithmic damping decrement K the quantities which are in general functions of stresses and temperature at which the measurement is taken. In the light of the above reasoning, it is evident that the mechanical properties of the nal goods will be decided by the structures of PU chains and by the phase structures of PUs. That problem has been extensively described in literature since mechanical properties aect directly the elds of applicability for PU foams, PU elastomers and PU coatings [2,55]. Alike materials thermal properties, its behaviour under the eect of mechanical forces is determined by the polymer phase structure, and that in turn is controlled by the organisation of its segments. The presence of soft segments with negative Tg imparts the elastomeric performance to the polymer, while hard segments contribute to its good strength. The lower the Tg value is and the higher the plasticity point or melting point is, the more advantageous elastomeric features can be found in a PU. The elastomeric performance of PUs declines for the growing content of hard segments. The linear polyurethanes with the contents of hard segments exceeding 65% usually start performing like plastomers and they reveal the area which is specic for the amorphous phase of a viscoelastic liquid. That becomes apparent when mechanical properties are studied versus the plastics content of rigid segments, i.e. when the discontinuity limits are observed for physicalmechanical parameters [278]. The quality of a PU elastomer is dened not only by the negative value of its Tg but also by its mechanical properties, and in particular by its tensile strength, ultimate elongation, hardness, elasticity, abrasion resistance and impact resistance. The exemplary
1005
properties of PU elastomers versus chemical structures of raw materials [structures] which are decisive for the content of hard segments have been provided in Table 9. The data show that the eect of chemical structure of polyurethanes, which is primarily controlled by the employed raw materials, on mechanical properties of those PUs is much complicated. That eect may even seem incidental. No randomness becomes visible only after phase structures have been considered in the analysis. This is because the mechanical properties make the resultant of structural factors and such physicalchemical interactions like size and exibility of hard and soft segments, ability to form hydrogen bonds, van der Waals force, size and symmetry of aromatic rings, entanglement of chains, orientation of segments, cross-linking bonds, micro-phase separation and content of crystalline phase. The most important contribution comes from the chemical structure and from the size and structure of hard and soft segment resulting therefrom. The soft phase and hard phase are inter-soluble in the case of elastomers with low contents of hard segments. The sizes of hard segments increase when the number of those segment increases. Initially, they form a system of separate islands which do not contact each other and are dispersed within the matrix of soft segments. Above a certain limit number, some of them start touching each other which forms the system of hard domains. Further increase in the number of hard segments favours their association and the roles of phases become opposite. Both the cohesion energy and hydrogen bonds in hard domains are higher than in soft domains. Hence, the role of hard domains is sometimes compared to that of a ller material which is used to reinforce the elastomer structure and to improve its mechanical properties: in particular strength and hardness. On the other hand, higher elasticity is favourable for intermolecular interactions. In contrast to mechanical strength, which is controlled rst of all by the structure of hard segments, elasticity is aected mainly by soft segments. Lower energy of interactions in polyether urethanes makes them much more exible than polyester urethanes [218]. The capacity for crystallisation of phases, which is conditioned by the structural regularity, contents of individual segments and ecient phase separation, is favourable for superior tensile strength, tearing strength, hardness, abrasion resistance and higher stresses at pre-dened elongation levels. The highest mechanical strength is oered by PUs obtained from diisocyanates with symmetrical structures, like aromatic MDI or its alicyclic equivalent HMDI [13]. PUs produced from polyoxypropylene glycols (POG or PLURONICS) with asymmetrical structures have lower mechanical strength than their analogues derived from poly(oxytetramethylene) glycol (PTMO) its hydrophobic nature enhances the phase separation potential and its regular structure is favourable for crystallisation. The presence of covalent cross-linking bonds can sometimes impair intermolecular interactions which makes the reason for lower mechanical strength. A small level of cross-linking can, however, favourably reduce the permanent set or improve the strength [55,279]. The mechanical properties of PUs can be also considerably aected by the method adopted for the nal treatment of the product, like soaking or racking employed in the production of bres. That increases phase separation and orderly arrangement of polymer within its crystalline structures, i.e. polymer strength is advantageously improved in that way [280]. The PUs mechanical properties are generally aected by numerous structural factors which depend on the product forming method. Those factors are so much
1006 P. Krol / Progress in Materials Science 52 (2007) 9151015
Table 9 Mechanical properties of polyurethane elastomers Type of isocyanate Type of polyol Type of chain extender Contents of the hard segments (%) 70.0 60.0 55.0 45 Tensile strength (MPa) 0.55 0.21 0.17 5.2 Elongation (%) Hardness (Sh A] Grindability Ref.
MDI MDI MDI MDI
MDI 2.4-TDI 2.4-TDI (80%) + 2.6TDI (20%) IPDI HMDI HDI MDI MDI HMDI
POG M n 1000 POG M n 1000 POG M n 1000 Hydrogenated polybutadiene M n 3400 PTMO M n 2000 PTMO M n 2000 PTMO M n 2000
BD BD BD Ethylenediole propanedioel BD BD BD
130 68.9 54.3 850
48 37 30 60
[282] [282] [282] [279]
40 40 40
42.9 16.8 14.0
1160 1480 1290
96 80 77
139 (kN/m) 64 (kN/m) 61 (kN/m)
[283] [283] [283]
PTMO M n 2000 PTMO M n 2000 PTMO M n 2000 PTMO M n 1000 Poly(oxybutyleneadipate) M n 1000 PCD and POG M n 2000 (2:1)
BD BD BD BD BD DMPA
40 40 40 37.4 33.6 29.7
9.5 24.3 10.4 5.5
1280 710 200 867
75 94 94
55 (kN/m) 110 (kN/m) 76 (kN/m) 140 ARI 190 ARI
[283] [283] [283] [284] [284] [285]
Line missing
Diisocyanate 5,5 0 isopropylidenebis(2-furfuryl) MDI 2,4-TDI (80%) + 2.6TDI (20%) 2,4-TDI (80%) + 2.6TDI (20%) MDI
PTMO M n 2030
PCD M n 2000 Polyoxypropylene glycol M n 2000
2,5Bis(hydroxymethyl) furane BD Methylene dianiline
23.7
2.1
460
[286]
22.8 21
4.7 7.9
580 360
78
[286] [287]
Pyromellitic anhydride Poly(etyleneadipate) M n 2000 and oligo(ethyleneterephthalate) copolymer M n 1200 Poly(oxypropylene) triole M n 3500 BD
21
2.0
172
[288] P. Krol / Progress in Materials Science 52 (2007) 9151015
17.8
4.80
260
77
[230]
2,4-TDI (80%) + 2.6TDI (20%) 2,4-TDI
BD
9.8
0.21
120
13
[281]
BD
8.8
0.19
240
12
1007
1008
complicated that they can be hardly described by theoretical equations. Then, considerable prots can be derived from empirical models which have been developed with the use of the mathematical experiment planning methods. Those models, however, are extensively utilised not earlier than at the optimisation stage of a specic technology within materials engineering [35,84]. The situation becomes even more complicated when the feeding equipment with a few feeding heads is used, each head for a dierent colour, to convert thermoplastic elastomers into precisely tailored series of products [68]. 14.2. Biomedical materials The exceptional combination of good mechanical properties of special PU elastomers with their high hydrolytic stability and biological stability, which is e.g. the case for PELLETHANE polyurethanes, makes it possible to use polyurethanes as highly specialised biomedical materials. They can be utilised to produce endoprostheses, cardiac valves and/or regenerative membranes for damaged internal organs, they do not induce any inammatory condition of tissues, they do not undergo any destruction by body uids, and no blood components are deposited on them [19,20]. The properly synthesised polyurethane elastomers and PU-PDMS copolymers, owing to their lowered free surface energy, are capable of oering considerable resistance to biodegradation. They are additionally known for their physiological inertness in relation to living organisms, hence making the interesting choice as materials for medical implants [191,205]. The advantageous reduction of adhesion, which prevents aggregation of blood cells, results from the level of phase separation and hydrophilic performance of surfaces of such materials [19,20,39]. 14.3. Protective coatings, waterborne ecological lacquers, adhesives and binders. Polyurethane ionomers One of the latest trends in applications for PUs is the production of ionomers from which aqueous dispersions can be obtained with no involvement of external emulsiers. Such dispersions are then employed inter alia as environmentally friendly lacquers applicable to metal, ceramic, glass and wood substrates [8,9,169] or as water-repellent glass nishes [171]. With a relatively high concentration of ionic groups which readily undergo solvation, PUs (which are usually hydrophobic) become highly hydrophilic and soluble in typical organic solvents like methanol or acetone, and they form homogeneous solutions or stable emulsions and dispersions in water [170]. The increasing content of ionic groups in a PU chain is followed by the improved hydrophilic performance of the coatings obtained from PU ionomers, better mechanical strength and elasticity of those coatings. The spectrum of stress relaxation broadens for the polymer which in case of elastomers is advantageous for their fatigue life [173]. By combining emulsions of PU ionomers with emulsions of other polymers, like poly(vinyl alcohol) or poly(vinyl acetate), one can produce interpenetrating polymer networks with superior adhesion to metals and ceramic materials and with improved water resistance [10,168]. An interesting eld of applications is the production of polymeric coatings with the use of polyurethane IPNs and other chain polymers like poly(methyl methacrylate) [11] and polystyrene [12], or condensation polymers, e.g. unsaturated polyesters [13], epoxides [14] and polysiloxanes [15].
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14.4. Modern materials for ceramics and electronics The polymeric binders applicable in ceramics technologies seem to make an interesting application of the future for water-dilutable polyurethanes. The powder materials like corundum (Al2O3) or zirconia (ZrO2) can be press moulded with the use of environmentally friendly PU ionomers or polyurethaneacrylate copolymers, and then subjected to preliminary machining as the so-called green ceramics. Such elements, e.g. corrosion resistant components of machines or chemical process equipment, are given shapes and dimensions which are very close to the nal requirements and thus the nal machining with the use of hard and expensive diamond tools can be minimised [178,179]. Another outlet for polyurethane dispersions is their use in the form of ceramic-polymeric slurries for the production of thin lms in the tape casting (doctor blade) method. The lms are then used in the manufacture of capacitors [180,181]. Yet another interesting development was the PU material with built-in stilbene-based chromophores [172]. Thus synthesised cationomer coating was characterised by considerable UV absorption (kA = 313332 nm) which under specic conditions was followed by secondary uorescence of violet-blue light at the wavelength of 420470 nm [175]. The tests applications of linear PU-PDMS copolymers as polymeric electrolytes seem promising, too [225227]. Not all expectations, however, concerning the use of liquid crystal linear PUs, which contain rigid aromatic mesogens in their chains (formulas (29)(31)), as sensitisers of mechanical vibrations, as optical materials and as materials for electronics have so far been completely met [5153]. The elastomeric polyurethane mixes with increased contents of aromatic segments by the use of for example Dianole-type polyols are useful for the production of chemically resistant coatings and lling compounds for electronic circuits [35,50,281]. 14.5. Biodegradable materials The use of vegetable feeds: starch [16], castor oil [17], natural rubber [18], lignin, wood our, molasses, cellulose, glucose, fructose or saccharose, makes it possible to obtain components for linear polyurethane plastics with improved biodegradability. That is advantageous for recycling of some polyurethane goods, e.g. foamed polyurethane packages. 15. Summary The above analysis takes the chemical structures, manufacturing methods and selected physicalmechanical properties of linear polyurethanes (i.e. both nal products and intermediates in the production of various polyurethane goods) described in literature reports as the reference point. It goes through numerous research reports and applications which have already been learned and described. Despite that, there are still many opportunities to synthesis new polymer systems and to modify known chemical structures and phase structures where linear polyurethanes are involved. The combination of specialised knowledge within the polymer technology, and in particular the kinetics of the step-growth polymerisation process, with the use of the computer simulation methods in designing the synthesis of required macromolecular structures yielded a new potential for the synthesis of linear polyurethanes and development of their applications. The new chemical molecules can be utilised for example in the production of copolymers with chain polymers
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and condensation polymers, like PU-PDMS systems, i.e. purpose-oriented tailored materials intended for medicine, electronics, automotive industry and civil engineering. The possibility of producing modern biomedical materials in that way makes the challenge of the near future. Such new materials would have to be resistant to hydrolysis in the presence of physiological uids, they would have no negative impact on blood cells, and they would not induce any inammatory condition of tissues in contact with those polymers. No progress would have been possible without the use of the newest test methods: GPC, ESI or MALDI-ToF mass spectrometry, DSC, TG, SAX and WAXS X-ray analysis, or modern SEM and AFM microscopic methods, in structural investigations of the synthesised materials. The chemical industry still faces the problem of developing ecient polyurethane processes, i.e. production of monomers, ecient polyaddition processes, environmentally safe applications moulding techniques for nal products, and nally safe utilisation methods for spent goods, as expected by many users of polyurethane product. References
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Progress in Materials Science 52 (2007) 9151015 www.elsevier.

Tel.: +48 17 86 51579; fax: +48 17 85 43655. E-mail address: pkrol@prz.rzeszow.pl

P. Krol / Progress in Materials Science 52 (2007) 9151015

11. 12. 13. 14.

P. Krol / Progress in Materials Science 52 (2007) 9151015

P. Krol / Progress in Materials Science 52 (2007) 9151015

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P. Krol / Progress in Materials Science 52 (2007) 9151015

P. Krol / Progress in Materials Science 52 (2007) 9151015

P. Krol / Progress in Materials Science 52 (2007) 9151015

and 4,4 0 -methylenebis(phenyl isocyanate) (MDI) (formula (12)),

P. Krol / Progress in Materials Science 52 (2007) 9151015

or 1,5-naphtylene diisocyanate (NDI) (formula (13)), which is not so frequently used,

P. Krol / Progress in Materials Science 52 (2007) 9151015

or bisphenol-S polysulfone with oxiranes (formula (21)) [36]:

P. Krol / Progress in Materials Science 52 (2007) 9151015

P. Krol / Progress in Materials Science 52 (2007) 9151015

CH3 HO CH2 CH2 O C CH3 O CH2 CH2 OH

P. Krol / Progress in Materials Science 52 (2007) 9151015

P. Krol / Progress in Materials Science 52 (2007) 9151015

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P. Krol / Progress in Materials Science 52 (2007) 9151015

Reference [72] [72] [73] [72] [73] [73] [23]

THF (catal. DBTL) Chlorobenzene Chlorobenzene

Oligo(oxypropylene-adipate) 2,4-TDI 2,6-TDI

THF (catal. DBTL)

P. Krol / Progress in Materials Science 52 (2007) 9151015

Concentration of process solution = 50 wt% [82].

P. Krol / Progress in Materials Science 52 (2007) 9151015

NCO (E) monomer EF

P. Krol / Progress in Materials Science 52 (2007) 9151015

CH3 NCO O R2 trimer ff O C NH

P. Krol / Progress in Materials Science 52 (2007) 9151015

7000 6000 5000 4000 __ Mn 3000 2000 1000 0 0 5000 10000

0.0030 0.0025 0.0020 0.0015 -1 ] -1 0.0010 3 ol s m m 0.0005 [d k1 0.0000

P. Krol / Progress in Materials Science 52 (2007) 9151015

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6 4 2 0 2000 4000 t [s ] 2 6000 8000 0 1

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0.0 0 2000 4000 t [s] 2 6000 8000 0 1

2000 1600 1200 800 400 0 0 5000 10000

2.5 2.0 1.5 1.0 20000 25000 0.0 0.5

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400 300 200 100 0 500 1000 1500 2000 2500 1 3 2 4

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(continued on next page)

P. Krol / Progress in Materials Science 52 (2007) 9151015

Polyaddition stage no. IV

Basic reaction in polyaddition stage A3B4 + 3A ! A5B4 + A

Extraction solvent system for excess monomer Like at stage II

P. Krol / Progress in Materials Science 52 (2007) 9151015

substrates products before extraction products after extraction