POLYMER 4.1 Introduction We live in an era of polymer. If you look around You, everywhere you will get polymer. The food (starch and protein) you eat is polymer. The cloth you wear is polymer. The materials you use for the construction of your house (PVC pipe, glass, rubber, cover of electric cable, rope ete.) are mostly polymer, However, a century back scientists believed that there was no existence of Polymer. The organic compounds Polymers are organic compound), which could not be crystallized (polymers are no ‘ ‘ -erystalline substance) were considered asthe tars and were thrown into the sink. The idea of polymer first came ftom German scientist, Herman Staudinger. In 1920 he Published a Paper on structure of macromolecules. In that and in many other subsequent papers he argued that there is the existence of polymeric material, According to him in polymer many molecules of a substance are held together by the normal valence bond. The tendency of the formation of such compound is observed particularly in organic compounds due to the special nature of. carbon, Carbon isthe central element of al organic compounds, The above described idea of scientist Staudinger met with a great deal of objection from the then many famous scientists, Henreich Wieland a noble prizewinner was a front liner among them, He declared': “Dear colleague, please leave aside the idea of big molecules with molecular weight greater than 5000, Purify your products, then it could be crystallized and it would be found that it is a low molecular weight substance.” Within a few years the Staudinger's idea about polymeric material got support from some other Scientists. K. H, Mayer and H. F. Merk were the early supporters. In 1929 WH. Carothers Published his work on synthetic polymers and established the existence of polymer molecule, Thus Staudinger and Carothers were the two scientists who Put polymer chemistry on a firm footing, 4.2 Definition of Polymer The word polymer has been derived from two Greek words: ‘poly’ and “meros’. Poly means many and meros means parts or units. Therefore [polymer may be defined as the molecule in which many units of a single molecule are united together.| There are substances in which the molecules are also united together. But these are not called polymers. The examples of such substances are sodium chloride crystals, liquid water etc. In sodium chloride crystals many molecules of sodium chloride are united together by ionic bond. In liquid water WER Sorensen and TW. Campbell, Preparative Method Polymer Chemistry. Interscience Publisher, Wiley & Sons. New York, 1968.262 Chemistry of Water, Corrosion & Engineering Materials many. water molecules are united together by hydrogen bond. But in polymers several units of a single molecule or two different molecules (in case of copolymer) are united together by covalent bond. ‘Therefore{polymer may be defined as a substance in which many units of a single or two different molecules are united together by covalent bond. | [ithe starting molecule from which the polymer molecule is formed is called monomer] [ne number of monomer units, which are united together to form a polymer molecule, is called degree of polymerization] Polymers with a high degree of polymerization are called high polymers and those with low degree of polymerization are known as oligomers. High polymers have very high molecular weight in which the repeating units are more than 100. Hence polymers are also called macromolecules. There are some substances whose molecules are also known as macromolecules but these are not polymers. Examples of such macromolecules are carotene, vitamins etc. Here, the basic difference is: polymers are composed of repeating units (monomer) but these macromolecules are not composed of any repeating units. «43 Classification of Polymers ‘There are many ways by which polymers may be classified. A brief description about the classification of polymers is given below: ABA Classification based on degree of polymerization With respect to the degree of polymerization polymer may be classified as (i) high polymers and (i) low polymers. Low polymers are also known as oligomers. In oligomer the degree of polymerization (number of repeating units) is less than 100. The average molecular weight of high polymers usually varies from 10° to 10°. 4.3.2 Classification based on source Depending upon the source, polymer may be classified as (i) natural polymers and (ii) synthetic polymers. Natural polymers are obtained from the nature and synthetic polymers are man made Polymers. These are synthesized in the laboratory. The number and industrial application of natural polymers are very limited. Their physical properties are fixed by the nature and cannot be varied largely. The best example of industrially applicable natural polymer is rubber. CH; The — rubber is cis-polyisoprene (-CH;-CH=C-CH,),, The examples of synthetic polymers are polyethylene (polythene), nylon, poly vinyl chloride, teryline, styrene, butadiene rubber etc.Polymer 263 Preparation, properties and application of some industrially important synthetic polymers will be discussed in this chapter. 4.3.3 Classification based on structure of molecule Based on structure of molecule synthetic polymers are mainly divided into two groups: (i) linear polymer and (ii) branched polymer. 4.3.3.1 Linear polymer In linear polymers the repeating units (monomers) are linked in a straight chain. Because of its linearity (there is no branching) in linear polymers, always there exists flexibility in its chain. This is due to twisting of (internal rotation around) the single bond. As a result coiling of chain invariably exhibits in linear polymers. Linear polymer 4.3.3.2 Branched polymer In branched polymer there is always side chain. The length of the side chain may be different in a branched polymer. The branching may be random or it may occur at regular intervals with equal length of branches. Some times the branches may join to each other and in some cases they join to the adjacent chain also. As a result of different types of branching, different mechanical properties appears in the branched chain polymers. The various types of branched polymers are shown in fig. 4.1. () @ © @ Fig. 4.1: Various types of branched polymers: (a) simple branched, (b) comb type; (c) ladder type, (d) network typeChemistry of Water, Corrosion & Engineering Materials in general linear and non-cross linked chain polymers are thermoplastic. Cross linked polymers are thermosetting polymers (for more detail see section 4.3.5), 4.3.4 Organic and inorganic polymer Polymers may again be classified into two classes: (i) organic polymer and (ii) inorganic polymer, Organic polymer may be defined as the polymer in which the backbone chain is essentially made up of carbon atoms, The other valences of carbon atoms are satisfied with atoms of hydrogen, oxygen, nitrogen, sulfur, chlorine etc, Almost all natural polymers are organic polymers. In comparison to the huge number of organic polymers, the number of inorganic polymers is. very limited. ‘An inorganic polymer may be defined as the polymer in which the backbone of the polymeric chain is made up of atoms other than carbon atom. However, the back bone atoms should be multivalent. Examples of inorganic polymer are glass, silicon rubber, titoxane, poly phosphoric acid, poly phosphate, poly arsenate etc. The formation of polymer back bones in such molecules is shown below: Poly Titoxanes: whoo I Ono Poly phosphoric Acid: ~~} —}_on | OH OH Poly phosphate: ~~9—p—o—p—O~~~ | | OR OR 9° i i Poly arsenates:~9—As—O—As—O~~~ OR OR Fig. 4.2. Structural formula of some inorganic polymers. jPolymer 265 4.3.5 Classification of polymer based on heat effect Dependi upon the effect of temperature on mechanical properties, polymers may be classified into two classes: (i) thermoplastic polymer and (ii) thermosetting polymer Thermoplastic polymer: Thermoplastic polymer may be defined as the polymer, which becomes soft on heating thereby it can be given any desired shape. These polymers are able to retain that given shape on cooling. However, on further heating they become soft again with ormation of given shape. Thus the softening on heating and stiffen on cooling can be repeated many times, As a result, thermoplastic polymer may be recycled several times. This type of polymer has in general linear or branched chain having no cross-linking in its chain. Some common examples of thermoplastic polymer are: PVC (polyvinyl chloride), PE (polyethylene), PP (polypropylene), nylon 6 6 ete. Thermosetting Polymer: Similar to thermoplastic polymer thermosetting polymers may also be the polymers, which become soft on heating thus it can be given any desired shape. The shape is also retained on cooling. However, during heating this type of polymers undergo some chemical changes in their structure and convert themsel iato infusible and insoluble masses. As a result, on further heating they never be soft again. At extremely high temperature these polymers decompose but do not soft. Thus thermosetting polymer cannot be recycled, Bakelite is the most common example of thermosetting polymer. The polymer of this type undergoes a permanent change upon melting and there after sets to a solid mass on cooling which cannot be remoulded, This is attributed due to the presence of excessive cross-linking between the chains, forming a three-dimensional network structure on heating, Melamine is another common example of such polymer. 4.3.6 Classification based on form and use Depending on the ultimate form and use, polymers may be classified into plastic polymer, elastomeric polymer, polymer fiber, polymer resin etc. (i) Plastic polymer: These are the polymers, which can be given shape of any hard and tough articles by the application of heat and pressure. These are mainly synthetic polymer. The common example of this type of polymer is PVC. The other examples of such polymers are poly acryl amide, poly methyl methacrylate, Nylone 6 6 etc. (ii) Elastomer: These are rubber like elastic polymer. These substances deform by the application of load but on withdrawing load they return back to their original shape. That is, these polymers readily undergo reversible deformation and elongation. Examples of elastomers are natural rubber, synthetic rubber, silicon rubber etc. These are mostly linear polymer having some degree of unsaturation in its backbone. As a result, these polymers lie in the form of coil, which permits the> 266 Chemistry of Water, Corrosion & Engineering Materials polymers to be stretched under stress but regain its original shape when the stress is withdrawn, In this regard natural rubber is different from other natural polymers. The physical properties of natural rubber can be modified to a large extent on chemical treatment (such as vulcanization) 30). However, this cannot be carried to any other natural polymer such, as (See chapter 5, page protein, starch etc, p Gii) Fiber polymer: Fiber polymer is that kind of polymer, which can be drawn into a long filament like threads. Typical examples of such fiber polymer are nylon, terylene ete, The special characteristic of these polymer is the inter particle forces in these polymers are quite strong, (iv) Polymer resin: These polymers are usually obtained in liquid or semisolid form. These are used as adhesive particularly in paint and varnish industry. Polymer resin may be synthesized in the laboratory as well as it may be obtained from plant as the extruded liquid, The examples of such polymers are epoxy resin (synthesized in the laboratory), shellac (extruded from plant) etc. These polymers have got sealant properties too. 4.3.6.1 Ionic polymer and nonionic polymer Depending on the polarity of polymer molecule it can be classified into two classes. ‘These are (i) ionic polymer and (ii) nonionic polymer. Tonic polymers are synthesized in the laboratory however natural polymers are nonionic polymers. The examples of such polymers are ion exchange resins. Both anionic and cationic type of ion exchange resin can be synthesized in the Isboratory. These are used in the modem technique of softening water. Water of almost 0 (zero) ppm hardness can be obtained by using cationic and anionic exchange resin in the softening process. The structural formula of typical ion exchange resins are: CH—CH)~CH—CH;-CH— : —CH—CH,-CH—CH,-CH— | | SO;H" | Gty—CH—CH, pk, CHyMe,Nou ] “cht Gia CH-cHh | ~cHy—tH GH-cH- | SO;H" SOsH” Cationionic Guggiate,OHF CaRMejOH™ pohmer Anionic polymer Fig, 4.3: Ion exchange resins.Polymer 267 4.3.7 Homo-polymer and copolymer Depending on the monomer molecules polymers may again be lassified into two other (different) classes. These are: (i) Homo-polymer and (ii) Co-polymer. (i) Homo-polymer: When a polymer molecule consists of a single type of monomer units then it is called homo-polymer. Polyethene, polypropylene, polystyrene, polyvinyl alcohol ete. are the examples of homopolymer. (-A-A-A-A-A-A-, Homopolymer (ii) Copolymer: These are invariably synthetic polymers and are made by using two or more different monomers. Thus co-polymer may be defined as the polymer whose molecule consists of vo or more different monomer units. In most of the commercially used co-polymers only two different kinds of monomer units are found but in a few of them three different units of monomer are also found. Similar to the ordinary polymer, copolymers may also be linear, branched or cross- linked, In a co-polymer molecule monomers may be arranged at random or in a regular manner. Copolymers of the former group are called irregular polymer whereas those of latter group are called regular polymer. The structures of these polymers are shown below: -A-A-B-A-B-B-A- (a) Random co-polymer -A-B-A-B-A-B-A-B- (b) Alternating (regular) copolymer 4.3.8 Stereo specific polymer Stereo characteristic of an organic compound depends upon the presence of asymmetric carbon atom in the molecule. [An asymmetric carbon atom is one in which four valences of the carbon atom are satisfied with four different groups or atoms]. A polymer consists of monomeric units containing an asymmetric carbon atom may be classified into three classes: (a) isotactic, (b) syndiotactic and (c) atactic polymer. These terms may be explained by taking a simple example, poly propylene. The structural formula of polypropylene is: For example, polypropyline268 Chemistry of Water, Corrosion & Engineering Materials “The above structure of polypropylene has got the following three dimensional configurations (Fi, 44) Fig. 4.4: Polypropylene (a) Isotactic (b) Syndiotactic and (c) Atactic'. These three polymers are structurally different from each other, particularly in their stereo specific arrangements. Isotactic polymer is a cis-polymer in which methyl groups of the asymmetric carbon atoms are directed towards the same direction. Syndiotoctic polymer is a trans- polymer in which methyl groups of the asymmetric carbon atoms are directed in space alternately. Atactic polymer is one in. which, methyl groups of asymmetric carbons atoms do not follow any regular order. 4.3.9 Classification of inorganic polymer Based on polymer chain composition similar to organic polymers inorganic polymer may also be classified into two classes, such as - (a) homo-chain and (b) hetero-chain polymer. Homo-chain polymer: Homo-chain polymer is the polymer in which the back bone of polymeric chain consists of single atoms. Most of the organic polymers contain only carbon atom in the back T RT Morrison and RN Boy. Organic Chemis aPolymer 269 bone of it i vr eee chain. So they may be considered as homo-polymer. In inorganic polymer sulphur and selenium have a high tendency to form homochain polymeric compound. For example, ordi i . or example, ordinary rhombohedric sulphur has cyclic molecules containing eight sulphur atoms. When this sulphur is heated, in the molten state a linear chain polymer appears. aN a—n—ua ——n—i Qe Hetero-chain polymer: The backbone of hetero-chain polymer chain consists of two or more different atoms. The examples are polysilicon dioxide, polysilicic acid, poly phosphoric acid, silicon rubber etc. The structural formulas of these polymers are shown below: Poly-phosphoric acid 4.4 Synthesis of polymer There are four methods by which polymer molecules may be synthesized. The methods are: (a) Addition polymerization (b) Condensation polymerization (©) Ring opening polymerization (4) Oxidative polymerization 4.4.1 Addition polymerization It may be defined as the process in which many units of monomer molecules are added together to form a big (polymer molecule) without losing any small molecules like COs, HO ete.270 Chemistry of Water, Corrosion & Engineering Materials Example: Synthesis of polyethylene from ethylene. = CHy>—> on—an fe n There are hundreds of polymers which are made by addition polymerization. Mechanism of their anism addition polymerization may be classified nCH, synthesis is also different. Depending on the mech into three classes. These are: (a) Free radical addition polymerization (b) Cationic addition polymerization (c) Anionic addition polymerization Whatever may be the mechanism, addition polymerization always consists of three steps. These are: (i) Initiation (i) Propagation and (ii) Termination 4.4.1.1 Free radical addition polymerization The term free radical is given to this polymerization process as because in this process the polymerization reaction is initiated by the formation of free radical. The formation of free radical is usually done by the action of light, heat or an ionizing radiation («, B or y - radiation) or by the addition of external substances which are readily decomposed into free radicals (such as H,02, CéHsCO-O., OCHSC, etc.). Depending upon the way of generating free radicals, the free radical addition polymerization process may be termed as thermally initiated, photo chemically initiated, radiation initiated and chemically initiated free radical polymerization. Among these various ways of initiation, the chemical initiation of the free radical polymerization is widely used. |n chemically initiated the polymerization reaction is initiated by the decomposition of some organic or inorganic peroxides. The examples of such peroxides are: benzoyl peroxide, hydrogen peroxide, diazo compounds etc. The decomposition is usually carried out by the application of heat. 4 Peroxides—* » Radical, These radicals serve as the active centers and cause chain propagation by combining with monomer. Rad: + CH; = CH, + Rad-CH, -CH,- Rad-CH;-CH, + CH;=CH, > Rad-CHy-CH--CH,-CHy + — etc.Polymer 2 radical polymerizati : = polymerization the union of two free radicals terminates the chain propagation of Rad-CH;-CH;" + Rad-CH,-CH,: — Rad-CH)-CH,-~CH;-CH-Rad In free radical polymerization chain termination may also be occurred by the disproportionation reaction. Disproportionation reaction may be defined as the reaction in which the transfer of hydrogen atom from one macro radical to another one takes place. Thereby two macromolecules; one with a double bond at its end and other is a saturated molecule are formed. 2. Rad — CH; -CH,-CH,-CH» + Rad - CH)- CH)-CH,-CH, + CH,=CH~-CH)~-CH:-R ‘There are some substances, which are also capable of reacting with fee radical to terminate the reaction, These substances are known as polymerization inhibitors. The examples of such substances are hydroquinone, trinitrobenzene ete. Thus the propagation of addition reactions is terminated by any of the following three ways: (i) by the combination (union) of two free radicals, (fi) by disproportionation reaction as well as (iii) by using polymerization inhibitors. 4.4.1.2 Ionic addition polymerization Ionic addition polymerizations are carried out through the formation of ions of monomer by using . different types of initiators. Depending upon the type of initiators, the polymerization reaction may be carried out through the formation of cation or through the formation of anion. ‘Accordingly, these polymerization reactions are called cationic polymerization and anionic polymerization respectively. is (particularly Lewis acids) are used as initiators, On the other hand In cationic polymerization ac i eS (particularly Lewis bases) are used as initiators. in anionic polymerization bas (a) Cationic polymerization: The schematic diagram of the mechanism cationic polymerization is shown below: GE 2 y + CH) =CH,—> Y: CH; - CH2 od a carbonium ion Cha CAT RECOV: CH CHC CHee 272 Chemistry of Water, Corrosion & Engineering Materials (b) Anionic polymerization: Similar to the cationic polymerization the mechanism of anionic polymerization is may be presented in the following diagram: fn ene Z: + CH=CH, —Z: CH)—CH base acarbanion om ZCH)—CH2: +CH)==CH)—* ZCH)-CH)—CHy én, “A ZCH)-CH)-CH)-CHy + CH>=CH, > —> —> ete. In the initiation step of cationic polymerization carbonium ion forms, which interacts with a monomer molecule thereby forms a bigger carbonium ion, which again interacts with another monomer molecule as a result chain growth starts, This is accompanied with communication of positive charge along the chain. Thus the growing chain is itself cation and the molecular mass increases in the course of polymerization. In cationic polymerization the chain termination takes place by the following processes: (i) mutual collision at the ends of growing ions, (ii) splitting of catalyst from the polymer chain. [This is assumed because catalyst is not found in the macromolecule (polymer) of cationic polymerization]. In anionic polymerization initiator interacts with the monomer molecule and forms a carbanion. The carbanion ion just like the carbonium ion of cationic polymerization interacts with another monomer molecule and forms a bigger carbanion. In this way chain growth starts. This is accompanied with the communication of negative charge along the chain, Thus the growing chain becomes a bigger carbanion and the molecular mass increases in the course of polymerization. In anionic polymerization chain termination occurs as a result of collision between growing ions with a molecule of the medium such as ammonia molecule. 4.4.1.3 Thermodynamics of addition polymerization The ease of polymerization of monomer mainly depends on the polarization of the double bond. If the double bond is present in a symmetrically arranged molecules e.g, ethylene, the double bond is. not easily polarized. In that case the molecules polymerizes with difficulty, The substituents introduce into the monomer molecule containing double bonds make the molecule unsymmetrical and promote the polymerization reaction, Thus Propylene, isobutylene polymerize more easilyPolymer n than ethylene and n-butylene. The double bond of styrene molecuie is aiso unsymmetrical, Thus, polymerization of styrene molecule is much easier than ethylene. ‘ The nonpolar monomer molecules, which polymerize themselves with difficulty, may polymerize under the influence of other polar molecules, Therefore, the monomer itself may not polymerize but it may co-polymerize with other monomer. For exarnple, butadiene is not easily polymerized, but polymerization takes place more easily in the presence of styrene. Hence Styrene Butadiene Rubber is easily formed. The polarizability of monomer affects the initiation stage only. The propagation step depends on the activity of free radical that is being formed in the initiation step. The activity of the "-2nomer and that of the radical varies in many cases. The less is the conjugation present in the molecule the less active it is and more active is the radical that is formed from it. The overall process depends both on the activity of monomer (initiation step) and also on the acti (propagation step). ty of the radical Like other chemical reactions the possibility of polymerization reaction may also be predicted from the value of change of free energy (AG) during the process. It is well known that the negative value of AG indicates the possibility of reaction to occur. The value of AG is calculated from the following equation: AG = AH-TAS Where, AH = Change of enthalpy ‘AS. = Change of entropy T = Absolute temperature ‘AG = Change of free energy In the polymerization process formation of a long and ordered macromolecule takes place from relatively disordered small molecules. Thus there is always a decrease in entropy in the polymerization process. This makes the value of ~TAS of the above equation postive. As a result, the probability of negative value of AG becomes less. Thus it does not promote the process. The negative value of AG for the polymerization reaction will only be possible ifthe reaction is highly exothermic. That is the value of AH is negative and its magnitude i larger than the magnitude of the positive value of TAS. The possibility of negative values of AH for polymerization reaction may be described as follows: - Im addition polymerization double bonds of alkenes break up and in lieu of that two single bonds are formed, The energy of aC = C double bond in an unsaturated hydrocarbon is 608.77 ki/mol and that of a C-—C single bond 351.46 kimol. Hence in the polymerization 608.77 KI / mol energy is consumed and 2 x 351.46 = 702.92 kJ / mol energy is liberated. Therefore, the difference 702.92 - 608.77 = 94.15 ki / mol is the enthalpy of polymerization. The average2714 Chemistry of Water, Corrosion & Engineering Materials 42 kJ / mol. Thus the overall value of AG is value of TAS of polymerization reaction is 29 — lace spontaneously. negative, Therefore, the polymerization reaction will take pl 4.4.2 Condensation polymerization molecules of smaller monomer compound are In condensation polymerization many monomer ecule) with the loss of some simple united together to form a big macromolecule (polymer mol molecules (usually water, carbon dioxide etc.). ‘The most common example of condensation polymerization is the formation of nylon 6 6 from adipic acid and hexamethylene diamine. The reaction may be depicted as follows: 0 () HOOC(CH;)4COOH + HyN(CH):NEb>——> adipic acid hexamethylene diamine. cml { oon {CHa —(CH2)6N aie. —(CH2)s-Now 3 0 Nylon 6 6 (a polyamide) Other examples of condensation polymerization are: (ji) Formation of dacron from the reaction between methyl terephthalate and ethylene glycol cxso0c{C))—cooess + HO—CHy-CHy-OH eee —CH,OH pO) poorer Oooo Deca 2 2 0 {a pokester) (iii) Formation of glyptal (an alkyl resin) from the reaction between phthalic anhydride and glycerol. . ce —H,0, OL + Cla FH GH)" Gh (anak resin 1 OH OH OH Phthalic O anhydride Glycerol ‘Among these polymers Nylon 6 6 and Dacron molecul les have got long lit molecules of these polymers can be stretched and oriented along fe om oe aQ=0Polymer 215 | stretching and orientation along the axis of the polymer molecule is the characteristic of synthetic | fibre. Therefore, these two polymers (Nylon 6 6 and Dacron) are known as synthetic fibre and | their uses depend upon the ability to form fibres and hence threads. On the other hand polymer like Glyptal and Bakelite (see section 4.8.1, page 322) do not have linear molecular structure but they have highly cross-linked network like structures. This cross- linked network like structures do not permit stretching or twisting along their own axes. AS a result they do not form fiber. However, they may get the form of resin, which is suitable for protective coatings. 4.4.3 Ring opening polymerization The primary condition of a monomer for taking part into polymerization reaction is, it should be bi-functional. However, cyclic compounds (such as cyclo-propane, ethylene oxide ete.) do not have any functional group. So the question is, if cyclic compounds do not posses any functional group, then how they take part in the polymerization reaction as monomer? Ring opening reaction of cyclic compound always provides a species, which has two sites for reacting with other substance. That is this reaction produces a bifunctional species, which is a fundamental requirement of polymerization as stated above. The examples of such reactions are - CH, oe @ [ So —+ GhrO~ __, —c-ci-0- cH CH)— | ethylene oxide befunctional species | 9 i: q 1 + ~o— (ii) (ema C ro il 0 3 | Phthalic anlydride bifunctional specters | CHs $s Ge nCHs-CH. Polymerization, Ho—CH—CH,-- H—CH,-O7-CH,-CH—OH cHy in-2 ‘Thermodynamies of ring opening polymerization reaction codynamics of polymerization of cyclic compounds depend upon the strain of the ring. The in energy, the easier will be the polymerization reaction. The lower are known to be strained. The strain energy decreases as the number of Therm higher will be the strai membered carbon rings276 Chemistry of Water, Corrosion & Engineering Materials increases. Six membered rings are virtually strain free. The strain of the grows with the subsequent increase in the number of carbon atoms. When a non- re will be no evolution or absorption of heat. That is AH = 0 (zero) f bonds. In addition to the chaotic movement dom, An open chain molecule has always. ‘As a result, polymerization of cyclic carbon atoms in the ring ring again strained ring polymerizes, the ‘as because there will be practically no change ©} entropy depends also on the number of degrees of frees higher degrees of freedom than the cyclic molecule. involved with the increase in entropy. That is tl = +10.46 ki/mol. Since AH = 0 and AS = is positive therefore s always lower than the molecules is i he value of AS is positive. In general for opening of a ring the value of AS the value of AG is negative (AG = AH negative value involved in the polymerization of strained ring. This is due to fact that the enihalpy ined ring is always higher than the enthalpy of the extended chain. Thus the opening of a iberation of heat. Consequently, polymerization reaction is ange. Thus the polymerization of strained ring is The values of AG for different ring opening _T AS). But this negative value i of strait accompanied with the lil associated with higher negative free energy always advantageous than the nonstrained ring. reactions are given below: Number ofatoms present inthering | AG (KJ) 3 92.47 -89.96 -9.20 $5.86 -20.50 46.02 ww Aus ‘ It is evident from the table that AG for six member ring opening reaction is positive. The AG values of ring opening reactions of other cyclic (three, four, five, seven and eight member rings) compounds are negative. So, cyclic compounds having both lower and higher number (than 6) of carbon atoms are easily polymerized. 4.4.4 Oxidative polymerization ‘The oxidati ee .e oxidative polymerization is carried out by the polymerization of monomeric materials. ‘There are two different oxidative polymerizations: (i) Electrochemical oxidation; (ii) Chemical oxidation solution of “ _ . city 8 ae prepa ile-sulphuric acid mixture. Electricity . ough the solution either at constant cuent density or at a constant voltage Jatinum sheet: Pl sheets as the electrodes, The polymerization reaction takes place at anode. Noma! us Polymerization by electrochemical oxidati oxidation: In thi izati i monomeric substance is prepared normally in sc Poem ae niPolymer an polymeric materials are deposited in the form solid film, which may be scratched out from the anode surface. The properties of polymeric materials to some extent depend upon the monomer, bath composition, temperature and current density of polymerization. Polymerization by chemical oxidation: In chemical oxidation of the polymerization process, Some well-known oxidizing agents such as ammonium persulphate (NH,)»S:O1, hydrogen peroxide HO, etc. are used. The monomeric materials are usually taken in water acetonitrile mixture using as solvent. Required amount of oxidizing agent is added and then stirred for several hours (10-14 hours). The polymeric materials are formed and settled down at bottom of the flask which is then filtered off, In oxidative polymerization normally a new type of polymeric material (conductive polymers) is formed. The common examples of such conductive polymers are: poly-acetylene, poly-aniline, Poly-pyrole, poly-thiophene etc. and their derivatives also. The mechanism of oxidative polymerization of aniline is shown below: The science of conducting polymer is developing very rapidly because of their important use in micro-electronic industry. The main use of conducting polymers is in the manufacturing of rechargeable battery, Electronic sensors, diodes etc. 4.5 Polymer processing In general polymers obtained by the different methods described above in section 4.4 are generally obtained in the form of granules, powder or chips. To convert these polymers into usable articles it Imust be processed. During processing of polymer some substances are invariably added. These substances are known as additives. The common additives of polymer processing are: (a) Binders (b) Fillers