Polym. Bull.

(2016) 73:1459–1496
DOI 10.1007/s00289-015-1546-6

REVIEW

Progress in non-isocyanate polyurethanes synthesized

from cyclic carbonate intermediates and
di- or polyamines in the context of structure–properties
relationship and from an environmental point of view

Janusz Datta1 • Marcin Włoch1

Received: 30 April 2015 / Revised: 30 September 2015 / Accepted: 23 October 2015 /

Published online: 30 October 2015
 Springer-Verlag Berlin Heidelberg 2015

Abstract Commercially, polyurethanes are produced by the reaction of diiso-

cyanates, polyols (polyester or polyether) and low molecular weight chain extender.
Toxicity, moisture sensitivity and phosgene-based synthesis of diisocyanates
resulted in investigations focused on obtaining the non-isocyanate polyurethanes
(NIPUs). This work presents the review of synthesis and structure–properties
relationship of non-isocyanate polyurethanes obtained by reacting cyclic carbonated
intermediates with diamines or polyamines. Moreover, the presented methods of
NIPU synthesis were analysed from the environmental point of view. Described
five-membered ring cyclic carbonate intermediates were obtained by carbonation of
glycidyl ethers or thiol-ene coupling of unsaturated cyclic carbonate monomers and
thiols. The special interest was put on the bio-based non-isocyanate polyurethanes,
obtained from chemically modified bio-based substances, e.g. carbonated veg-
etable oils. The mechanical and thermal properties of NIPUs are affected by
functionality, structure and molecular weight of cyclic carbonate intermediates and
diamines or polyamines.

Keywords Non-isocyanate polyurethanes  Carbonated glycidyl ethers  Thiol-ene

coupling  Structure–properties relationship

Introduction

Polyurethanes for industrial applications are obtained by polyaddition of aliphatic

(e.g. hexamethylene diisocyanates, HDI) or aromatic (e.g. 4,40 -methylene diphenyl
diisocyanate, MDI) diisocyanates, polyols (based on polyesters or polyethers, e.g.

& Janusz Datta

jandatta@pg.gda.pl
1
Department of Polymers Technology, Faculty of Chemistry, Gdańsk University of Technology,
G. Narutowicza Str. 11/12, 80-233 Gdańsk, Poland

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poly(tetrahydrofuran), PTHF) and low molecular weight chain extenders (e.g.

ethylene glycol). Synthesis can be realized by one- or two-step method. The two-
step method, called prepolymer method (Fig. 1), includes in the first-step reaction
between diisocyanates and polyols to obtain urethane-prepolymer terminated with
isocyanate groups, and in the next step reaction of this semi-product with low
molecular weight chain extender [1, 2].
High moisture sensitivity and toxicity of diisocyanates initiated in international
scientific world investigations connected with the synthesis of polyurethanes
without using diisocyanates [1]. Non-Isocyanate Polyurethanes (NIPUs) can be
obtained by the reaction of cyclic carbonates and primary diamines (Fig. 2). During
mentioned synthesis, primary or secondary hydroxyl group is formed, and due to
this fact, obtained polymers are also called polyhydroxyurethanes. The presence of
the hydroxyl groups in polymer chain favours formation of intra-molecular
hydrogen bonds, which resulted in increasing of the chemical resistance of polymer
[3, 4]. The proposed applications of NIPU include especially chemical-resistant
coatings, [5, 6], adhesives [7–9], imitation leathers [10, 11] or foams [12, 13].
Polyurethanes can be also synthesized by polycondensation route [14–24]. This
type of methods includes, e.g.,

• self-polycondensation of dihydroxyurethanes obtained by the reaction of

ethylene carbonate with diamines [14],
• self-polycondensation of dihydroxyurethanes obtained by the reaction of
aminoalcohols with ethylene carbonate [15],
• polycondensation of dialkylcarbamates and diols [16],
• polycondensation of diphenylcarbonates and diamines [17].

Fig. 1 Two-step synthesis of polyurethanes by reacting aromatic diisocyanates and polyetherol with low
molecular weight chain extender

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Fig. 2 Synthesis of non-isocyanate polyurethanes by polyaddition of bis(cyclic carbonate)s and diamines

Fig. 3 Synthesis of the non-isocyanate polyurethanes by selected polycondensation methods

Mentioned methods, in comparison with polyaddition-based methods, result in

obtaining NIPU without internal hydroxyl groups in structure of final polymer
(Fig. 3). The comparison of non-isocyanate polyurethanes synthesis methods is
shown in Fig. 4.
Unsaturated derivatives of cyclic carbonates are useful for obtaining semi-
products (to synthesis of NIPU for, e.g. coating applications) by free radical co-
polymerization of vinyl ethylene carbonate with vinyl ester monomers [25]. Another
method includes thiol-ene coupling reaction of unsaturated derivatives of cyclic
carbonates (e.g. 4-vinyl-1,3-dioxolan-2-one) and thiols, which permit to obtain
difunctional or polyfunctional cyclic carbonate intermediates (Fig. 5). Obtained by
this way, semi-product can be cross-linked using diamines and polyamines [26].
Cyclic carbonate oligomeric intermediates for the synthesis of non-isocyanate
polyurethanes, can be also obtained by reaction of diglycidyl ethers (e.g. diglycidyl
ether of bisphenol A) with carbon dioxide (Fig. 6). It is also possible to obtain cyclic
carbonate intermediates by cycloaddition of carbon dioxide into, e.g. epoxidized
soybean [27] or linseed oil [28]. In the next step, obtained semi-products are cured
with diamines or polyamines to obtain non-isocyanate polyhydroxyurethanes

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Fig. 4 Comparison of non-isocyanate polyurethanes in the terms of synthesis methods

Fig. 5 Thiol-ene coupling of cyclic carbonates unsaturated derivative with dithiol

Fig. 6 Cycloaddition of carbon dioxide into diglycidyl ethers

(Fig. 7). The fixation of CO2 during the synthesis of NIPU and applying bio-based
substances (e.g. carbonated vegetable oils) as monomers is favourable from the
environmental point of view and it is connected with actual trends of green
chemistry. The environmental benefits of NIPU are shown in Fig. 8.
Other methods focused on obtaining cyclic carbonate intermediates, e.g. by (1)
reaction of acids or acid chlorides with glycerol carbonates [29, 30], (2) tosylation
of macrodiols [31] and (3) reaction of di- or multi-functional alcohols and dialkyl
carbonates [32].
Non-isocyanate polyurethanes can be also synthesized from six-membered (B6CC)
[33–36] and seven-membered cyclic (B7CC) [37] carbonates and diamines (Fig. 9).
These intermediates (i.e. B6CC and B7CC) are more reactive than five-membered
cyclic carbonates (5CC), which resulted from larger ring strain than in case of five-

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Fig. 7 Synthesis of carbonated vegetable oil by cycloaddition of carbon dioxide to epoxidized

vegetable oil and preparing non-isocyanate polyurethanes by reacting obtained cyclic carbonate
intermediate with diamine or/and polyamines

Fig. 8 Advantages of non-isocyanate polyurethanes from an environmental point of view

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Fig. 9 Synthesis of non-isocyanate polyurethanes using six-membered and seven-membered cyclic

carbonates and diamines

Table 1 Rate constants for reactions of cyclic carbonates with n-hexylamine and benzylamine [34, 37,
38]
Amine Rate constant of reaction cyclic carbonate with amine k (dm3/mol)

Five-membered cyclic Six-membered cyclic Seven-membered cyclic

carbonate (5CC) carbonate (6CC) carbonate (7CC)

n-Hexylamine 0.02 1.19 48.5

Benzylamine 0.01 0.29 11.0

membered cyclic carbonates [34, 37, 38]. The rate constants for reaction of cyclic
carbonates with aliphatic and aromatic amines are compared in Table 1. Unfortu-
nately, these semi-products are synthesized using pathogen-based compounds, e.g.
ethyl chloroformate and triphosgene. Some works concerned on polyaddition of
B6CC or B7CC with diamines (e.g. PXDA, DODDA) were realized using solvent as a
reaction medium. The highest obtained Mn was 26,000 for 6CC and 35,700 for 7CC.
The main aims of the presented work were (1) to review the structure–properties
relationship of non-isocyanate polyurethanes obtained by reacting cyclic carbonated
intermediates with diamines or polyamines, and (2) to analyse the presented methods
of NIPU synthesis from the environmental point of view. This review is focused
especially on five-membered ring cyclic carbonate intermediates, which were obtained

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by cycloaddition of carbon dioxide to selected glycidyl ethers, thiol-ene coupling of

unsaturated cyclic carbonates monomers with thiols, etc. The special interest was put
on the synthesis and properties of bio-based non-isocyanate polyurethanes, obtained
from, e.g. carbonated vegetable oils. Amine curing agents (diamines and polyamines),
which are used for prepare of NIPUs described in this review, were also characterized.

Synthesis, structure and properties of intermediates for synthesis

of non-isocyanate polyurethanes

Cyclic carbonate intermediates obtained by cycloaddition of carbon dioxide

to glycidyl ethers

Cyclic carbonates for synthesis of non-isocyanate polyurethanes can be obtained by

catalytic conversion of epoxides using carbon dioxide. The conversion process is
realized with the presence of a catalyst (e.g. tetra-n-butylammonium bromide or lithium
bromide), under the proper pressure of carbon dioxide (ranged from atmospheric
pressure to 3 MPa) and at sufficient temperature (ranged from 80 to 140 C). Starting
molecules to obtain cyclic carbonate intermediates include terephthalic acid, bisphenol
A, ethylene and butylene glycols and also bio-based substances—e.g. isosorbide
(derived from sugars), glycerol (obtained from plants), limonene (derived, e.g. from
orange peels) and pentaerythritol or trimethylolpropane (obtained by biotechnical and
chemical processing of raw materials, e.g. starch and sugars). Table 2 summarizes the
structure of glycidyl ethers subjected to cycloaddition of carbon dioxide, structure and
properties of obtained cyclic carbonate intermediates and conversion conditions. Also
the commercial epoxy and epoxy-novolac resins [10, 11, 49–52] were used to obtain
cyclic carbonate intermediates by cycloaddition of carbon dioxide (Fig. 10).
The carbonated commercial epoxy-based resins have generally linear structure,
but according to the literature hyperbranched cyclic carbonates, intermediates are
also known. Rokicki et al. [53] synthesized bicyclic carbonate containing phenol
group in a structure, i.e. N,N-bis(2,3-dihydroxypropyl)-4-hydroxy aniline. The
mentioned compound can be reacted with trimethylolpropane triglycidyl ether to
obtain hyperbranched cyclic carbonate intermediates (Fig. 11).
Epoxidized vegetable oils (EVO) can be also used as a starting compound for
synthesis of cyclic carbonate intermediates by cycloaddition of carbon dioxide to
glycidyl ethers [54–65]. Epoxidized soybean oil (ESBO) is commercially available
product and it is used, e.g. as a modificator of epoxy resin or plasticizer in the
processing of poly(vinyl chloride), so it can be also used for preparing a semi-
products to synthesis of non-isocyanate polyurethanes. Cyclic carbonate interme-
diates (based on epoxidized soybean and linseed oils) were produced by chemical
fixation of carbon dioxide with the presence of catalyst (mainly tetra-n-butylam-
monium bromide) at proper pressure of CO2 (ranging in different studies from 1 to
5.65 MPa) and temperature of reaction (ca. 140 C). The conversion of EVO to
carbonated vegetable oil practically equals 100 %. Reaction conditions, properties
of used epoxidized and obtained carbonated vegetable oils are presented in Table 3.

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Table 2 Synthesis and properties of carbonated glycidyl ethers

Viscosity
Reaction Mw at 25ºC
Structure of glycidyl ether Structure of carbonated glycidyl ether Ref.
conditions a) (g mol-1) (Pa·s) b)

O O

O
O
O O CO2,
O
O O atmospheric
O O O
O
366.3 n.s. [38]
O pressure, 100ºC,
O O 30h, LiBr
diglycidyl terephthalate terephtaloyl dicyclocarbonate
O O
O O
O O O O O O
O O
0.1 MPa CO2,
100ºC, 24h 428.4 n.s. [39]
H3C CH3 LiCl
H3C CH3
diglicydyl ether of bisphenol A
bisphenol A-based dicyclocarbonate
O O O O
O O
O O O O
O O CO2, NMP,
H3C CH3 n.s. n.s. [11]
80°C, 30h, NaI
diglicydyl ether of bisphenol A
H3C CH3
(epoxy resin - EPICOAT 828, Japan Epoxy
Resin Co. - epoxy equivalent: 187 g/mol) bisphenol A-based dicyclocarbonate
O O O O
O O
O O O O
O O CO2, NMP,
n.s. n.s [11]
80°C, 30h, NaI
diglicydyl ether of bisphenol F
(epoxy resin YDF-170, Tohto Kasei Co.)
EEW: 172 g/mol) bisphenol F-based dicyclocarbonate
O O O O
O
O O
O P O O O O

O P O
10 MPa CO2,
80°C, 3h, n.s. n.s. [40]
TBAB
bis(4-glycidyloxy phenyl)-phenyl-phosphine
oxide (BGPPO) BGPPO-based dicyclocarbonate
O
O
O 10 MPa CO2,
O O O O
O
O O 80°C, 3h, [40]
cyclic aliphatic epoxy resin O O TBAB
(Cyracure UV-6107, Dow Chemical) Cyracure UV-6107-based dicyclocarbonate

CH3 CH3 O
O O
O O 10 MPa CO2,
O O O 80°C, 3h,
O n n [40]
O TBAB
diglicydyl ether of poly(propylene glycol)
O
poly(propylene glycol)-based
dicyclocarbonate
O

O
O 3MPa CO2,
O
O O
O O 100ºC, 4h,
O
O 262.2 n.s. [41]
O
TBAB
diglicydyl ether of 1,2-ethanediol Fe(BPMCDA)
O
1,2-ethanediol-based dicyclocarbonate
O O
OH 3 MPa CO2,
O O O OH O
O O O
O O O 120ºC, 10h, 292.2 n.s. [42]
diglicydyl ether of glycerol TBAB
glycerol-based dicyclocarbonate
O
O
O
O O O
O O 1 MPa CO2,
O
O 290.3 n.s. [43]
O
80ºC, 24h, LiBr
diglicydyl ether of 1,4-butanediol
O
1,4-butanediol-based dicyclocarbonate
O
O
O O
O O
O O
O CO2, NMP,
diglicydyl ether of 1,6-hexanediol O n.s. n.s. [11]
O
80°C, 30h, NaI
(epoxy resin EX-212, Nagase ChemteX Co.)
EEW: 151 g/mol O
1,6-hexanediol-based dicyclocarbonate
O O
O O
O O O O O O
O O 1 MPa CO2,
310.3 n.s. [43]
80ºC, 24h, LiBr
diglicydyl ether of resoricinol
resoricinol-based dicyclocarbonate

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Table 2 continued

Viscosity
Reaction Mw at 25ºC
Structure of glycidyl ether Structure of carbonated glycidyl ether Ref.
conditions a) (g mol-1) (Pa·s) b)

O
O O
3 MPa CO2,
OH O 120ºC, 10h, 432 13000 [42]
O OH TBAB
O

O
O O
O O O
O O O O 1 MPa CO2,
440 n.s. [43]
O
80ºC, 24h, LiBr
triglicydyl ether of pentaerythritol O
pentaerythritol-based tricyclocarbonate
O
O
O
CH3 O
O
CH3
O
3 MPa CO2,
O
120ºC, 10h, 389 133 [42]
O
O TBAB
O O
O
O O O O
triglycidyl ether of trimeytlolpropane O
O
trimeytlolpropane-based tricyclocarbonate
O O O
O O
O
O 3 MPa CO2,
O 256 310 [44]
H3C H3C 140ºC, TBAB
H3C H3C
limomene oxide
limonene-based dicyclocarbonate
O
O
O O
O H O O
H O
O OH O H
n H O
O O O O OH O 0.6 MPa CO2,
H O O
n 392 n.s. [45]
O O O
80ºC, 18h, LiBr
H H
O O O
H

diglycidyl ether of isosorbide

isosorbide-based dicylcocarbanate
O O

O O O O
O O O O O O 10 MPa CO2,
120ºC, 100 min,
O O n.s. n.s. [46]
7 5 7 O O TBAB
terminal epoxidized fatty acid diesters (TEFAD) 7 5 7
terminal carbonated fatty acid diesters
(TCFAD)
O O

O O O O 10 MPa CO2,
O O O O O O
H H 140ºC, 100 min,
O O H H n.s. n.s. [46]
8 7 5 7 8 O O TBAB
8 7 5 7 8
internal epoxidized fatty acid diesters (IEFAD)
internal carbonated fatty acid diesters
(ICFAD)
O O
O O
O O O O O O
O O
5 MPa CO2,
O O
8 8 O O 80ºC, 24h, n.s. n.s. [47]
8 8
fatty acid-based bis-epoxide TBAB
fatty acid-based bis-cyclic carbonate
(linker: 1,3-propanediol) (linker: 1,3-propanediol)
UndPdE-bEpoxide UndPdE-b5CC
O
O O O
O
NH NH O
NH NH
6 MPa CO2,
O
8 8
O 8 8 O O
140ºC, 24h, n.s. n.s. [47]
O
O
TBAB
fatty acid-based bis-epoxide
(linker: butane-1,4-diamine) fatty acid-based bis-cyclic carbonate
UndBdA-bEpoxide (linker: butane-1,4-diamine)
UndBdA-b5CC
O O
O O
O O O O O O
O O
5 MPa CO2,
N N
8 8 N N 135ºC, 24h, n.s. n.s. [47]
8 8 TBAB
fatty acid-based bis-epoxide
(linker: piperazine) fatty acid-based bis-cyclic carbonate
UndPipdA-bEpoxide (linker: piperazine)
UndPipdA-b5CC

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Table 2 continued

Viscosity
Reaction Mw at 25ºC
Structure of glycidyl ether Structure of carbonated glycidyl ether Ref.
conditions a) (g mol-1) (Pa·s) b)

O O
O O
O O O O O O

N N O O 5 MPa CO2,
8 8 N N 80ºC, 24h, [47]
8 8 n.s. n.s.
TBAB
fatty acid-based bis-epoxide fatty acid-based bis-cyclic carbonate
(linker: N,N’-dimethylpropane-1,3-diamine) (linker: N,N’-dimethylpropane-1,3-diamine)
UndPMedA-bEpoxide UndPMedA-b5CC
O O O O
O O
O O O O 6 MPa CO2,
N N O O
8 8 8 80ºC, 24h,
n.s. n.s. [47]
N N
8 8 8 TBAB
4 4
fatty acid-based bis-epoxide 4 4
(linker: N,N’-dihexyldecane-1,10-diamine) fatty acid-based bis-cyclic carbonate
UndDHexdA-bEpoxide (linker: N,N’-dihexyldecane-1,10-diamine)
UndDHexdA-b5CC
O O
O O O O
6.9 MPa CO2,
O 7 O O 7 120ºC, 10h,
O O
O n.s. n.s. [48]
TBAB
6
6
diglycidyl ether of cardanol cardanol-based dicyclocarbonate
O O

O CH3 CH3 O O O
CH3 CH3
O O O O O O
Si O Si Si O Si CO2, NMP, 396
CH3 CH3
n n n.s. [10]
CH3 CH3 80°C, 30h, NaI 970
epoxy-modified polysiloxane dicyclocarbonate polysiloxane
(DCPS-396, DCPS-970)
O O

O CH3 CH3 O O O
CH3 CH3
O O
O Si O Si O CO2, NMP,
O Si O Si O
n n
1066 n.s. [10]
CH3 CH3 CH3 CH3 80°C, 30h, NaI
epoxy-modified polysiloxane dicyclocarbonate polysiloxane
(DCPS-1066)
a
Catalysts: TBAB tetra-n-butylammonium bromide, Fe(BPMCDAC) [N,N0 -bis-2-pyridinylmethyl-cyclo-
hexane-1,2-diamine]iron(II) chloride; solvents: NMP N-methyl-2-pyrrolidone
b
n.s. not specified

The most important advantages of this route to obtain cyclic carbonate interme-
diates are eco-friendly and renewable nature of vegetable oils, utilization of carbon
dioxide as reactant and solventless synthesis. The application of carbonated
vegetable oils in the synthesis of non-isocyanate polyurethanes resulted in obtaining
bio-based polymeric material.
According to the literature, there are also known potential intermediates for
synthesis of non-isocyanate polyurethanes, which were obtained using vanillin [66]
as a starting molecule (Fig. 12). The presented cyclic carbonates were obtained by
cycloaddition of carbon dioxide into glycidyl ether derivatives of vanillin. The
vanillin-based diamines were synthesized by thiol-ene coupling of cysteamine
hydrochloride to unsaturated derivatives of vanillin.

Cyclic carbonate intermediates obtained by thiol-ene coupling

of unsaturated derivatives of cyclic carbonates and thiols

The preparation of cyclic carbonate intermediates for synthesis of non-isocyanate

polyurethanes by thiol-ene coupling is a one-step synthesis, which include reaction

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Fig. 10 Cyclic carbonate intermediates obtained from epoxy and novolac resins

Fig. 11 Starting molecule (a) and hyperbranched cyclic carbonates intermediate (b) obtained using this
compound

between dithiol and cyclic carbonate monomer with unsaturated C=C bond at the
end of side chain (Fig. 5). This reaction is realized with a thiol/double bond ratio
equal to 1:1 and the reaction mixture is irradiated using a UV source. The most

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Table 3 Synthesis and properties of carbonated vegetable oils

Characteristic of epoxidized Reaction Conversion Average Mw References
vegetable oila conditionsb (%) viscosity at (g mol-1)
25 C
(Pas)

Epoxidized soybean oil (Flexol 5.65 MPa 99.8 33 n.s. [54]

EPO, Dow chemicals), CO2,
EOC = 6.8 % (4 mol epoxy 140 C,
groups per triglyceride) 22 h,
TBAB
Epoxidized soybean oil (Epoxol 5.65 MPa 99.8 41.9 n.s. [55]
7-4, American Service), CO2,
EOC = 7.1 % 140 C,
22 h,
TBAB
Epoxidized soybean oil (Cognis), 1 MPa CO2, 100 27 1648 [56]
EOC = 6.8 % (4.2 mol epoxy 140 C,
groups per triglyceride) TBAB
Epoxidized linseed oil (HOBUM 1 MPa CO2, 100 2.5 1998 [56]
Oleo chemicals), EOC = 8.9 % 140 C,
(5.2 mol epoxy groups per TBAB
triglyceride)
a b
EOC epoxy oxygen group content, Catalyst: TBAB tetra-n-butylammonium bromide

Fig. 12 Intermediates for the synthesis of non-isocyanate polyurethanes obtained by chemical

modification of vanillin

important advantages of these reactions are absence of by-products, high yields

connected with short reaction time and optionality of photoinitiator and solvent
using.

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Table 4 summarizes the thiol-ene coupling reaction conditions, substrates for

reaction and molecular weight of obtained products. Table 4 is connected with
Fig. 13, which presents the structure of obtained cyclic carbonate intermediates by
thiol-ene coupling reaction, resulting in branched cyclic carbonates intermediates.
As can be seen in Table 4, researches used linear aliphatic thiols (i.e. 1,2-
ethanedithiol and 1,6-hexanedithiol) and linear ether-thiols (e.g. diethanethiol) and
branched ester-thiols [e.g. trimethylolpropane tris(3-mercaptopropionate)] [26, 34,
67]. Application of thiol couplers with more than two thiol groups (e.g.
pentaerythritol tetrakis(3-mercaptopropionate)) resulted in obtaining the branched
cyclic carbonates intermediates, which should make final NIPU material more rigid
[26].

Cyclic carbonate intermediates obtained by radical polymerization,

tosylation and other methods

Cyclic carbonate intermediates can be also obtained by other methods, especially

(1) reaction of multifunctional hydroxyl compounds with dialkyl carbonates [32,
68], (2) reaction of acids or acid chlorides with glycerol carbonates [29, 30], (3)
tosylation of polymer diols [31] and (4) radical polymerization or co-polymerization
of unsaturated derivatives of glycerol carbonate or cycloaddition of carbon dioxide
to polyepoxides [69–76].
Cyclic carbonate intermediates can be synthesized by transesterification of
multifunctional hydroxyl compounds—i.e. D-sorbitol (Fig. 14) or hyperbranched
polyglycerol (Fig. 15)—using dimethyl carbonate. The reaction is carried out at
80 C in the presence of potassium carbonate as a catalyst. Obtained semi-products
possess potential as component for the synthesis of non-isocyanate polyurethanes.
Moreover, hyperbranched polyglycerol-based tricyclocarbonate can be used as a
modificator (low viscosity toughener) of epoxy resin [32, 69].
Bis(cyclic carbonate)s based on terephthalic acid moiety can be obtained by two
different ways (Fig. 16). The first route is one-step method connected with
esterification of terephthalic acid using glycerol carbonate, and the second route
contains two steps, i.e. reaction of terephthaloyl chloride with glycidol and
cycloaddition of carbon dioxide under atmospheric pressure [29, 30].
The tosylation method, which includes functionalization of macrodiols using
glycerol carbonate tosylate, permits to obtain bis(cyclic carbonate)s with good
yields, and synthesized intermediates can be applied for the synthesis of non-
isocyanate polyurethanes by catalyst-free route [31]. The general procedure of
polymer diol tosylation with examples obtained by Annunziata et al. [31] products
is shown in Fig. 17.
Another way of cyclic carbonates synthesis is connected with a,x-di(cyclic
carbonate) telechelic poly(trimethylene carbonate)s, which are obtained by ring-
opening polymerization of trimethylene carbonate using a glycerol carbonate (or
1,3-propanediol) as a chain transfer agent (Fig. 18). The ring-opening polyaddition
of obtained bis(cyclic carbonate)s (Fig. 19) using diamines results in obtaining
poly(carbonate-hydroxyurethane)s [78].

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Table 4 Synthesis and properties of carbonated intermediates obtained by thiol-ene coupling

Cyclic carbonate Thiol intermediate Reaction Product Mw (g Ref.

unsaturated intermediate condition mol-1)
O HS SH UV, 2h bis(VD)- n.s. [67]
O
O OETH
O
diethanethiol

4-vinyl-1,3-dioxolan-2-
one
O HS SH UV, 5h bis(AOD)- n.s. [67]
O
O OETH
diethanethiol
O O
4-
[(prop-2-en-1-
yloxy)methyl]- 1,3-
dioxolan-2-one
O HS
SH
60ºC, bis(BD)- n.s. [34]
O 24h, EDTH
O 1,2-ethanedithiol
AIBN
4-(3-butenyl)-1,3-
dioxolan-2-on
O HS UV, 1h, bis(VD)- 378.12 [26]
SH
O DMPA HDTH
1,6-hexanedithiol
O

4-vinyl-1,3-dioxolan-2- O SH UV, 1h, tris(VD)- 740.18 [26]

one O
DMPA TMPTMP
O
O

O SH

HS O
trimethylolpropane
tris(3-
mercaptopropionate)
O SH UV, 1h, tetra(VD)- 944.19 [26]
HS O
DMPA PERTMP
O
O

O
O O SH

HS O
pentaerythritol tetrakis(3-
mercaptopropionate)
AIBN 2,20 -azobisisobutyronitrile, DMPA 2,2-dimethoxy-2-phenylacetophenone

Another route (Fig. 20), connected with coating applications, includes

• radical polymerization of unsaturated derivatives of glycerol carbonate-glycerol

carbonate methacrylate (GCM) [69], 2-methacrylic acid 2-(2-oxo-1,3-dioxolan-
4-ylmethoxycarbonylamino)ethyl ester (CUMA) [70], (2-oxo-1,3-dioxolan-4-yl)

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Fig. 13 Cyclic carbonate intermediates obtained by thiol-ene coupling of cyclic carbonate unsaturated
derivatives and thiols

Fig. 14 Synthesis of sorbitol-based dicyclocarbonate

methyl vinyl ether (OVE) [71] and norbornene-based cyclocarbonate (NCC)

[72],
• radical co-polymerization of unsaturated derivatives of glycerol carbonate with
unsaturated monomers, e.g. vinyl ethylene carbonate (VEC) co-polymerization
with vinyl acetate and butyl acrylate [73] or vinyl neodecanoate and vinyl
neononanoate [25], CUMA co-polymerization with butyl acrylate, butyl
methacrylate, and diethylene glycol methyl ether methacrylate [70], 3-(2-
vinyloxyethoxy)-1,2 propylene carbonate and N-phenyl maleimide [74],
norbornene-based cyclocarbonate copolymerized with cyclooctane [72],

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Fig. 15 Synthesis of hyperbranched polyglycerol-based tricyclocarbonate

Fig. 16 Synthesis of terephthaloyl dicyclocarbonate

• cycloaddition of carbon dioxide to polyepoxides—the multifunctional epoxy

polymers can be also obtained by radical polymerization of unsaturated
compounds with oxirane group in the structure [75], or epoxidation of
unsaturated polymers obtained by radical polymerization [76, 77].

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Fig. 17 General procedure for tosylation of polymer diols and semi-products obtained by this way

Cyclic carbonates can be also used as substrates for preparing surface

functionalized fillers, e.g. silica. Hoşgör et al. [40] described phosphine oxide-
based polyurethane/silica nanocomposite obtained via non-isocyanate route. Silica
particles used in this study were modified by cyclic carbonate functional silane
coupling agent (i.e. 4-(3-(trimethoxysilyl)propoxyl)methyl-1,3-dioxolan-2-one,
CPS) to improve the compatibility of silica particles and non-isocyanate
polyurethane matrix. The functionalization method is presented in Fig. 21. The
similar way of filler modification (by using 4-(3-(trimethoxysilyl)propoxyl)methyl-
1,3-dioxolan-2-one) was applied by Kathalewar et al. [79] in the case of zinc oxide
non-isocyanate polyurethane nanocomposites.

Diamines and polyamines used as a curing agents in the synthesis of NIPU

from cyclic carbonate intermediates

Diamines and polyamines are used as a curing agents in the synthesis of non-
isocyanate polyurethanes from cyclic carbonates, which was synthesized by

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Fig. 18 Synthesis of a,x-

di(cyclic carbonate) telechelic
poly(trimethylene carbonate)s

Fig. 19 Intermediates for the synthesis of non-isocyanate poly(carbonate-urethane)—i.e. a,x-di(cyclic

carbonate) telechelic poly(trimethylene carbonate)s

carbonation of glycidyl ethers and thiol-ene coupling of unsaturated derivatives of

cyclic carbonates and thiols. Table 5 summarizes the structure and properties of
diamines and polyamines, which were used to obtain non-isocyanate polyurethanes
described in this review. The group of diamines includes aliphatic (e.g. 1,6-
hexamethylenediamine), cycloaliphatic (e.g. isophorone diamine), aromatic diami-
nes (e.g. m-xylene diamines) and linear polyetheramines (e.g. 3,6-dioxaoctane-1,8-
diamine, JEFFAMINE amines from HUNTSMAN). The group of polyamines
consists of linear polyamines (e.g. diethylenetriamine, triethylenetetramine),
branched polyamines (e.g. tris(2-aminoethyl)amine, LUPASOL amines from
BASF) and branched amino amides (e.g. citric acid hexamethylene amino-amide).

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Fig. 20 Multifunctional cyclic carbonates obtained by radical polymerization or co-polymerization of

unsaturated monomers

The branched amino amides used as curing agents were synthesized by

aminolysis reaction between triethyl citrate and diamine (1,6-hexanediamine or
1,12-dodecanediamine) in excess. Obtained amino amides 1,6-CAA and 1,12-CAA
are characterized by high melting temperature, equal to 130–145 and 125–135 C,

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1478 Polym. Bull. (2016) 73:1459–1496

Fig. 21 Preparation of cyclic carbonate functional silane coupling agent and surface-functionalization of
silica particles

respectively, and due to this fact, these compounds were used in the form of mixture
with other diamines. Bähr et al. [44] prepared the mixtures of obtained amino
amides with isophorone diamines 1,6-CAA/IPDA and 1,12-CAA/IPDA at the molar
ratio of amines 1:1 and 1:1,75, respectively. Fleisher et al. [42] conducted the
synthesis of 1,6-CAA with excess of 1,6-HDA, and after the reaction, the unreacted
diamines were not distilled off, which resulted in obtaining the mixture 1,6-CAA/
1,6-HDA at the molar ratio 1:4,5.

Synthesis, structure and properties of non-isocyanate polyurethanes

obtained from cyclic carbonates intermediates and diamines/polyamines

Non-isocyanate polyurethanes based on cyclic carbonate intermediates

obtained by cycloaddition of carbon dioxide to glycidyl ethers

Table 6 presents synthesis conditions and properties of non-isocyanate polyur-

ethanes obtained by reacting carbonated glycidyl ethers with several different
amines, linear aliphatic diamines, cycloaliphatic diamine (IPDA) and linear
etherdiamines (DOODA, JEFFAMINE D-400) and also with polyamines, i.e.
DETA and TETA. Described polyurethanes were synthesized in solvent (especially
DMF) or mainly in atmosphere of inert gas (i.e. argon or nitrogen). The use of
solvent as a reaction medium or for purification of obtained polymers is a
disadvantage of presented methods.
In the case of terephthaloyl dicyclocarbonate-based NIPU, the average molecular
weight and polydispersity of obtained polyurethanes increase with growing length
of carbon chain in the structure of used aliphatic diamine. The glass transition
temperature in the case for NIPU obtained using 1,2-EDA and 1,3-PRDA was
comparable, but for 1,6-HDA was found to be lower than in case of earlier
mentioned lower molecular weight aliphatic diamines [30].

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Table 5 Structure and properties of difunctional and polyfunctional amine curing agents

PAG
Mw
Amine curing agent Abbreviation (mol Ref.
(g mol-1)
mol-1)
H2N
NH2 [30, 41,
1,2-EDA 60.10 2
1,2-ethanediamine 54, 56]
H2N NH2 [29, 30,
1,3-PRDA 74.12 2
1,3-propanediamine 41]
NH2
H2N [47, 54,
1,4-BDA 88.15 2
1,4-butanediamine 56]
H2N NH2
1,5-PNDA 102.18 2 [30]
1,5-pentanediamine
NH2 [10, 26,
H2N 1,6-HDA 116.20 2 30, 41,
1,6-hexanediamine 42, 54]
NH2
H2N [29, 45,
1,10-DDA 172.31 2
1,10-decanediamine 67]
NH2
H2N
1,12-DDDA 200.36 2 [39]
1,12-dodecanediamine
NH
H2N NH2
2,2 ′-diaminodiethylamine [26, 29,
DETA 103.17 2
(diethylenetriamine) 45]

NH NH2
H2N NH
N,N'-Bis(2-aminoethyl)ethane-1,2-diamine TETA 146.23 2 [29, 44]
(triethylenetetramine )
NH NH
H2N NH NH2
N-(2-Aminoethyl)-N'-{2-[(2- TEPA 189.30 2 [43]
aminoethyl)amino]ethyl}-1,2-
ethanediamine(tetraethylenepentamine)
NH2

[29, 44,
NH2 45, 46,
IPDA 170.30 2
47, 55,
5-amino-1,3,3- 56]
trimethylcyclohexanemethylamine
(isophorone diamines)
NH2
N
N BAPP 200.32 2 [10]
H2N
1,4-bis(3-aminopropyl)piperazine

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Table 5 continued

PAG
Mw
Amine curing agent Abbreviation (mol Ref.
(g mol-1)
mol-1)
H2N NH2

MXDA 136.13 2 [55]

1,3-bis(aminomethyl)benzene
(m-xylylene diamine)
NH2
H2N PXDA 136.13 2 [55]
1,4-bis(aminomethyl)benzene
(p-xylylene diamine)
O OH O
H2N NH2
NH NH
3
NH2
3
1,6-CAA 486 3 [42, 44]
O NH
3
citric acid 1,6-hexamethylene amino-amides
O OH O
H2N NH2
NH NH
6
6
NH2 1,12-CAA 739 3 [44]
O NH
6
citric acid 1,12-dodacane amino-amides
H2N NH2
O
x x ~ 6.1 JEFFAMINE [29, 45,
430 2
JEFFAMINE ® D-400 (polyetheramine), D-400 47]
HUNTSMAN
O NH2
H2N O
DOODA 148.20 2 [29]
3,6-dioxaoctane-1,8-diamine
H2N O
O NH2
DODDA 204.31 2 [34]
4,9-dioxadodecane-1,12-diamine
...
LUPASOL ® FG
(hyperbranched LUPASOL ®
[44]
HN
NH
800 8.1
polyethylenimine
2
FG
N ), BASF
N
LUPASOL ®
HN G20(hyperbranch
NH LUPASOL ®
2
ed 1300 12.2 [44]
G20
N
polyethylenimine
NH
), BASF
N
H N NH
LUPASOL ® PR
2 2
(hyperbranched LUPASOL ®
NH 2000 16.8 [44]
polyethylenimine PR
... ), BASF
CH3 CH3
H2N NH2
Si O Si
APSi-262 262
n
APSi-860 860 2 [11]
CH3 CH3 APSi-1480 1480
amino-modified polysiloxane

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Table 5 continued

PAG
Mw
Amine curing agent Abbreviation (mol Ref.
(g mol-1)
mol-1)
amine derivative of dimmerized fatty acids PRIAMINE
(PRIAMINIE 1075, Croda)
n.s. 2 [47]
1075
O OH

LysHCl 182.6 2 [80]

H2N NH2 HCl
L-(+)-lysine hydrochloride
OH

LysOH 132.2 2 [80]

H2N NH2
lysinol
Mw weight average molecular weight, PAG primary amine groups content

The glass transition temperature and thermal stability for isosorbide-based NIPU
were found to be highest (Tg = 59 C, Td 5 % = 255 C) for the application of
IPDA as a curing agent, which resulted from rigid structure of these cycloaliphatic
diamines. Cross-linking using long chain aliphatic diamine 1,10-DDA and aliphatic
triamine DETA resulted in decreasing of Tg and thermal stability, and higher
reduction was observed in the case of applied polyamine. The lowest value of Tg,
equal to -8 C, was observed for high-molecular weight polyetherdiamine, which
suggests that JEFFAMINE D-400 makes final NIPU material more flexible and
tough, but its thermal stability (242 C) is comparable to polyurethanes obtained
using DETA (243 C) [45].
Table 7 presents synthesis conditions and properties of non-isocyanate
polyurethanes obtained from polysiloxane-based bis(cyclic carbonate)s and
polysiloxane-based diamines. Synthesis of NIPUs was realized by the solvent
method, as applications of prepared polymers were proposed, e.g. imitation leathers
[10, 11].
Synthesis and properties of non-isocyanate polyurethanes obtained by environ-
mental friendly and solvent-free method from cyclic carbonates and diamines or
polyamines are shown in Table 8. The curing of obtained materials is realized at the
temperature from 70 to 100 C by 2 h to 15 h. In some cases, curing consists of the
two steps, with different times and temperatures. Some of the cyclic carbonate
intermediates presented in Table 2 are derived from bio-based and renewable
natural sources—e.g. glycerol, limonene—which is beneficial from environmental
point of view.
In the case of NIPUs obtained from glycerol dicyclocarbonate (GDC),
trimethylolpropane tricyclocarbonate (TTC) and pentaerythritol tricyclocarbonate
(PTC), it was found that with rising cyclic carbonate groups in the structure of
intermediate, the tensile modulus, tensile strength and glass transition temperature
increase, but elongation at break decreases. Application of curing agent mixture
(1,6HDA/1,6-CAA), in comparison with single diamine 1,6-HDA, resulted in the

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 Table 6 Synthesis and properties of non-isocyanate polyurethanes obtained from carbonated glycidyl ethers and diamines or polyamines
1482

Cyclic carbonate component Diamine or Reaction conditionsa Mn PD Tg DSC Td 5 % Td 10 % References

polyamine (g mol-1) (Mw/Mn) (C) (C) (C)

123
Bisphenol A-based 1,12-DDDA NMP, air, 75 C, 48 h, LiCl 10,500 1.74 31.1 – – [39]
dicyclocarbonate
Bisphenol A-based LysHCl DMAc, 100 C,24 h, DBU 24,000 1.58 – – – [80]
dicyclocarbonate LysOH NMP, 100 C, 24 h 16,000 1.39 – – –
Terephthaloyl dicyclocarbonate 1,2-EDA DMF, N2, r.t., 72 h 7800 1.54 21 – – [30]
1,3-PRDA 8700 1.52 29 – 182
1,5-PNDA 11,800 1.63 n.s. – 177
1,6-HDA 13,200 1.80 3 – 208
Terephthaloyl dicyclocarbonate 1,3-PRDA DMF, N2, 75 C, 48 h – – 72 – – [29]
1,10-DDA – – 44 – –
IPDA – – 78 – –
DOODA – – 28 – –
JEFFAMINE D-400 – – 4 – –
DETA – – 54 – –
TETA – – 31 – –
Isosorbide dicyclocarbonate 1,10-DDA DMF, Ar, r.t., 12 h, catalyst 7788 2.55 15 243 – [45]
IPDA – – 59 255 –
DETA – – 0 234 –
JEFFAMINE D-400 – – -8 242 –

Synthesis of NIPUs was realized by solvent method

Mn number average molecular weight, Mw weight average molecular weight, PD polydispersity, Tg DSC glass transition temperature determined by DSC method, Td 5 %/
Td 10 % temperature at which 5 %/10 % weight loss of sample occurred (by TGA method)
a
Solvents: N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-Dimethylacetamide (DMAc); catalyst: 1,8-diazabicycloundec-7-ene (DBU)
Polym. Bull. (2016) 73:1459–1496
Polym. Bull. (2016) 73:1459–1496 1483

Table 7 Synthesis and properties of non-isocyanate polyurethanes obtained from cyclic carbonate- and
amine-modified polysiloxane components. Synthesis of NIPUs was realized by solvent method
Cyclic carbonate component Diamine Reaction Mn dm eb References
conditionsa (g mol-1) (MPa) (%)

Bisphenol A-based APSi- NMP, 90 C, 28,000 7.1 15 [11]

dicyclocarbonate 1480 10 h
Bisphenol F-based APSi- 37,000 16.8 73
dicyclocarbonate 860
Hexamethylene glycol-based APSi- 41,000 26.2 90
dicyclocarbonate 262
Polysiloxane-based 1,6- DMF, 90 C, 38,000 32.1 15 [10]
dicyclocarbonate (DCPS-396) HDA 10 h
Polysiloxane-based BAPP 43,000 23.8 83
dicyclocarbonate (DCPS-970)
Polysiloxane-based XDA 31,000 35.2 50
dicyclocarbonate (DCPS-1066)

Mn number average molecular weight, dm tensile strength, eb elongation at break

a
Solvents: N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF)

improvement of mentioned earlier mechanical properties, due to higher stiffness of

NIPU, which resulted from higher cross-linked structure. The Tg in all cases also
increases, when the mixture of diamine (1,6-HDA) and triamine-amide (1,6-CAA)
is applied. The application of tri- or tetra-cyclic carbonates caused reduction of
NIPU flexibility connected with drastically decreasing elongation at break (from
280 % for GDCC/1,6-HDA to 5 % for PTCC/1,6HDA) [42].
Ethylene glycol dicyclocarbonate (EGC)-based NIPU exhibited decreasing of
glass transition temperature and increasing of thermal stability with the growing
length of carbon chain between amine groups in applied curing agents. Reduction of
Tg resulted from higher mobility of polymer chains due to the presence of longer
aliphatic chains introduced by diamines. The improvement of thermal stability is
also affected by the presence of longer aliphatic chains by diamines [41].
In the case of butylene glycol dicyclocarbonate (BGDC), resorcinol dicyclocar-
bonate (RDC) and trimethylolpropane tricyclocarbonate (TTC)-based NIPUs cured
with polyamine TEPA with two primary –NH2 groups, it was found that Tg
(measured by DSC and DMA method) and storage modulus (measured by DMA
method) are rising in order BGDC \ RDC \ TTC. The increase of glass transition
temperature and stiffness of prepared materials (BGDC and TTC) is related to the
increase of cyclic carbonate group content, which resulted in the reduction of
polymer chains mobility due to higher cross-link density of prepared NIPUs
network. The difference between BGDC- and RDC-based NIPUs is related to more
rigid structure of resorcinol than in case of butylene glycol due to the presence of
aromatic ring in the structure of resorcinol [43].
NIPUs prepared using limonene dicyclocarbonate (LC) and TETA or 1,12-CAA
exhibit the similar values of Tg, but applying the LUPASOL polyethylenimines
results in increasing of Tg. Also using the curing agent mixtures (1,12-CAA/IPDA
or 1,6-CAA/IPDA) caused increasing of Tg. CL-based composites cured with 1,12-

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 Table 8 Synthesis and properties of non-isocyanate polyurethanes obtained from carbonated glycidyl ethers and diamines or polyamines
1484

Cyclic carbonate component Diamine or Curing conditions Em dm eb Tg DSC Tg DMA E0 Td 5 % Td max References
polyamine (MPa) (MPa) (%) (C) (C) (MPa) (C) (C)

123
Glycerol-based 1,6-HDA 70 C, 8 h 7 9 280 20 – – – – [42]
dicyclocarbonate (GDC) 1,6-HDA/1,6-CAA 7 6 310 36 – – – –
(molar ratio 4,5:1)
Trimethylolpropane-based 1,6-HDA 590 26 21 47 – – – –
tricyclocarbonate (TTC) 1,6-HDA/1,6-CAA 1230 40 5 56 – – – –
(molar ratio 4,5:1)
Pentaerythritol-based 1,6-HDA 660 33 5 51 – – – –
tricyclocarbonate (PTC) 1,6-HDA/1,6-CAA 1740 63 6 51 – – – –
(molar ratio 4,5:1)
1,2-Ethanediol-based 1,2-EDA Step I: 60 C, 20 min – – – 9 – – 206 241 [41]
dicyclocarbonate (EGDC) 1,3-PRDA Step II: 80 C, 2 h – – – 4 – – 234 276
1,6-HDA – – – -2 – – 266 319
1,4-Butanediol-based TEPA 100 C, 12 h – – – 16 38.5 664 – – [43]
dicyclocarbonate (BGDC)
Resorcinol-based TEPA – – – 56 71 1310 – –
dicyclocarbonate (RDC)
Trimethylolpropane-based TEPA – – – 67 93 1270 – –
tricyclocarbonate (TTC)
Polym. Bull. (2016) 73:1459–1496
 Table 8 continued

Cyclic carbonate component Diamine or Curing conditions Em dm eb Tg DSC Tg DMA E0 Td 5 % Td max References
polyamine (MPa) (MPa) (%) (C) (C) (MPa) (C) (C)

Limonene-based TETA Step I: 70 C, 12 h – – – 55 – – – – [44]

dicyclocarbonate (LC) LUPASOL FG Step II: 100 C, 3 h 2400 7 1 60 – – – –
LUPASOL G20 2700 21 2 62 – – – –
LUPASOL PR 4100 14 1 62 – – – –
1,12-CAA – – – 55 – – – –
1,6-CAA/IPDA – – – 60 – – – –
Polym. Bull. (2016) 73:1459–1496

1,12-CAA/IPDA – – – 70 – – – –

Synthesis of NIPUs was realized by solvent-free method

Em tensile modulus, dm tensile strength, eb elongation at break, Tg DSC glass transition temperature determined by DSC method, Tg DMA glass transition temperature
determined by DMA method, E’ storage modulus determined by DMA method, Td 5 % temperature at which 5 % weight loss of sample occurred (by TGA method), Td max
temperature at which maximum rate of degradation occurred (by TGA method)
1485

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CAA/IPDA or 1,6-CAA/IPDA exhibit higher glass transition temperature than in

case of 1,12-CAA cured NIPU, which suggest that rigid structure introduced by
IPDA diamines is the main reason of Tg rising [44].
Analysing the properties of LC/LUPASOL non-isocyanate polyurethanes also
showed that rising molecular weight and content of –NH2 groups of hyperbranched
polyethylenimines did not affect Tg value, and increases stiffness of prepared
NIPUs, but the highest tensile strength was obtained for LUPASOL G20 (with
average molecular weight and primary amine groups content between LUPASOL
FG and LUPASOL PR) [44].
High bio-based content non-isocyanate polyurethanes can be also obtained by the
reaction of carbonated vegetable oils and diamines. According to the literature, it is
known that the NIPUs obtained from carbonated soybean or linseed oil are cured
using different aliphatic, cycloaliphatic and aromatic diamines. The curing
conditions and properties of mentioned NIPUs systems are presented in the
Table 9. The general procedure of curing consists of two steps. In the first step, the
material is cured at 70 C by 6 or 10 h, and in the next step at 100 C by 15 or 3 h,
respectively. The cross-linking of CSBO using aliphatic (i.e. 1,2-EDA, 1,4-BDA
and 1,6-HDA), cycloaliphatic (IPDA) and aromatic (i.e. MXDA, PXDA) diamines
was investigated in the terms of molar ratio of cyclic carbonate to amine, equal to
1:0.5, 1:1 and 1:2. Results of investigations show that the optimal molar ratio 1:1
resulted in obtaining NIPUs with the highest tensile strength, hardness and glass
transition temperatures, which indicate the higher cross-link density. The molar
ratio 1:0.5 resulted in incomplete cross-linking, which resulted in very low tensile
properties and glass transition temperature, when the molar ratio 1:2 caused
aminolysis of ester groups and formation of amide groups [54, 55].
Non-isocyanate polyurethanes obtained by reacting CSBO with 1,2-EDA, 1,4-
BDA and 1,6-HDA exhibited decreasing of tensile strength and hardness (connected
with increasing of elongation at break) with increasing of carbon chain length in the
structure of applied aliphatic diamines. It is suggested that mentioned fact is
connected with flexibility of polymer materials, which resulted from higher mobility
of polymer movements. The glass transition temperature was similar in all
mentioned NIPUs. In the case of NIPUs obtained by reacting CSBO, two aromatic
diamines (MXDA and PXDA) were observed, which on applying PXDA resulted in
higher tensile strength (connected with lower elongation at break), hardness and
glass transition temperature, which is probably caused by non-linear molecular
geometry, which make more difficult the formation of hydrogen bonds between
urethane groups. Applying IPDA as a curing agent of CSBO resulted in obtaining
NIPU material with the highest hardness and glass transition temperature, which
resulted from rigid structure of IPDA due to the presence of cyclic ring, which
decreased the mobility of polyurethane chains. The value of tensile properties of
CSBO/IPDA-based NIPU was between properties of CSBO cured with applied
aromatic diamines, i.e. MXDA and PXDA [54, 55].
In the case of carbonated linseed oil, as in earlier presented examples of NIPUs
reacted with IPDA, obtained polyurethanes exhibited lower tensile strength and
elongation at break, but higher tensile modulus and glass transition temperature than
in curing with aliphatic diamines, i.e. 1,2-EDA and 1,4-BDA. Non-isocyanate

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 Table 9 Synthesis and properties of non-isocyanate polyurethanes obtained from carbonated vegetable oils and diamines, at a carbonate to amine ratio equal to 1:1
Carbonated vegetable oil Diamine or Curing conditions Em dm eb H (8Sh Tg DSC Tg DMA References
polyamine (MPa) (MPa) (%) A) (C) (C)

Carbonated soybean oil 1,2-EDA I step: 70 C, 10 h II step: 100 C, – 5.77 90 83 22.0 38.0 [54]
Polym. Bull. (2016) 73:1459–1496

(CSBO) 1,4-BDA 3h – 4.71 131 59 19.3 40.1

1,6-HDA – 3.80 189 47 22.5 35.3
Carbonated soybean oil MXDA I step: 70 C, 6 h II step: 100 C, – 5.5 154 80 20.7 40.7 [55]
(CSBO) PXDA 15 h – 11.1 129 95 24.2 41.1
IPDA – 7.1 150 98 26.1 44.6
Carbonated soybean oil 1,2-EDA I step: 70 C, 10 h II step: 100 C, 4 6 240 – – 20 [56]
(CSO) 1,4-BDA 3h 2 2 310 – – 17
IPDA 20 5 200 – – 40
Carbonated linseed oil 1,2-EDA I step: 70 C, 10 h II step: 100 C, 180 18 57 – – 55 [56]
(CLO) 1,4-BDA 3h 300 17 84 – – 45
IPDA 1460 10 1 – – 60

Em tensile modulus, dm tensile strength, eb elongation at break, H hardness determined by Shore method, Tg DSC glass transition temperature determined by DSC method,
Tg DMA glass transition temperature determined by DMA method
1487

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polyurethanes obtained using CLBO exhibited higher tensile strength, tensile

modulus and glass transition temperature than in case of CLSO-based NIPUs. This
fact is connected to higher cyclic carbonate content in the structure of carbonated
linseed oil, which resulted in higher cross-link density and higher reduction of
polyurethane chains mobility. The improvement of tensile strength and modulus is
connected with decrease of elongation at break. It was also found that using the
mixture CLBO/CSBO (in different wt%, e.g. 20/80, 33/67, 50/50) for preparing
NIPUs by curing with 1,2-EDA, 1,4-BDA and IPDA resulted in obtaining bio-based
polyurethanes, which possess intermediate tensile properties and glass transition
temperature between CLBO- and CSBO-based NIPUs [54–56].
The non-isocyanate polyurethanes obtained from carbonated vegetable oils are
the most environmental friendly polymers described in this review. It resulted from
(1) solvent-free method synthesis of semi-products and final products, (2) fixation of
CO2 during the synthesis of cyclic carbonate intermediates, and (3) using natural
and renewable substances (i.e. vegetable oils) as a starting molecules for synthesis
of semi-products.
Table 10 presents synthesis conditions and properties of non-isocyanate
polyurethanes obtained from carbonated internal and terminal carbonated fatty
acid derivatives. Synthesis of the presented NIPUs was realized by non-solvent
method. It is evident that the application of TCFAD possesses higher reactivity
(higher molecular weights of NIPUs connected with shorter time of reaction) than
ICFAD, which resulted from its chemical structure. The glass transition temper-
atures were lower in the case of ICFAD, which is connected with the presence of
additional pendant alkyl chains (C8H17), which can act as plasticizers. Moreover,
lower Mw of ICFAD-based NIPUs can also caused lower Tg than in case of TCFAD-
based NIPUs [46]. The glass transition temperature in the case of isocyanate-free
poly(hydroxyurethane-amide)s is strongly affected by the type of used diamine, and
Tg decreasing in order IPDA [ PRIAMINE-1075 [ JEFFAMINE-400. This trend
resulted from the rigid cycloaliphatic structure of IPDA, long alkyl backbones
(which can acts as plasticizers) in the case of PRIAMINE-1075, and flexible
polyether nature of JEFFAMINE-400.

Non-isocyanate polyurethanes based on cyclic carbonate intermediates

obtained by thiol-ene coupling reactions

Table 11 shows the synthesis conditions and properties of non-isocyanate

polyurethanes prepared from cyclic carbonates (obtained by thiol-ene coupling)
and diamines or polyamines. Curing of two different cyclic carbonates bis(VD)-
OETH and bis(AOD)-OETH using long chain aliphatic diamines 1,10-DDA showed
that longer chain of cyclic carbonate intermediate (and the presence of ether bond in
the structure) resulted in increasing of thermal stability of NIPUs and decreasing of
glass transition temperature, which is connected with higher flexibility of polymer
chains [67]. On the other hand, this method has some disadvantages from the
environmental point of view. Synthesis realized in this way generates demand for
synthetic solvents which are used as a reaction medium and also as a purifaction
agents.

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 Table 10 Synthesis and properties of non-isocyanate polyurethanes obtained from carbonated internal and terminal carbonated fatty acid diesters
Cyclic carbonate component Diamine Reaction conditions Mn (g mol-1) PD (Mw/Mn) Tg DSC (C) References

Internal carbonated fatty acid diesters (ICFAD) IPDA 70 C, 20 h 9100 1.3 -21 [46]
110 C, 12 h 11,700 1.4 -19
Terminal carbonated fatty acid diesters (TCFAD) 70 C, 12 h 10,700 1.4 -16
110 C, 9 h 13,500 1.5 -13
Polym. Bull. (2016) 73:1459–1496

Fatty acid-based bis-cyclic carbonate (linker: 1,3-propanediol) 1,4-BDA 70 C, 1 day 25,400 1.6 -17 [47]
UndPdE-b5CC
Fatty acid-based bis-cyclic carbonate (linker: butane-1,4- IPDA 140 C, 13 day 18,900 2.4 40
diamine) UndBdA-b5CC JEFFAMINE-400 140 C, 6 day 20,900 2.6 -21
PRIAMINE 1075 140 C, 6 day – – 2
Fatty acid-based bis-cyclic carbonate (linker: piperazine) IPDA 140 C, 6 day – – 55
UndPipdA-b5CC JEFFAMINE-400 140 C, 1 day – – -15
PRIAMINE 1075 140 C, 6 day 19,200 1.7 -2
Fatty acid-based bis-cyclic carbonate (linker: N,N0 - IPDA 120 C, 6 day – – 32
dimethylpropane -1,3-diamine) UndPMedA-b5CC JEFFAMINE-400 120 C, 6 day 20,700 1.4 -17
PRIAMINE 1075 120 C, 1 day -4
Fatty acid-based bis-cyclic carbonate (linker: N,N0 - 1,4-BDA 120 C, 1 day – – -13
dihexyldecane-1,10-diamine) UndDHexdA-b5CC IPDA 120 C, 6 day – – 3
JEFFAMINE-400 120 C, 6 day – – -29
PRIAMINE 1075 120 C, 1 day – – -18

Synthesis of NIPUs was realized by non-solvent method

Mn number average molecular weight, Mw weight average molecular weight, PD polydispersity, Tg DSC glass transition temperature determined by DSC method
1489

123
 1490

123
Table 11 Synthesis and properties of non-isocyanate polyurethanes prepared from cyclic carbonates (obtained by thiol-ene coupling) and diamines or polyamines
Cyclic carbonate obtained by Amine or mixture Reaction Mn (g mol-1) PD (Mw/Mn) Tg DSC (C) Td 5 % (C) References
thiol-ene couplinga of amines conditionsc

bis(VD)-OETH 1,10-DDA DMF, N2, 75 C, 48 h 7000 1.5 -14 227 [67]
bis(AOD)-OETH 1,10-DDA DMF, N2, 75 C, 48 h 9000 3.2 -31 249 [67]
bis(BD)-EDTH DODDA DMAc, 50 C, 336 h 15,000 n.s. n.s. n.s. [34]
bis(VD)-HDTH DETA 80 C, 24 h n.s. n.s. 5 217 [26]
1,6-HDA ? DETA (10 mol %)b 80 C, 24 h n.s. n.s. -1 230
1,6-HDA ? DETA (24 mol %)b 80 C, 24 h n.s. n.s. 7 231
tris(VD)-TMPTMP DETA 80 C, 24 h n.s. n.s. 16 193 [26]
tetra(VD)-PERTMP DETA 80 C, 24 h n.s. n.s. 16 186 [26]

Mn number average molecular weight, Mw weight average molecular weight, PD polydispersity, Tg DSC glass transition temperature determined by DSC method, Td 5 %
temperature at which 5 % weight loss of sample occurred (by TGA method)
a
The structure of abbreviated cyclic carbonates obtained by thiol-ene coupling are presented in the Fig. 13
b
Mole ratio of DETA to cyclic carbonate
c
Solvents: N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc)
Polym. Bull. (2016) 73:1459–1496
Polym. Bull. (2016) 73:1459–1496 1491

In the case of polyurethanes obtained by reaction of bis(VD)-HDHT, tris(VD)-

TMPTMP or tetra(VD)-PERTMP with polyamine DETA (with two primary –NH2
groups) is visible that, with increasing content of cyclic carbonate groups the glass
transition temperature increasing, which resulted from higher cross-link density and
reduction of polymer chains mobility. The thermal stability decreases with
increasing content of C-S bonds (connected with increasing content of cyclic
carbonate groups) in the structure of NIPUs. It was found that curing of bis(VD)-
HDHT with mixture 1,6-HDA/DETA resulted in decreasing of thermal stability and
also affects the glass transition temperature of prepared polyurethanes [26].
Moreover, synthesis of NIPUs from bis(VD)-HDHT, tris(VD)-TMPTMP and
tetra(VD)-PERTMP is realized by solvent-free method, which is more beneficial
from the environmental point of view.
The comparison of NIPU systems obtained from bis(cyclic carbonate)s, i.e.
bis(VD)-OETH/1,10-DDA, bis(AOD)-OETH and bis(VD)-HDTH/DETA, showed
that the higher thermal stability of obtained polymers is affected by the presence of
ether groups in the structure of substrates for thiol-ene coupling reaction, which on
the other hand resulted in more flexible structure of obtained NIPUs and its lower
glass transition temperature [26, 67].

Conclusions

One of the non-isocyanate polyurethane synthesis methods is realized by reacting

cyclic carbonates intermediates with diamines or polyamines. The cyclic carbonates
intermediate can be obtained by (1) catalytic reaction of glycidyl ethers with carbon
dioxide (2) thiol-ene coupling, which include reaction between dithiol and cyclic
carbonate monomer with unsaturated C=C bond at the end of side chain.
Unfortunately, some of the methods presented in the literature include application
of synthetic solvents as a reaction medium and purification agent. From
technological point of view, it generates additional cost. Moreover, it is well
known that synthesis of polymers in solvent generally resulted in obtaining
unsatisfactory molecular weights of final polymeric products.
In the case of catalytic conversion of epoxides using CO2, special interest is
focussed on carbonation of epoxidized bio-based substances, e.g. vegetable oils,
limonene or glycerol. The usage of carbonated vegetable oils allows to obtain high
bio-based content NIPUs. The application of bio-based and renewable feedstock in
the synthesis of polyurethanes is connected with actual trends of green chemistry
and makes the material more environmental friendly. Moreover, synthesis of NIPU
from, e.g. carbonated vegetable oils, is a solvent-free method, which is the next
benefit from the environmental point of view. Fixation of carbon dioxide during the
synthesis of carbonated intermediates is also ecological advantage of those
materials.
The review of literature in the context of structure–properties relationship of non-
isocyanate polyurethanes obtained by reacting cyclic carbonate intermediates
permits to formulate following conclusions:

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1492 Polym. Bull. (2016) 73:1459–1496

• Longer aliphatic carbon chains introduced to NIPUs structure by applied

diamines are connected with higher reduction of glass transition temperature,
which resulted from higher mobility of polymer chains due to the presence of
long aliphatic chains in structure of amine curing agent. The improvement of
thermal stability is also affected by the presence of longer aliphatic chains by
diamines.
• Cyclic carbonate intermediates cured with isophorone diamine resulted in
obtaining polyurethanes that exhibited lower tensile strength and elongation at
break, but higher tensile modulus and glass transition temperature than in curing
with aliphatic diamines, i.e. 1,2-ethanediamine and 1,4-butanediamine. This fact
resulted from rigid structure of isophorone diamine.
• The increase of cyclic carbonate group content in the structure of intermediates
for the synthesis of NIPUs results in improvement of polyurethanes stiffness.
This effect can be strengthened by the application of curing agents mixture
consisting of diamines (e.g. 1,6-hexanediamine) with triamines (e.g. citric acid
1,6-hexamethylene amino amides).
• The increase of glass transition temperature of NIPUs is also related to increase
of cyclic carbonate group content, which resulted in the reduction of polymer
chains mobility due to higher cross-link density of prepared NIPUs network. The
increase of glass transition temperature is also affected by the presence of
aromatic rings in the structure.
• Curing of carbonated vegetable oils should be conducted at optimal molar ratio
of carbonate to diamines, and it is equal to 1:1, because obtained at this ratio
NIPUs exhibited the highest tensile strength, hardness and glass transition
temperatures, which indicate the higher cross-link density. The molar ratio 1:0.5
resulted in incomplete cross-linking, which resulted in decreasing of tensile
properties and glass transition temperature, when the molar ratio 1:2 caused
aminolysis of ester groups and formation of amide groups.
• Higher cyclic carbonate content in the structure of CLO resulted in higher cross-
link density and higher reduction of polyurethane chains mobility than in the
case of CSBO. The improvement of tensile strength and modulus is connected
with the decrease of elongation at break. The use of the CLO/CSO mixture
resulted in obtaining NIPUs, which possess intermediate tensile properties and
glass transition temperature between CLO-and CSO-based NIPUs.
• In the case of NIPUs based on cyclic carbonate intermediates obtained by thiol-
ene coupling, the higher thermal stability of obtained polymers is affected by the
presence of ether groups in the structure of substrates for thiol-ene coupling
reaction, which on the other hand resulted in more flexible structure of obtained
NIPUs and its lower glass transition temperature.

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