Accepted Manuscript

A Perspective Approach to Sustainable Routes for Non-Isocyanate Polyur-

ethanes

Adrien Cornille, Rémi Auvergne, Oleg Figovsky, Bernard Boutevin, Sylvain

Caillol

PII: S0014-3057(16)31359-3
DOI: http://dx.doi.org/10.1016/j.eurpolymj.2016.11.027
Reference: EPJ 7619

To appear in: European Polymer Journal

Received Date: 21 October 2016

Revised Date: 19 November 2016
Accepted Date: 22 November 2016

Please cite this article as: Cornille, A., Auvergne, R., Figovsky, O., Boutevin, B., Caillol, S., A Perspective Approach
to Sustainable Routes for Non-Isocyanate Polyurethanes, European Polymer Journal (2016), doi: http://dx.doi.org/
10.1016/j.eurpolymj.2016.11.027

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
 A Perspective Approach to Sustainable Routes for Non-Isocyanate
Polyurethanes

a a b a a*
Adrien Cornille , Rémi Auvergne , Oleg Figovsky , Bernard Boutevin , Sylvain Caillol

a
Institut Charles Gerhardt - UMR 5253 – CNRS, UM, ENSCM, 8 rue de l’Ecole Normale, 34296 Montpellier, France
b
Hybrid coatings technologies, 950 John Dale Boulevard, Daly City, CA94015, USA
*Corresponding author: sylvain.caillol@enscm.fr

Abstract

Sustainable routes for the synthesis of polyurethanes with industrial applications are discussed in this article. Polyurethane
is currently one of the most commonly used polymers worldwide for various applications such as rigid and flexible foams,
coatings, elastomers, adhesives and sealants. However, isocyanate precursors are very harmful at each stages of the life
cycle of the polymers. Hence, new synthesis routes for isocyanate-free polyurethanes are reported in literature, but most of
them suffer from significant lacks that prevent any industrial application. This feature article focuses on the new challenges
and new opportunities of these routes. A first part is dedicated to the market, the manufacture and the hazards of
polyurethanes. In a second part, this article deals with the synthesis routes leading to non-isocyanate polyurethane. Hence,
the advantages and limits of these routes are reported and discussed. Finally the outlooks for a future and industrial use of
non-isocyanate polyurethane in industry are examined.

Keywords

Polyurethane; non-isocyanate polyurethane; hybrid non-isocyanate polyurethane; polyhydroxyurethane; cyclic carbonate

I. Polyurethane, interesting materials for various allowed to obtain flexible polyurethane foams for

applications applications in furnishing and automotive areas.

Nowadays, PUs find applications everywhere in everyday
I.1 Brief history life: furnishing, cars, clothing, shoes, elastomers,
coatings, wall and roofing insulation, etc.
Polyurethanes were invented back in the 1930’s by Otto
[8]
Bayer and coworkers from the works of Wûrtz, who I.2 Polyurethane market
discovered in 1849 the reaction between alcohol and
isocyanate yielding urethane (carbamate) groups. These The value chain of polyurethanes involves three key

polymers were developed to obtain materials with players. The first ones are the industrial chemists that

properties similar than polyamide fibers (nylon) produce the raw materials for the synthesis of polymers.

discovered earlier but protected by American patents. The second players are the formulators that produce

The versatility of polyurethanes, and their ability to polyurethanes from raw materials; and the last ones are

substitute to other materials, stimulated the assemblers, who include polyurethanes in their final

development of numerous applications. Around mid- products. The economic players are involved in one, two

50’s, polyurethanes (PUs) found applications in coatings, or these three sectors. In 2016, with a global production

adhesives, elastomers and rigid foams. In the next years, of 18 Mt, PUs rank 6th among all polymers based on

the development of polyether polyols at low cost annual worldwide production. The major part of this

1
 [2]
production is performed in Asia with around 8 Mt, then a two-step process (Scheme 1) . The first step
in Europe with around 4 Mt and finally in the United corresponds to the reaction between a polyol and an
States of America with around 3 Mt. The global market excess of diisocyanate which yields a polyurethane
of polyurethane is valuated around 53 billion euros and prepolymer with NCO end-groups. The second step
the five first Companies, BASF, Bayer, Dow, Huntsman consists in the reaction of this prepolymer with another
and Yantai Wanhua, account for over 35% share of the polyol as chain extender or crosslinking agent. This two-
total market. step process allows to circumvent the difference of
reactivity between polyols and consequently to improve
I.3 Polyurethane properties
the material properties. The resulting polyurethanes
then composed of soft and rigid segments.
Due to the diversity of isocyanates and polyols, various
polyurethanes can be synthesized, therefore the term
I.5 Hazards of polyurethanes synthesis
"polyurethane" represents actually an important range
of products with different macromolecular structures. Environmental impacts of chemical substances are
The polyurethane market is segmented in three large evaluated through three stages of life cycle of a polymer:
product families: flexible foams, rigid foams and non- during the synthesis of the monomers; during the
porous materials. This classification corresponds to PU polymerization and at the end of life of materials. Hence,
density and rigidity. The non-porous PUs find polyurethanes present hazards at these three stages.
applications in coatings, adhesives, sealants, elastomers
Firstly, the synthesis of isocyanates requires the use of
and binders. Polyurethane RIMs are materials obtained
phosgene, which is a lethal gas, to convert amines into
by Reaction-
isocyanates. Moreover, the two most widely used
Injection-Molding and consist of poly (urethane-urea) isocyanates in PU industry, MDI (methylene diphenyl
copolymers. The rigid foams are mainly used as diisocyanate) and TDI (Toluene diisocyanate), are
insulation panels for building, fridge-freezer while the classified as CMR (Carcinogenic, Mutagenic and
[3-5]
flexible foams find applications in mattresses, seats, Reprotoxic) . These substances have harmful effects
sofas, automotive … on human and environment. Prolonged exposure to
them presents dramatic health risks such as asthma,
I.4 Polyurethane manufacture [5, 6]
dermatitis, conjunctives and acute poisoning . In
conjunction with these serious health concerns, the
Currently, most of the polyurethanes are synthesized by
environmental regulations limit or banish the use of
some isocyanates [3]. Finally, at their end of life, PUs are
either burnt or put into landfills. However, during
combustion, polyurethanes are degraded and release
isocyanates that decompose mainly in HCN, a poisonous
[7-10]
substance . In the landfills, polyurethanes undergo
hydrolysis reaction that yields toxic amines. To
summarize, polyurethanes exhibit hazards during their
whole life cycle, mainly due to the presence of harmful
precursors such as isocyanates and phosgene. Therefore,
in Europe, with REACH regulation, isocyanates will be
Figure 1: Properties of polyurethane range [1] progressively banned [3]
. Therefore, this context urges
the development of isocyanate-free polyurethane. Thus,

2
Scheme 1: Synthesis of polyurethane in a two-step process

considerable works were reported in literature on the II.2 Synthesis routes to isocyanate-free
synthesis of isocyanate-free polyurethanes, but until polyurethanes
now, the various technologies that were proposed have
pros and cons and none of them was chosen and For the past several years, NIPUs have gained a great

developed by industry. The objective of this article is to deal of attention in scientific community. Literature

summarize the state of the art and to propose, for the reports four synthesis routes: polycondensation,

first time, a perspective approach for the choice of a rearrangement, ring-opening-polymerization and

sustainable route to isocyanate-free polyurethanes, polyaddition. All these routes are summarized in Scheme

based on industrial expectations and scientific 2. Recently, some interesting reviews dedicated to the
[11-16]
challenges. synthesis of NIPU were published and provided a
complete overview of all these methods. Among
II. Substitution of isocyanates in polyurethanes polycondensation routes, we can find the reactions
between polychloroformate and polyamine,
II.1 Nomenclature
polycarbamate and polyol by transurethanization,

In the literature, several names are given to isocyanate- polycarbamoyl chloride and polyol, and polycarbonate

free polyurethanes: NIPU, PHU, H-NIPU. Therefore, and polyamine. Nevertheless, these routes require the

nomenclature should be defined for the rest of this use of phosgene or derivatives for the synthesis of

article. The name NIPU (Non-Isocyanate PolyUrethane) precursors. Moreover, during polycondensation, side-

corresponds to the generic name of isocyanate-free products, such as HCl or alcohols, are released, which is

polyurethanes. Among the NIPUs, the PHUs a significant limitation to industrial applications. Another

(PolyHydroxyUrethane) are a kind of NIPUs obtained by polycondensation route consists in the reaction between

reaction between cyclic carbonates and amines that polycarbamate and polyaldehyde. This reaction seems

yields hydroxyurethane repeating units. Finally, recently, interesting but this route, yet little studied, entails also

the new terms HUM (Hydroxy Urethane Modifier) and H- the release of water during polymerization [17].

NIPU (Hybrid Non-Isocyanate PolyUrethane) emerged in

The synthesis of NIPUs by rearrangement of acyl azides
the literature in order to describe respectively
(Curtius rearrangement), carboxamides (Hoffman
monomers and co-polymers of NIPU with other
rearrangement) or hydroxamic azides (Lossen
polymers such as polyacrylates or polyepoxides. [18-26]
rearrangement) are also described in literature .
During these rearrangements, isocyanates are produced

3
Scheme 2: NIPU routes

in-situ, hence in presence of alcohols, polyurethanes are due to the presence of both primary and secondary
synthesized. These routes also use isocyanates, even if hydroxyl groups hanging off the main polymer chain.
they are produced in-situ, but more important, the Hence, the structure of PHUs differs from classical PUs.
reactants such as acyl azides, carboxamides and Moreover, the presence of these hydroxyl groups has an
hydroxamic azides, are very harmful substances. influence on the properties of polymers. Indeed, these
hydroxyl groups could participate to intra- and inter-
The third way for the synthesis of NIPUs is the ring
molecular hydrogen bonds with carbamate groups,
opening polymerization of aliphatic cyclic carbamates [27-
allowing improved chemical resistance to nonpolar
31] [32-34]
or aziridines . Although these NIPUs are [12, 35]
solvents . This reaction has been studied for 60
synthesized without any release of side-products, these [36]
years. The first patents were obtained in the 1950’s .
reactions are often performed at high temperature and [37]
Very recently, Figovsky et al. proposed a
the cyclic carbamates are generally produced from
comprehensive list of PHU patents showing the huge
phosgene. The toxicity of aziridines remains also a
interest of industrial Companies for these emerging
significant issue.
PHUs. However, the authors disagree on the thermal

Finally, the last synthesis pathway leading to NIPU is the stability of PHUs compared to classical PUs. Some

polyaddition of cyclic carbonates and amines. This authors claim a higher thermal stability thanks to the
[12,
reaction seems the best route for the synthesis of NIPU extra hydrogen bonds created with hydroxyl groups
35]
since it avoids the use of isocyanate and phosgene. but other authors report a lower thermal stability due

Moreover, the cyclic carbonates are not toxic, they are to the influence of hydroxyl groups on the polymer

non-moisture sensitive like isocyanates that lead to side stability [10, 38]. This is also the case for water absorption
[39]
products such as urea and CO2. Therefore their storage properties. Indeed, Nohra et al. described in their

does not require any particular caution [12]. Furthermore, works a lower water absorption of PHU compared to
[40]
the reaction between cyclic carbonates and amines does classical PU whereas Tomita et al. reported opposite

not release any volatile organic compound which allows results. Finally, one of the main advantages of PHUs is

the use of this route for coating applications [11]

. The the possibility to post-functionalize the hydroxyl groups

resulting polymer is called poly(hydroxyurethane) PHU

4
 [36, 59-75]
hanging off the chain with chemical and biological Paint, Wacker also recently filed patent
[41]
functionalities . applications in this field. All these international actors
(academic and industrial) work in order to increase both
To summarize, among the numerous pathways leading
the reactivity of cyclic carbonate/amine reaction and the
to NIPUs, the polyaddition of cyclic carbonates with
molar masses of PHUs. The rest of this article is focused
amines seems to be the most interesting route.
on the methods to improve this PHU technology and the
Moreover, the list of publications, reviews and patents
perspective applications of PHUs.
found in literature confirms the large interest of both
scientific and industrial communities for this technology. II.3 The stakes of the reactivity of cyclic
However, this route displays two major drawbacks: the carbonates / amines reaction
low reactivity of reaction between cyclic carbonates and
amines, and a limited degree of advancement of A 3-step mechanism of the ring opening of cyclic

reaction during the room temperature polymerization carbonate by amine was proposed by Garipov et al. [76] in

that leads to low molar mass PHUs. Considerable works 2003 (Scheme 3). The first step of the reaction consists

were carried out in different research laboratories in in the nucleophilic attack of the amine on the carbonyl

Europe (in France, the Universities of Bordeaux, of carbonate which yields a tetrahedral intermediate,

Toulouse, Strasbourg, Rennes; in Belgium, the University and is considered as the limiting step of the reaction. In

of Liège, Mons…; in Germany, the Universities of the second step, a second amine entails the

Freiburg, Aachen, Karlsruhe…), Asia (Kinki University…) deprotonation of the tetrahedral intermediate. In the

and America (University of North Dakota State…) to third step, the significant electron density initiates the

circumvent the limitations of this reaction. Moreover, rupture of the carbon-oxygen bond which yields the

the main industrial actors of PUs such as BASF, DOW and hydroxyurethane. However, depending on the geometry

Huntsman [42-58]
pay serious attention to this technology of intermediate molecules, the opening reaction leads to

to produce PHU or H-NIPU. Furthermore, PPG, Solvay, the production of repeating units with primary or

Henkel, Polymate, American Cyanamid, Hoechst, Kansai secondary alcohols.

Scheme 3: Mechanism of cyclic carbonate/amine reaction

5
 [77]
Generally, secondary alcohols are favored . syntheses of 5-, 6-, and 7-membered cyclic carbonates
[78]
Steblyanko et al. explained this selectivity since were summarized in literature [40, 77, 85, 86]. In 2001, Endo
[85]
secondary alcohols present a lower energy potential. et al. compared the reactivity of these carbonates
From the mechanism described in Scheme 3, several respectively noted CC5, CC6 and CC7. Their works
parameters can influence the reactivity, including the revealed the reactivity order of cyclic carbonate with
nature of solvent, the carbonate structure and the aliphatic amines according to their structure:
substituents, the structure of amine and the catalysis of CC5<CC6<CC7. The corresponding speed constants (k in
-1
reaction. L.mol ) are 0.02, 1.19 and 48.5 respectively. Ochia et al.
[80]
observed the same reactivity order between CC5 and
II.3.1 Influence of solvent on the cyclic
CC6. They attributed this difference of reactivity to a
carbonate/amine reaction
stronger ring strain in the case of CC6 compared to CC5.
[82]
The solvent (polarity) used for the reaction has an Lamarzelle et al. showed (Figure 3-A) the difference

influence on the kinetics of mechanism [76]

(Scheme 3). of reactivity between CC5 (blue curve) and CC6 (red
[86]
In aprotic solvents, the first step is the limiting step of curve) with the same substituent. He et al.

reaction. The global order of the cyclic carbonate/amine synthesized a biscyclic carbonate containing both CC5

reaction is 2 [77, 79-84]

. However, the first step is more and CC6. After reaction with one equivalent of

rapid in protic solvents. Indeed, the positive charge on monoamine, the conversion of CC6 was quasi-

carbonyl carbonate increases due to hydrogen bonds quantitative which proved, once again, the high

between solvent molecules and oxygen atoms of cyclic reactivity of CC6 compared to CC5. Finally, very recently,
[87]
carbonate (Figure 2). Therefore, in this case, the second Yen et al. synthesized the first 8-membered cyclic

step which corresponds to the deprotonation of carbonate (CC8) and compared its reactivity with CC5

tetrahedral intermediary is the limiting step. and CC6. Their results confirm the previous works: the
CC8 is more reactive than CC5 and CC6. Therefore, the
This phenomenon is interesting to increase the kinetic reactivity of ring opening reaction increases with the
reaction but most the polyurethanes are formulated in number of members of the cyclic carbonate.
bulk. Therefore, most of the researches concerning PHUs
are focused on the influence of cyclic carbonate and However, the preparation of highly reactive cyclic

amine structures on kinetics of reaction and on catalysis. carbonates (CC6, CC7 and CC8) involves phosgene or its
derivatives (ethylchloroformate) which are harmful
II.3.2 Influence of the structure of cyclic carbonate reactants [77, 79, 85, 86, 88]
. Other works presented the
[89, 90]
preparation of CC6 by carbonation of oxetanes or
The cyclic carbonate size plays a preponderant role on
[91]
halohydrins but the reaction yields depend strongly
the cyclic carbonate/amine kinetics of reaction. Actually,
on the structure of precursors and on catalysts.

Despite their low reactivity compared to CC6, CC7 and

CC8, the CC5 cyclic carbonates and their synthesis have
been extensively studied. Hence, the CC5 can be
[92, 93]
obtained from linear oligocarbonates , diols (with
[40, 77, 94-107] [42, 91]
numerous precursors) , halohydrines
[108, 109] [110]
Figure 2: Increasing of electrophilicity of cyclic carbonate olefins , substituted propargyl , halogenated
[111, 112]
in presence of protic solvent carbonates . Moreover, the modification of
epoxydized compounds with β-butyrolactone [113] can be
used to produce CC5. However, the most interesting

6
route for the synthesis of CC5 is the carbonation of suspected of damaging fertility which restricts its use in
[114-117]
epoxides in presence of CO2 . This method industry.
presents numerous advantages; Indeed, the use of CO2 is
To summarize, CC6, CC7, CC8 and CC5S cyclic carbonates
beneficial regarding both the economic and
[118] are more reactive that C5. However, their syntheses with
environmental points of view . CC5 are synthesized
high yield need harmful precursors such as phosgene,
with high yields [10, 119, 120] and the CO2 can be used both
[121] ethylchloroformate or CS2 that should be banned in a
as an aprotic solvent and reagent . These
consistent approach to sustainable polyurethanes.
particularities explains the growing interest of
Therefore, only CC5 cyclic carbonate can be prepared
researchers to produce PHU from CC5 compared to CC6,
with safe and economical process (carbonation of
CC7 or CC8. Finally, CC5 monomers could be synthesized
epoxide groups or from glycerol). However, if the
directly from commercial biobased glycerol carbonate
nucleophilic attack of amine on CC5 is relatively slow,
which entails great interest in the scientific community
[122-124] several research groups worked on the influence of
.
substituent groups on the CC5 reactivity.
Among CC5, cyclic dithiocarbonates noted CC5S, are also
II.3.3 Influence of substituents on CC5 reactivity
highly reactive carbonates [125]. Their aminolysis reaction
leads to Poly(ThioUrethane) (PTU) with thiol groups Garipov et al. [76]
demonstrated that the electron-
[126, 127]
hanging off the main chain instead of hydroxyl withdrawing substituents (-I) increase the electophilicity
groups. Indeed, the leaving ability of thiol is higher than of carbonyl and, therefore, enable nucleophilic attack of
[128]
alcohol in a nucleophilic substitution reaction . CC5S the amine. Conversely, electron-donor substituents (+I)
are directly synthesized by reaction between the disfavor the opening of cyclic carbonate by the amine.
corresponding epoxy precursors and carbon disulfide Lamarzelle et al. [82]
and Tomita et al. [79]
studied the
(CS2) in the presence of catalyst such as neutral metal influence of the substituents on cyclic carbonate
[129-131]
halides (LiBr) . Moreover, CS2 reacts at room reactivity and obtained results in agreement with those
temperature with epoxy precursor, whereas addition of of Garipov et al. [76] (Figure 3).
carbon dioxide needs a thermal activation. However, CS2
is a very toxic substance, is very flammable and

Figure 3: Time-conversion curves in the reaction with (A) CC5 or CC6 carrier of different substituents (Aliphatic, Ether or
-1
Ester) and hexylamine at 50°C, 1 mol.L in DMO-d6 [82] and (B) CC5 carrier of different substituents and hexylamine at 70°C, 1
mol.L-1 in DMSO-d6 [79]

7
 [79] [50, 54]
Tomita et al. reported the following reactivity order: agents . The double bond on CC5 is an electron-
R=Me<H<Ph<CH2OH<CF3 (Figure 3-B). CF3 is a promising withdrawing groups which increases the reactivity of
substituent which allows a quantitative conversion of CC5. In order to increase the reactivity of CC5,
CC5. Nevertheless, no work has been published on the researches were conducted to graft activating groups on
synthesis of PHU from fluorinated CC5. These curves CC5 (CF3, ester, double bonds). However, the results
show also the limited advancement of reaction despite reported in different works and patents proposed the
elevated temperature. Such results are reported in activation with ether group. Indeed, the ether-CC5 is
[77, 85, 132, 133]
numerous publications and are a real easier to synthesize by direct carbonation of ether-
drawback of the PHU: low molar masses due to non- epoxides and doesn’t lead to side-reactions. Therefore,
quantitative reaction. This point will be discussed later in the rest of this article will be dedicated to the study of
the part dedicated to molar masses of PHUs. the influence of amine and catalyst on the synthesis of
PHUs from ether-CC5.
[82]
Lamarzelle et al. showed that CC5 with ester
substituent exhibits a similar reactivity than CC6 in II.3.4 Influence of the structure of amine
model reactions with amine and a higher reactivity than
[134]
Lots of authors, such as Diakoumakos et al. , studied
CC5 with alkyl or ether substituents Figure 3-A).
the model reaction at room temperature between ether-
However, amidification side-reaction could occur on
CC5, and different amines. Their works showed that the
ester group, leading to side-products and reducing the
structure of amines has a strong influence on reactivity
molar mass.
(Scheme 4). Firstly, aromatic primary amine and
Moreover, He et al. [81] modified the position of electron- secondary amine are non-reactive at room temperature.
donor groups on CC5. They showed that more the Concerning primary amines, the main parameters are
electron-donor substituent is far from carbonyl group their nucleophilicity and size. Indeed, the more the
and slower is the reaction. Finally, BASF company filed a amine is nucleophile, the higher is its reactivity [76, 77, 135,
136] [134]
patent application on the synthesis of a CC5 with double . Furthermore, Diakoumakos et al. showed that
bonds and its use as reactive diluent for polyepoxide some groups increase significantly the reactivity of the
formulations of H-NIPU with epoxides and amino curing

Scheme 4: Reactivity of various amines toward ether-CC5 at room temperature [134]

8
amine: electron-withdrawing groups at α and β position Different kinds of catalysts activate the aminolysis
or imino and amino groups (polyamines). These results reaction by one of these three mechanisms: Lewis acids
were confirmed by Webster et al. [135]. Tabushi et al. [137] [140-148]
, bases [149-151], phosphoric acids [152, 153], carbenes
[150, 151, 154-158] [159] [160, 161]
showed that primary amines attached to a primary , phosphines , enzymes ,
[148, 150, 151, 155, 162-164] [151, 155, 157,
carbon reacts more rapidly than primary amines guanidines and thioureas
[138] 165-169] [164]
attached to a secondary carbon. Nohra et al. varied . Among all these catalysts, Lambeth et al.
the alkyl chain length of aliphatic amine and showed the showed that 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)
decrease of amine reactivity with the increase of the and phenylcyclohexyl thiourea allowed to increase
alkyl chain length. significantly the kinetics of aminolysis reaction. These
[170, 171]
results were confirmed by Blain et al. . Indeed,
Hence, the most reactive amines are primary aliphatic
these studies show that among all catalysts tested, the
amines attached to a primary carbon with electron-
thiourea and the TBD (Figure 4) are the most effective
withdrawing groups at α or β position.
catalysts for cyclic carbonate aminolysis.

II.3.5 Catalyst of cyclic carbonate/amine reaction

II.4 Influence of reaction parameters on PHU
Cyclic carbonate could react at room temperature with molar masses
the most reactive amines. Kinetics studies showed that
[136, 138] Lots of works report the limitations of molar masses of
elevated temperatures activate the reaction and
thermoplastic PHUs. In most of the cases, molar masses
allow the reaction with weakly reactive amines (aromatic
are determined by Size Exclusion Chromatography (
or sterically hindered). However, high temperature can
or . Therefore, in order to compare molar masses,
lead to side-reaction and formation of side-products,
[82, 136, 139] same conditions must be applied (eluent, columns and
such as ureas . If the reactivity is low at room
calibration standards). Most of the authors use DMF
temperature, it could be increased with the use of
with LiBr as eluent and Polystyrene (PS) standards, but
catalysts. There are three ways to catalyze the
some of them use other conditions such as THF as eluent
aminolysis of cyclic carbonate (Scheme 5): the increase
and PS standards or DMF with Polymethylmethacrylate
of electrophily of carbonyl of cyclic carbonate; the
standards or DMAC with LiCl and PS standards.
increase of nucleophilicity of amine and the opening of
[14]
Maisonneuve et al. summarized the study of
cyclic carbonate with a nucleophilic catalyst.
thermoplastic PHU molar masses in their review. Among
the parameters that influence the molar masses are

Scheme 5: Different catalytic mechanisms of cyclic carbonate aminolysis

9
 [177-179]
ammonium cation (Scheme 6-2) that reduces the
amine concentration.

[180]
Secondly, Huntsman Company reports the
production of in-situ CO2 when the amine attacks on α
Figure 4: Structure of TBD and thiourea catalysts position of the urethane function, yielding a
reported the solvent [172, 173], the structure of monomers hydroxyalkylamine with release of CO2 (Scheme 6-3). The
[40, 78, 82, 174, 175]
and the catalyst [132, 143, 164]
. Moreover, production of in-situ CO2 can also lead to the
thetemperature plays also an important role. Indeed, in carbonation of amine, reducing its availability for
the reviews of Maisonneuve et al. [14]
and Rokicki et al. aminolysis.
[13]
, no thermoplastic PHU was synthesized with high
Thirdly, the trans-urethanization reaction corresponds to
molar masses at room temperature by polyaddition of
the production of non-reactive urea by nucleophilic
CC5 and diamine. This is probably due to the limitation
attack of amine on carbamate groups (Scheme 6-4). This
of advancement of reaction that leads to low molar [139, 170, 181,
reaction was reported in several publications
masses, in agreement with Carothers theory. Indeed, 182]
but was observed for temperatures higher than
numerous model studies show only a partial reaction, [170]
100°C or in presence of catalyst such as TBD .
despite a high reactivity at the beginning [77, 79, 85, 132, 133].
Furthermore, in the case of aminolysis of ester-CC5, an
Two parameters can explain this phenomenon. The first
amidification reaction could occur between amine and
one is linked to a problem of diffusion of monomers
ester (Scheme 6-5). This reaction was reported by
during the polymerization. Indeed, during polyaddition
Lamarzelle et al. [82] and Besse et al. [139].
of cyclic carbonates and amines, the viscosity increases
with the polymer content. This is an important Finally, the production of oxazolidinone was reported by
phenomenon in which are involved the hydrogen bonds Clements et al. [183]
and Besse et al. [139]
(Scheme 6-6).
[176]
created with carbamate groups . Proempers et al. This side reaction was observed only on glycerol

[173]
carbonate at 80°C without catalyst.
reported the polyaddition of non-activated bis-cyclic
carbonate (3,4-isopropylidene-D-manitol-1,2:5,6- Despite the interest of PHUs, the literature shows the
dicarbonate) with hexamethylene diamine at different limitations of molar masses obtained by cyclic carbonate
temperatures in THF. The molar masses ( ) of PHUs aminolysis at room temperature. The next section will
-1 -1
were 7 kg.mol at 25°C and 17 kg.mol at 65°C. The focus on solutions that could help to increase the molar
increase of the temperature allows to decrease the masses of synthesized PHUs, and on the interesting
viscosity, and to increase the mobility, and thus the properties that could obtained thereof and guide their
advancement of reaction and the molar masses. applications.

The second parameter that could explain the limitation III. Outlooks for PHUs synthesis and applications
of the reaction is a difference of stoichiometry between
the monomers consumed by side reactions such as It is obvious from the present article that considerable

amine carbonation, in-situ CO2 production, urea effort has been made during the last years to develop

synthesis, amidification reaction or oxazolidinone environmentally friendly processes to produce

synthesis. All these side reactions are described in isocyanate-free polyurethanes, and particularly at room

Scheme 6. temperature. Hence, the PHU alternative represents a

significant opportunity to replace isocyanate in the
Firstly, the carbonation of amines with CO2 present in synthesis of polyurethanes. Despite a lower reactivity,
the atmosphere leads to a carbamate anion and an the CC5 cyclic carbonate seems the best compromise in

10
Scheme 6: Possible reactions between 5-membered cyclic carbonate and amine: (1) classic aminolysis, (2) carbonation of
amine, (3) CO2-in-situ formation, (4) urea formation by trans-urethanization, (5) amidification reaction and (6)
oxazolidinone formation by dehydration

terms of costs, process, stability and hazards to III.1 Access routes to circumvent PHU limitations
synthesize PHUs. To increase the kinetics of the reaction,
III.1.1 Synthesis of PHU with additives
it is possible to use activated cyclic carbonate, highy
reactive amines and effective catalyst that allow good
The synthesis of PHU at lower temperature can be
reactivity of aminolysis reaction. High temperature
performed with additives that will increase chain
allows sufficient energy to break inter- and intra-
mobility. Firstly, plasticizers such as alcohols or polyols of
molecular interactions, decrease the viscosity and reach
low molar masses (methanol, ethanol, di- or tri-glycerol)
quantitative advancement of reaction and sufficient
could create hydrogen bonding with the PHUs and
molar masses. Hence, PHU elastomers [184], adhesives[185,
reduce the inter- and intra-molecular hydrogen bonds,
186]
, foams[119, 187]
, coatings [188]
, hydrogels [189]
,
and thus increase the mobility of the PHU chains
vitrimers[190] or latexes [191] are examples of applications.
(Scheme 8). A recent study has highlighted the influence
[192]
Moreover, Endo and al. showed that PHUs have
of these plasticizers on the cyclic carbonate aminolysis
interesting gas barrier properties for food and beverage [193]
reaction . Moreover, protic solvents (methanol,
packaging. However, in most of the applications,
ethanol, …) catalyze the cyclic carbonate/amine reaction
polyurethanes are synthesized at room temperature,
as mentioned by Garipov et al. [76].
therefore, this is a real challenge to propose room
temperature routes for the synthesis of PHUs. These Secondly, the use of a blowing agent that entails chains
ways are reported in the rest of this article and are mobility at microscopic scale allows to increase
summarized in Scheme 7. These ways constitute the advancement of reaction at room temperature. This
outlooks for the synthesis of polyurethane at room method demonstrated by our team allowed for the first
temperature for industrial applications in the coming time to obtain quantitative reaction of cyclic carbonate
years. aminolysis at room temperature for the synthesis of
[10]
porous PHUs (Scheme 9). The use of such additives
allows to reach PHUs with high molar masses, that will
find applications in area such as latexes (synthesis in

11
Scheme 7: Outlooks of synthesis routes for PHUs at room temperature and their industrial applications

solvent) or foams (synthesis with blowing agent). In A); the crosslinking of PHU prepolymers with carbonate
order to cover all applications of polyurethanes, another (Scheme 10-B) or amine (Scheme 10-B’) end groups; or
route is needed. This new technology consists in the the crosslinking of hydroxyurethane modifiers (HUM)
synthesis of Hybrid Non-Isocyanate Polyurethane (H- (Scheme 10-C).
NIPU).
III.1.2.1 Synthesis of H-NIPU by crosslinking of partially
III.1.2 Synthesis of hybrid non-isocyanate polyurethane carbonated epoxide monomers
(H-NIPU)
This method was widely developed by Figovsky et al. [194-
196]
The most promising method to synthesize PHU at room and consists to the partial carbonation of epoxide
temperature is based on hybrid non-isocyanate monomers. The further reaction with amines allows both
polyurethanes (H-NIPU). Currently, three interesting aminolysis of cyclic carbonate and ring opening of
methods allow the synthesis of H-NIPU: the crosslinking epoxides which leads to high conversion of monomers.
of partially carbonated epoxide monomers (Scheme 10- (Scheme 10). The final interpenetrated network

Scheme 8: Diglycerol effect on the PHU chains mobility

12
Scheme 9: Synthesis of PHU foam by reaction between cyclic carbonates, di-amines, blowing agent (MH 15) and catalyzed
with thiourea

structure is a polyhydroxyurethane cross-linked with from PHU prepolymers with cyclic carbonate end groups.
polyepoxides. Such H-NIPUs exhibit better mechanical Then, the PHU prepolymers were extended with diamine
properties than PHUs. The preparation of these H-NIPUs such as 1,4-butanediamine (BDA) or m-xylene diamine
[136, 181]
was also studied by Buergel et al. and Rokicki et (mXDA). Nevertheless, as showed previously, the cyclic
[197]
al. from oligomerization of bisphenol A diglycidyl carbonate aminolysis reaction is not quantitative at
ether. A patent claims the methods of making H-NIPU room temperature and requires a thermal activation or
networks for use in composite materials with fiber additive to reach total conversion.
reinforcement (glass fiber, carbon fiber, basalt fiber, and
mixtures thereof), or metal oxide or aluminate
reinforcements [198]. III.1.2.3 Synthesis of H-NIPU by crosslinking of HUM

III.1.2.2 Synthesis of H-NIPU by crosslinking of PHU Finally, the third pathway to obtain H-NIPU is based on a
prepolymers novel patented concept of hydroxyurethane modifiers
[71]
(HUM) (Scheme 10-C) . The patent application
The second route to synthesize H-NIPUs consists to use
discloses a novel “cold” cure epoxy-amine composition
PHU prepolymers with cyclic carbonate [199] or amine [120]
modified with a HUM, which is obtained in a first step, as
end groups. These PHU prepolymers are subsequently
result of a reaction between a di-amine and a mono-
crosslinked with chain extenders able to react with them
cyclic carbonate. The HUM, having amino-reactive
to give H-NIPUs (Scheme 10). The main advantage of this
groups, is then added, in a second step, to a
route is the ability to obtain materials with a sequence of
polyepoxide. The crosslinking by epoxy/amine reaction
soft and hard segments as in polyurethanes. In 2015, our
leads to an epoxy-amine network with hydroxyurethane
team pioneered the synthesis of such H-NIPUs with a
groups that confer higher performance compared to
sequence of soft and rigid segments. Indeed, in our
[120] classic polyepoxides. In 2014, Polymate Ltd. developed
works , H-NIPUs were synthesized from PHU
and patented a new H-NIPU polymer with lengthy epoxy-
prepolymers with amine end groups, then extended with
[75]
amine chains and pendulous hydroxyurethane units .
biobased epoxide monomers such as epoxidized
The patent claimed linear hybrid epoxy-amine
cardanol (NC-514) or epoxidized phloroglucinol (PGTE).
[199] hydroxyurethane polymers with controlled numbers of
Very recently, Carré et al. reported biobased
crosslinking nodes. These polymers combine increased
thermoplastic PHUs with aliphatic-aromatic architecture

13
Scheme 10: Methods to synthesize H-NIPUs from (A) the crosslinking of partially carbonated epoxide monomers; the
crosslinking of PHU prepolymers with carbonate (B) or amine (B’) end groups; or (C) the crosslinking of hydroxyurethane
modifiers (HUM).

flexibility with well-balanced mechanical and physical- correspond to a real solution to propose PHUs at room
chemical properties of conventional epoxy-amine temperature and cover the rest of PU applications. In
[72, 200]
systems. These alternative routes for the synthesis of 2012, Birukov et al. patented a method of
PHUs at room temperature allow promising applications obtaining biobased H-NIPUs at room temperature for
that are summarized in the following section. adhesive and sealant applications from carbonated-
epoxidized unsaturated fatty acid triglycerides (CESBO).
III.2 Promising applications of PHUs
From these works, the development of adhesive and
sealant H-NIPUs compositions, in particular for bonding
The synthesis of PHUs with blowing agents could allow
metal surfaces, is a promising area for further research.
to obtain full conversion at room temperature. This is
Furthermore, the compositions can apply to the
very interesting since foams correspond to 66% of PU
preparation of curable hard and elastic foams [73].
applications. Moreover, the synthesis of PHU with
plasticizers or solvents covers 20% of the applications of
It is also possible to use H-NIPUs with acrylic polymers.
PUs. Furthermore, in 2016, our team showed that the Assumption et al. [201]
synthesized urethane
adhesion properties of PHUs were outstandingly higher
dimethacrylate monomers from hydroxyurethane diol
[185]
than the ones of PUs . However, these PHUs were (HUM) and methacrylic anhydride. The HUM were
synthesized at high temperature. Hence, H-NIPUs

14
Scheme 11: Synthesis of mono- and bis-urethane methacrylate

obtained by the reaction between 3-amino-1-propanol communities. The most exciting alternative to replace
or 2,2-dimethyl-1,3-porpanediamine and ethylene PU could well consist in the cyclic carbonate aminolysis
carbonate (Scheme 11). reaction that yields polyhydroxyurethanes PHUs. The
most promising routes could be based on the reaction
[202]
Figovsky et al. showed that the incorporation of
between activated CC5 cyclic carbonate, reactive amines
HUM monomers in UV-curable formulation allows
with effective catalysts such as thiourea or TBD.
improving hardness and wear resistance, while
However, this reaction suffers from drawbacks that
maintaining the other properties of the system.
could limit its development. Particularly, beyond the
Application is done by spraying, eliminating the negative
reactivity, the advancement of reaction at room
effects of sunlight during the coating process and uses
temperature is limited, which reduces the molar masses
sunlight during the curing process, which reduces the
and the properties of PHUs. New routes led recently to
total polymerization time. Furthermore, the uniqueness
PHUs or H-NIPUs at room temperature, therefore
of the developed formulation and the possibility of
allowing to cover most of PU applications. Hence, the
coating concrete without a primer, allows to cover even
use of plasticizers (or solvents) allowed quantitative
new areas of application. In order to improve the
reaction of cyclic carbonate aminolysis at room
hydrophobicity, lower the glass transition temperature
temperature. Moreover, the use of blowing agent
and keep thermal stability of the PHUs, the introduction
allowed also to open the way to room temperature PHU
of siloxane in polymers can confer interesting properties.
foams. Furthermore, H-NIPU routes allow to cross-link
Therefore, H-NIPUs including siloxane functions were
PHUs with other polymers such as polyepoxide,
synthesized [35, 70]. Figovsky et al. [202] developed a highly
polyacrylates, polysiloxanes…, to reach quantitative
curable composition at low temperature (10-30°C) from
yields and confer improved properties to these hybrid
polyepoxide, cyclic-carbonates, amines and acrylate
polymers. This technology presents a considerable
wherein at least one monomer contains alkoxysilanes.
interest in the coming years in order to target the total
The cured composition has excellent adhesion properties
replacement of polyurethane in various applications.
on a variety of substrates and resistance properties to
Polyepoxide-PHU hybrid coatings are currently
weathering, abrasion and solvents.
commercially available under the name Green
TM
Conclusion Polyurethane as an isocyanate-free and phosgene-free
alternative to conventional coatings and represent a
Despite the massive use of PUs in many applications, a successful application of H-NIPUs. The hydroxyl groups
great deal of attention is paid to their replacement, hanging off the main chain of PHU in these hybrid
particularly to avoid the use of isocyanates that are very polymers confer unique properties: 30 to 50% higher
toxic substances. Indeed, research efforts were resistance to chemical degradation, 10 to 30% increased
performed both by academic and industrial adhesion, 20% increased wear resistance compared to

15
conventional polyurethane without neither solvent nor [10] Cornille A., Guillet C., Benyahya S., Negrell C.,
volatile organic compounds. Boutevin B., Caillol S., Room temperature flexible
isocyanate-free polyurethane foams, Eur Polym J; 2016,
References
Accepted manuscript.

[1] Boujard C., Foray N., Caudron J. C., Panorama du

[11] Delebecq E., Pascault J. P., Boutevin B., Ganachaud
marché du polyuréthane et état de l'art de ses F., On the versatility of urethane/urea bonds:
techniques de recyclages, 2014
reversibility, blocked isocyanate, and non-isocyanate
polyurethane, Chem Rev; 113, 2013, 80-118.
[2] Boiteux G., Cuvé L., Pascault J.-P., Synthesis and
properties of polyurethanes based on polyolefin: 3.
[12] Kathalewar M. S., Joshi P. B., Sabnis A. S., Malshe V.
Monitoring of phase separation by dielectric relaxation
C., Non-isocyanate polyurethanes: from chemistry to
spectroscopy of segmented semicrystalline polyurethane
applications, RSC Adv; 3, 2013, 4110-4129.
prepared in bulk by the use of emulsifiers, Polymer; 35,
1994, 173-178. [13] Rokicki G., Parzuchowski P. G., Mazurek M., Non-
isocyanate polyurethanes: synthesis, properties, and
[3] Merenyi S., REACH: Regulation (EC) No 1907/2006:
applications, Polym Adv Technol; 26, 2015, 707-761.
Consolidated version (June 2012) with an introduction
and future prospects regarding the area of Chemicals [14] Maisonneuve L., Lamarzelle O., Rix E., Grau E.,
legislation: GRIN Verlag; 2012. Cramail H., Isocyanate-Free Routes to Polyurethanes and
Poly(hydroxy Urethane)s, Chem Rev; 115, 2015, 12407-
[4] Bello D., Herrick C. A., Smith T. J., Woskie S. R.,
12439.
Streicher R. P., Cullen M. R., Liu Y., Redlich C. A., Skin
exposure to isocyanates: reasons for concern, Environ [15] Figovsky O., Shapovalov L., Leykin A., Birukova O.,

Health Perspect; 115, 2007, 328-335. Potashnikova R., Recent advances in the development of
non-isocyanate polyurethanes based on cyclic
[5] Gupta S., Upadhyaya R., Cancer and p21 protein
carbonates, PU Magazine; 10, 2013, 256-263.
expression: in relation with isocyanate toxicity in
cultured mammalian cells, Int J Pharm Res Bio-Sci; 3, [16] Blattmann H., Fleischer M., Baehr M., Muelhaupt R.,

2014, 20-28. Isocyanate- and Phosgene-Free Routes to Polyfunctional

Cyclic Carbonates and Green Polyurethanes by Fixation
[6] Karol M. H., Kramarik J. A., Phenyl isocyanate is a
of Carbon Dioxide, Macromol Rapid Commun; 35, 2014,
potent chemical sensitizer, Toxicol Lett; 89, 1996, 139- 1238-1254.
146.
[17] Argyropoulos J. N., Bhattacharjee D., Ambient
[7] Saunders J. H., Reactions of isocyanates and
temperature curable isocyanate-free compositions for
isocyanate derivatives at elevated temperatures, Rub
preparing crosslinked polyurethanes, EP2397506A1,
Chem Technol; 32, 1959, 337-345.
2011.

[8] Chattopadhyay D. K., Webster D. C., Thermal stability [18] Illari G., Marenghi I., Tarantelli T., Phenylisocyanate
and flame retardancy of polyurethanes, Prog Polym Sci;
and aminophenols, Ann Chim (Rome, Italy); 43, 1953,
34, 2009, 1068-1133.
679-688.

[9] Benbow A. W., Cullis C. F., Combustion of flexible

[19] McKillip W. J., Sedor E. A., Culbertson B. M.,
polyurethane foams. Mechanisms and evaluation of Wawzonek S., Chemistry of aminimides, Chem Rev; 73,
flame retardance, Combust Flame; 24, 1975, 217-230. 1973, 255-281.

16
[20] Kinstle J. F., Sepulveda L. E., A novel "apparent [30] Neffgen S., Keul H., Hoecker H., Ring-opening
sublimation" of a polymer, J Polym Sci, Polym Lett Ed; polymerization of cyclic urethanes and ring-closing
15, 1977, 467-469. depolymerization of the respective polyurethanes,
Macromol Rapid Commun; 17, 1996, 373-382.
[21] Ghatge N. D., Jadhav J. Y., Synthesis,
characterization, and properties of novel poly(ether [31] Kusan J., Keul H., Hoecker H., Cationic ring-opening
urethanes), J Polym Sci, Polym Chem Ed; 21, 1983, 1941- polymerization of tetramethylene urethane,
1950. Macromolecules; 34, 2001, 389-395.

[22] Masuyama A., Tsuchiya K., Okahara M., Preparation [32] Lundberg R. D., Montgomery D. R., Carbon dioxide
and thermolysis of N-ammonioamidates containing polymers, US3523924 A, 1970.
hydroxyl group in acyl moiety, Bull Chem Soc Jpn; 58,
[33] Soga K., Chiang W.-Y., Ikeda S., Copolymerization of
1985, 2855-2859.
carbon dioxide with propyleneimine, J Polym Sci, Polym
[23] Scriven E. F. V., Turnbull K., Azides: their Chem Ed; 12, 1974, 121-131.
preparation and synthetic uses, Chem Rev; 88, 1988,
[34] Ihata O., Kayaki Y., Ikariya T., Synthesis of
297-368.
thermoresponsive polyurethane from 2-methylaziridine
[24] Palaskar D. V., Boyer A., Cloutet E., Alfos C., Cramail and supercritical carbon dioxide, Angew Chem, Int Ed;
H., Synthesis of Biobased Polyurethane from Oleic and 43, 2004, 717-719.
Ricinoleic Acids as the Renewable Resources via the AB-
[35] Figovsky O., Shapovalov L., Leykin A., Birukova O.,
Type Self-Condensation Approach, Biomacromolecules;
Potashnikova R., Advances in the field of nonisocyanate
11, 2010, 1202-1211.
polyurethanes based on cyclic carbonates, Chem Chem
[25] Neumann C. N. D., Bulach W. D., Rehahn M., Klein Technol; 7, 2013, 79-87.
R., Water-Free Synthesis of Polyurethane Foams Using
[36] Drechsel E. K., Groszos S. J., Method of preparing a
Highly Reactive Diisocyanates Derived from 5-
polyurethane, US 2802022, 1957.
Hydroxymethylfurfural, Macromol Rapid Commun; 32,
2011, 1373-1378. [37] Figovsky O., Leykin A., Shapovalov L., Non-
isocyanate polyurethane - yesterday, today and
[26] More A. S., Gadenne B., Alfos C., Cramail H., AB type
tomorrow, ISJAEE; 3, 2016, 95-108.
polyaddition route to thermoplastic polyurethanes from
fatty acid derivatives, Polym Chem; 3, 2012, 1594-1605. [38] Shapovalov L., Figovsky O., Nonisocyanate
polyurethane: synthesis nano-structuring and
[27] Drechsel E. K., Polymerization of cyclic carbamates,
applications, Sci Isr -Technol Advantages; 6, 2004, 45-52.
US2806017 A, 1957.

[39] Nohra B., Candy L., Blanco J.-F., Guerin C., Raoul Y.,
[28] Neffgen S., Keul H., Hoecker H., Cationic Ring-
Mouloungui Z., From Petrochemical Polyurethanes to
Opening Polymerization of Trimethylene Urethane: A
Biobased Polyhydroxyurethanes, Macromolecules; 46,
Mechanistic Study, Macromolecules; 30, 1997, 1289-
2013, 3771-3792.
1297.

[40] Tomita H., Sanda F., Endo T., Polyaddition behavior

[29] Neffgen S., Keul H., Hoecker H., Polymerization of
of bis (five and six membered cyclic carbonate)s with
2,2-dimethyltrimethylene urethane. A disfavored
diamine, J Polym Sci Part A: Polym Chem; 39, 2001, 860-
process, Macromol Chem Phys; 199, 1998, 197-206.
867.

17
[41] Hahn C., Keul H., Moeller M., Hydroxyl-functional [53] Anderson J. R., Argyropoulos J. N., Bhattacharjee D.,
polyurethanes and polyesters: synthesis, properties and Foley P., Spilman G. E., Zhang H., Ambient temperature
potential biomedical application, Polym Int; 61, 2012, curable isocyanate-free compositions for preparing
1048-1060. crosslinked polyurethanes, US8653174 B2, 2014.

[42] Samuels J. W. P., Whelan J. J. M., Multiple cyclic [54] Klopsch R., Yu M., Curing of epoxy resin
carbonate polymers from erythritol dicarbonate, compositions comprising cyclic carbonates using
US2935494 A, 1960. mixtures of amino hardeners, US8586653 B2, 2013.

[43] Cotter R. J., Whelan J. J. M., Multiple cyclic [55] Klopsch R., Yu M., Epoxy resin compositions
carbonate polymers, US3072613 A, 1963. comprising a 2-oxo-[1,3] dioxolane derivative,
US9150709 B2, 2015.
[44] Bressler W. L., Gurgiolo A. E., Smith J. C.,
Polyhydroxyurethanes, US3084140 A, 1963. [56] GARCIA M. P., Weis M., Lanver A., BLANCHOT M.,
Flores-Figueroa A., Klopsch R., Haaf C., Kutzki O.,
[45] Meyer L. G., Polyether dihydroxyalkyl carbamate
Polymerizable alkylidene-1,3-dioxolane-2-one and use
epoxy additive for epoxy resins, US4122068 A, 1978.
thereof, US9062136 B2, 2015.

[46] Alexander D. C., Crawford W. C., Klein H. P., Epoxy

[57] Gehringer L., Daun G., Henningsen M., Klopsch R.,
curing agents, US5235007 A, 1993.
Fleischel O., Blends for composite materials, US9193862

[47] Crawford W. C., Marquis E. T., Klein H. P., B2, 2015.

Liquification of bis-carbonates of bis-glycidyl ethers,

[58] Lombardo V., Scheidt K., Leitsch E., Torkelson J.,
US5340889 A, 1994.
Dhulst E., Heath W. H., Wilmot N., Catalyst for Non-

[48] Diakoumakos C. D., Kotzev D. L., Nanocomposites Isocyanate Based Polyurethane, US20150247004 A1,

based on polyurethane or polyurethane-epoxy hybrid 2015.

resins prepared avoiding isocyanates, US8143346 B2,

[59] Hesse W., Hardenable cationic modification
2012.
products of epoxy resins, process for preparing them and

[49] MECFEL-MARCZEWSKI J., Walther B., Mezger J., their use, CA1247288 A1, 1988.

Staudhamer R., Water dispersable, cyclic-carbonate-

[60] Jacobs W., Parekh G. G., Blank W. J., Hydroxyalkyl
functionalized vinyl copolymer system, US8853322 B2,
carbamate-containing resins for cathodic
2014.
electrodeposition and method of making the same,

[50] Klopsch R., Lanver A., Kaffee A., Ebel K., Yu M., Use US4484994 A, 1984.

of cyclic carbonates in epoxy resin compositions,

[61] Tominaga A., Heat-curable resin coating
US8741988 B2, 2014.
composition, US4528363 A, 1985.

[51] Mecfel-Marczewski J., Walther B., Mezger J., Kierat

[62] Parekh G. G., Blank W. J., Jacobs W., Self-cross-
R., Staudhamer R., 2-Oxo-1,3-dioxolane-4-carboxylic Acid
linkable acrylic polymer containing hydroxyalkyl
and Derivatives Thereof, Their Preparation and Use,
carbamate groups and coating compositions containing
US20110313177A1, 2011.
the same, US4758632 A, 1988.

[52] Marks M. J., Bulick A. S., Athey P. S., Latham D. D.,

Cyclic carbonate monomers and polymers prepared
therefrom, US20140191156 A1, 2014.

18
[63] Hoenel M., Pfeil A., Budnick T., Schwan H., Liquid [73] Figovsky O., Potashnikov R., Leykin A., Shapovalov
two-component coating compositions, US5677006 A, L., Sivokon S., Method for forming a sprayable
1997. nonisocyanate polymer foam composition,
US20150024138 A1, 2015.
[64] Figovsky O., Shapovalov L., Blank N., Buslov F.,
Cyclocarbonate groups containing hydroxyamine [74] Figovsky O., Potashnikov R., Leykin A., Shapovalov
oligomers from epoxycylclocarbonates, US6407198 B1, L., Birukov O., Radiation-curable biobased flooring
2002. compositions with nonreactive additives, CA2876736 A1,
2015.
[65] Blank N., Buslov F., Figovsky O., Shapovalov L.,
Method of synthesis of polyaminofunctional [75] Birukov O., Figovsky O., Leykin A., Shapovalov L.,
hydroxyurethane oligomers and hybride polymers Hybrid epoxy-amine hydroxyurethane-grafted polymer,
formed therefrom, EP1070733 A1, 2001. US20150353683, 2014.

[66] Swarup S., Hart M. P., Jia C. Y., Pagac E. S., Taylor C. [76] Garipov R. M., Sysoev V. A., Mikheev V. V.,
A., Zezinka E. A., Polyether carbamate compounds, Zagidullin A. I., Deberdeev R. Y., Irzhak V. I., Berlin A. A.,
compositions containing such compounds, and methods Reactivity of Cyclocarbonate Groups in Modified Epoxy–
related thereto, US7288595 B2, 2007. Amine Compositions, Doklady Physical Chemistry; 393,
2003, 289-292.
[67] Herzig C., Process for the preparation of
organosilicon compounds having urethane groups, [77] Tomita H., Sanda F., Endo T., Reactivity comparison
US7842773 B2, 2010. of five‐and six‐membered cyclic carbonates with amines:
Basic evaluation for synthesis of poly (hydroxyurethane),
[68] Bernard J. M., Method for preparing polyhydroxy-
J Polym Sci Part A: Polym Chem; 39, 2001, 162-168.
urethanes, US8017719 B2, 2011.
[78] Steblyanko A., Choi W., Sanda F., Endo T., Addition
[69] Birukov O., Beilin D., Figovsky O., Leykin A.,
of five‐membered cyclic carbonate with amine and its
Shapovalov L., Liquid oligomer composition containing
application to polymer synthesis, J Polym Sci Part A:
hydroxyamine adducts and method of manufacturing
Polym Chem; 38, 2000, 2375-2380.
thereof, US20100144966 A1, 2010.
[79] Tomita H., Sanda F., Endo T., Model reaction for the
[70] Birukov O., Beilin D., Figovsky O., Leykin A.,
synthesis of polyhydroxyurethanes from cyclic
Shapovalov L., Nanostructured hybrid oligomer
carbonates with amines: Substituent effect on the
composition, US7820779 B2, 2010.
reactivity and selectivity of ring‐opening direction in the

[71] Birukov O., Figovsky O., Leykin A., Shapovalov L., reaction of five‐membered cyclic carbonates with amine,

Epoxy-amine composition modified with hydroxyalkyl J Polym Sci Part A: Polym Chem; 39, 2001, 3678-3685.

urethane, US7989553 B2, 2011.

[80] Ochiai B., Matsuki M., Miyagawa T., Nagai D., Endo

[72] Birukov O., Figovsky O., Leykin A., Potashnikov R., T., Kinetic and computational studies on aminolysis of

Shapovalov L., Method of producing hybrid bicyclic carbonates bearing alicyclic structure giving

polyhydroxyurethane network on a base of carbonated- alicyclic hydroxyurethanes, Tetrahedron; 61, 2005, 1835-

epoxidized unsaturated fatty acid triglycerides, 1838.

US9102829 B2, 2015.

19
[81] He Y., Goel V., Keul H., Moeller M., Synthesis, [89] Baba A., Kashiwagi H., Matsuda H., Cycloaddition of
Characterization, and Selectivity of Bifunctional oxetane and carbon dioxide catalyzed by
Couplers, Macromol Chem Phys; 211, 2010, 2366-2381. tetraphenylstibonium iodide, Tetrahedron Lett; 26,
1985, 1323-1324.
[82] Lamarzelle O., Durand P.-L., Wirotius A.-L., Chollet
G., Grau E., Cramail H., Activated lipidic cyclic carbonates [90] Darensbourg D. J., Moncada A. I., Tuning the
for non-isocyanate polyurethane synthesis, Polym Chem; Selectivity of the Oxetane and CO2Coupling Process
7, 2016, 1439-1451. Catalyzed by (Salen)CrCl/n-Bu4NX: Cyclic Carbonate
Formation vs Aliphatic Polycarbonate Production,
[83] Maisonneuve L., Wirotius A.-L., Alfos C., Grau E.,
Macromolecules; 43, 2010, 5996-6003.
Cramail H., Fatty acid-based (bis) 6-membered cyclic
carbonates as efficient isocyanate free [91] Reithofer M. R., Sum Y. N., Zhang Y., Synthesis of
poly(hydroxyurethane) precursors, Polym Chem; 5, 2014, cyclic carbonates with carbon dioxide and cesium
6142-6147. carbonate, Green Chemistry; 15, 2013, 2086.

[84] Nemirovskii V. D., Skorokhodov S. S., Kinetic study [92] Carothers W. H., Van Natta F. J., Polymerization and
of aminolysis of poly (vinylene carbonate) and related ring formation. III. Glycol esters of carbonic acid, J Am
model compounds, J Polym Sci, Polym Symp; No. 16, Chem Soc; 52, 1930, 314-326.
1967, 1471-1478.
[93] Spanagel E. W., Carothers W. H., Polymerization and
[85] Tomita H., Sanda F., Endo T., Polyaddition of ring formation. XXV. Macrocyclic esters, J Am Chem Soc;
bis(seven-membered cyclic carbonate) with diamines: a 57, 1935, 929-934.
novel and efficient synthetic method for
[94] Burk R. M., Roof M. B., A safe and efficient method
polyhydroxyurethanes, J Polym Sci, Part A: Polym Chem;
for conversion of 1,2- and 1,3-diols to cyclic carbonates
39, 2001, 4091-4100.
utilizing triphosgene, Tetrahedron Lett; 34, 1993, 395-
[86] He Y., Keul H., Möller M., Synthesis, 398.
characterization, and application of a bifunctional
[95] Wang H., Wu L.-X., Lan Y.-C., Zhao J.-Q., Lu J.-X.,
coupler containing a five- and a six-membered ring
Electrosynthesis of cyclic carbonates from CO2 and diols
carbonate, React Funct Polym; 71, 2011, 175-186.
in ionic liquids under mild conditions, Int J Electrochem
[87] Yuen A., Bossion A., Gomez-Bengoa E., Ruiperez F., Sci; 6, 2011, 4218-4227.
Isik M., Hedrick J. L., Mecerreyes D., Yang Y. Y., Sardon
[96] Gabriele B., Mancuso R., Salerno G., Ruffolo G.,
H., Room temperature synthesis of non-isocyanate
Costa M., Dibenedetto A., A novel and efficient method
polyurethanes (NIPUs) using highly reactive N-
for the catalytic direct oxidative carbonylation of 1,2-
substituted 8-membered cyclic carbonates, Polym Chem;
and 1,3-diols to 5-membered and 6-membered cyclic
7, 2016, 2105-2111.
carbonates, Tetrahedron Lett; 50, 2009, 7330-7332.
[88] Boyer A., Cloutet E., Tassaing T., Gadenne B., Alfos
[97] Shaikh A.-A. G., Sivaram S., Organic Carbonates,
C., Cramail H., Solubility in CO2 and carbonation studies
Chem Rev (Washington, D C); 96, 1996, 951-976.
of epoxidized fatty acid diesters: towards novel
precursors for polyurethane synthesis, Green Chem; 12, [98] Pyo S.-H., Persson P., Mollaahmad M. A., Soerensen
2010, 2205-2213. K., Lundmark S., Hatti-Kaul R., Cyclic carbonates as
monomers for phosgene- and isocyanate-free

20
polyurethanes and polycarbonates, Pure Appl Chem; 84, [109] Chen F., Dong T., Xu T., Li X., Hu C., Direct synthesis
2012, 637-661. of cyclic carbonates from olefins and CO2 catalyzed by a
MoO2(acac)2-quaternary ammonium salt system, Green
[99] Pearson D. M., Conley N. R., Waymouth R. M.,
Chem; 13, 2011, 2518-2524.
Palladium-catalyzed carbonylation of diols to cyclic
carbonates, Adv Synth Catal; 353, 2011, 3007-3013. [110] Della Ca N., Gabriele B., Ruffolo G., Veltri L.,
Zanetta T., Costa M., Effective Guanidine-Catalyzed
[100] Aresta M., Dibenedetto A., Dileo C., Tommasi I.,
Synthesis of Carbonate and Carbamate Derivatives from
Amodio E., The first synthesis of a cyclic carbonate from
Propargyl Alcohols in Supercritical Carbon Dioxide, Adv
a ketal in SC-CO2, J Supercrit Fluids; 25, 2003, 177-182.
Synth Catal; 353, 2011, 133-146.

[101] Yeo I. S., Woo B. W., Yoon S. W., Lee J., Park S. H.,
[111] Renga J. M., Periana-Pillai R. A., Preparation of
Jang N. J., Method of manufacturing vinylethylene
cyclic carbonates, US4332729 A, 1982.
carbonate, US20100048918 A1, 2010.
[112] Pews R. G., Synthesis of cyclic carbonates by a
[102] Takagaki A., Iwatani K., Nishimura S., Ebitani K.,
novel carbonate rearrangement, J Chem Soc, Chem
Synthesis of glycerol carbonate from glycerol and dialkyl
Commun; 1974, 119.
carbonates using hydrotalcite as a reusable
heterogeneous base catalyst, Green Chem; 12, 2010, [113] Nishikubo T., Iizawa T., Iida M., Isobe N.,
578-581. Convenient syntheses of cyclic carbonates by new
reaction of oxiranes with β-butyrolactone, Tetrahedron
[103] Mignani G., DEBRAY J., Da S. E., Lemaire M., Raoul
Lett; 27, 1986, 3741-3744.
Y., Procédé de préparation de (poly)carbonate de
polyglycérol, WO2014009421 A1, 2014. [114] Xu B.-H., Wang J.-Q., Sun J., Huang Y., Zhang J.-P.,
Zhang X.-P., Zhang S.-J., Fixation of CO2 into cyclic
[104] Su W. Y., Speranza G. P., Process for preparing
carbonates catalyzed by ionic liquids: a multi-scale
alkylene carbonates, US5003084 A, 1991.
approach, Green Chem; 17, 2015, 108-122.

[105] Bhanage B. M., Fujita S.-i., Ikushima Y., Arai M.,

[115] Dai W.-L., Luo S.-L., Yin S.-F., Au C.-T., The direct
Transesterification of urea and ethylene glycol to
transformation of carbon dioxide to organic carbonates
ethylene carbonate as an important step for urea based
over heterogeneous catalysts, Appl Catal, A; 366, 2009,
dimethyl carbonate synthesis, Green Chem; 5, 2003,
2-12.
429-432.
[116] Sun J., Fujita S.-i., Arai M., Development in the
[106] Lim Y. N., Lee C., Jang H.-Y., Metal-Free Synthesis
green synthesis of cyclic carbonate from carbon dioxide
of Cyclic and Acyclic Carbonates from CO2 and Alcohols,
using ionic liquids, J Organomet Chem; 690, 2005, 3490-
Eur J Org Chem; 2014, 2014, 1823-1826.
3497.

[107] Bruneau C., Dixneuf P. H., Catalytic incorporation

[117] North M., Synthesis of cyclic carbonates from CO2
of carbon dioxide into organic substrates: synthesis of
emissions, Chim Oggi; 30, 2012, 3-5.
unsaturated carbamates, carbonates and ureas, J Mol
Catal; 74, 1992, 97-107. [118] Olah G. A., Prakash G. K. S., Goeppert A.,
Anthropogenic Chemical Carbon Cycle for a Sustainable
[108] Sun J., Liang L., Sun J., Jiang Y., Lin K., Xu X., Wang
Future, J Am Chem Soc; 133, 2011, 12881-12898.
R., Direct Synthetic Processes for Cyclic Carbonates from
Olefins and CO2, Catal Surv Asia; 15, 2011, 49-54.

21
[119] Cornille A., Dworakowska S., Bogdal D., Boutevin [128] Patai S., Editor, The Chemistry of the Thiol Group,
B., Caillol S., A new way of creating cellular polyurethane Pt. 1: Wiley; 1974.
materials: NIPU foams, Eur Polym J; 66, 2015, 129-138.
[129] Kihara N., Tochigi H., Endo T., Synthesis and
[120] Cornille A., Serres J., Michaud G., Simon F., reaction of polymers bearing 5-membered cyclic
Fouquay S., Boutevin B., Caillol S., Syntheses of dithiocarbonate group, J Polym Sci, Part A: Polym Chem;
epoxyurethane polymers from isocyanate free oligo- 33, 1995, 1005-1010.
polyhydroxyurethane, Eur Polym J; 75, 2016, 175-189.
[130] Ochiai B., Nakayama J.-I., Mashiko M., Kaneko Y.,
[121] Beckman E. J., Supercritical and near-critical CO2 in Nagasawa T., Endo T., Synthesis and crosslinking reaction
green chemical synthesis and processing, J Supercrit of poly(hydroxyurethane) bearing a secondary amine
Fluids; 28, 2004, 121-191. structure in the main chain, J Polym Sci, Part A: Polym
Chem; 43, 2005, 5899-5905.
[122] Ochoa-Gomez J. R., Gomez-Jimenez-Aberasturi O.,
Ramirez-Lopez C., Belsue M., Brief review on industrial [131] Kihara N., Nakawaki Y., Endo T., Preparation of 1,3-
alternatives for the manufacturing of glycerol carbonate, Oxathiolane-2-thiones by the Reaction of Oxirane and
green chemical, Org Process Res Dev; 16, 2012, 389-399. Carbon Disulfide, J Org Chem; 60, 1995, 473-475.

[123] Behr A., Eilting J., Irawadi K., Leschinski J., Lindner [132] Ochiai B., Inoue S., Endo T., Salt effect on
F., Improved utilization of renewable resources: New polyaddition of bifunctional cyclic carbonate and
important derivatives of glycerol, Green Chem; 10, 2008, diamine, Journal of Polymer Science Part A: Polymer
13-30. Chemistry; 43, 2005, 6282-6286.

[124] Sonnati M. O., Amigoni S., Taffin de Givenchy E. P., [133] Kihara N., Endo T., Synthesis and properties of
Darmanin T., Choulet O., Guittard F., Glycerol carbonate poly(hydroxyurethanes), J Polym Sci, Part A: Polym
as a versatile building block for tomorrow: synthesis, Chem; 31, 1993, 2765-2773.
reactivity, properties and applications, Green Chem; 15,
[134] Diakoumakos C. D., Kotzev D. L., Non-Isocyanate-
2013, 283-306.
Based Polyurethanes Derived upon the Reaction of
[125] Besse V., Foyer G., Auvergne R., Caillol S., Boutevin Amines with Cyclocarbonate Resins, Macromolecular
B., Access to nonisocyanate poly(thio)urethanes: A Symposia; 216, 2004, 37-46.
comparative study, J Polym Sci Part A: Polym Chem; 51,
[135] Webster D. C., Crain A. L., Synthesis and
2013, 3284-3296.
applications of cyclic carbonate functional polymers in
[126] Adams H., Bell R., Cheung Y. Y., Jones D. N., thermosetting coatings, Progr Organ Coat; 40, 2000,
Tomkinson N. C. O., The cleavage of meso-epoxides with 275-282.
homochiral thiols: synthesis of (+)- and (-)-trans-1-
[136] Buergel T., Fedtke M., Franzke M., Reaction of
mercaptocyclohexan-2-ol, Tetrahedron: Asymmetry; 10,
cyclic carbonates with amines: linear telechelic
1999, 4129-4142.
oligomers, Polym Bull (Berlin); 30, 1993, 155-162.
[127] Yamashita H., METAL(II) D-TARTRATES CATALYZED
[137] Tabushi I., Oda R., A kinetic study of the reaction of
ASYMMETRIC RING-OPENING OF OXIRANES WITH
ethylene carbonate and amines, Nippon Kagaku Zasshi;
VARIOUS NUCLEOPHILES, Bulletin of the Chemical
84, 1963, 162-167.
Society of Japan; 61, 1988, 1213-1220.

22
[138] Nohra B., Candy L., Blanco J.-F., Raoul Y., [146] Soules A., Caillol S., Joubert J. P., Martins J.,
Mouloungui Z., Aminolysis Reaction of Glycerol Boutevin B., Method for preparing a compoud
Carbonate in Organic and Hydroorganic Medium, Journal comprising at least one -hydroxy-urethane unit and/or
of the American Oil Chemists' Society; 89, 2012, 1125- at least one -hydroxy-urethane unit, WO2013060950
1133. A1, 2013.

[139] Besse V., Camara F., Mechin F., Fleury E., Caillol S., [147] Darensbourg D. J., Holtcamp M. W., Catalysts for
Pascault J.-P., Boutevin B., How to explain low molar the reactions of epoxides and carbon dioxide, Coord
masses in PolyHydroxyUrethanes (PHUs), Eur Polym J; Chem Rev; 153, 1996, 155-174.
71, 2015, 1-11.
[148] Lombardo V. M., Dhulst E. A., Leitsch E. K., Wilmot
[140] Helou M., Guillaume S., Carpentier J. F., Miserque N., Heath W. H., Gies A. P., Miller M. D., Torkelson J. M.,
O., Procédé catalytique pour la polymérisation de Scheidt K. A., Cooperative Catalysis of Cyclic Carbonate
carbonates cycliques issus de ressources renouvelables, Ring Opening: Application Towards Non-Isocyanate
WO2010012562 A1, 2010. Polyurethane Materials, Eur J Org Chem; 2015, 2015,
2791-2795.
[141] Corma A., Garcia H., Lewis Acids: from
conventional homogeneous to green homogeneous and [149] Murayama M., Sanda F., Endo T., Anionic Ring-
heterogeneous catalysis, Chem Rev (Washington, DC, U Opening Polymerization of a Cyclic Carbonate Having a
S); 103, 2003, 4307-4365. Norbornene Structure with Amine Initiators,
Macromolecules; 31, 1998, 919-923.
[142] Helou M., Miserque O., Brusson J. M., Carpentier J.
F., Guillaume S. M., Organocatalysts for the controlled [150] Kiesewetter M. K., Shin E. J., Hedrick J. L.,
"immortal" ring-opening polymerization of six- Waymouth R. M., Organocatalysis: Opportunities and
membered-ring cyclic carbonates: a metal-free, green Challenges for Polymer Synthesis, Macromolecules; 43,
process, Chemistry; 16, 2010, 13805-13813. 2010, 2093-2107.

[143] Annunziata L., Diallo A. K., Fouquay S., Michaud G., [151] Kamber N. E., Jeong W., Waymouth R. M., Pratt R.
Simon F., Brusson J.-M., Carpentier J.-F., Guillaume S. M., C., Lohmeijer B. G. G., Hedrick J. L., Organocatalytic ring-
α,ω-Di(glycerol carbonate) telechelic polyesters and opening polymerization, Chem Rev (Washington, DC, U
polyolefins as precursors to polyhydroxyurethanes: an S); 107, 2007, 5813-5840.
isocyanate-free approach, Green Chem; 16, 2014, 1947-
[152] Miao Y., Mortreux A., Zinck P., Polyester
1956.
functionalized carbohydrates via organocatalyzed ring-
[144] Nijenhuis A. J., Grijpma D. W., Pennings A. J., Lewis opening polymerization, Carbohydr Chem; 40, 2014,
acid catalyzed polymerization of L-lactide. Kinetics and 298-311.
mechanism of the bulk polymerization, Macromolecules;
[153] Miao Y., Phuphuak Y., Rousseau C., Bousquet T.,
25, 1992, 6419-6424.
Mortreux A., Chirachanchai S., Zinck P., Ring-opening
[145] Dobrzynski P., Pastusiak M., Bero M., Less toxic polymerization of lactones using binaphthyl-diyl
acetylacetonates as initiators of trimethylene carbonate hydrogen phosphate as organocatalyst and resulting
and 2,2-dimethyltrimethylene carbonate ring opening monosaccharide functionalization of polylactones, J
polymerization, J Polym Sci, Part A: Polym Chem; 43, Polym Sci, Part A: Polym Chem; 51, 2013, 2279-2287.
2005, 1913-1922.

23
[154] Sardon H., Pascual A., Mecerreyes D., Taton D., [163] Duval C., Kebir N., Jauseau R., Burel F.,
Cramail H., Hedrick J. L., Synthesis of Polyurethanes Organocatalytic synthesis of novel renewable non-
Using Organocatalysis: A Perspective, Macromolecules isocyanate polyhydroxyurethanes, J Polym Sci, Part A:
(Washington, DC, U S); 48, 2015, 3153-3165. Polym Chem; 2015, Ahead of Print.

[155] Nederberg F., Lohmeijer B. G. G., Leibfarth F., Pratt [164] Lambeth R. H., Henderson T. J., Organocatalytic
R. C., Choi J., Dove A. P., Waymouth R. M., Hedrick J. L., synthesis of (poly)hydroxyurethanes from cyclic
Organocatalytic Ring Opening Polymerization of carbonates and amines, Polym; 54, 2013, 5568-5573.
Trimethylene Carbonate, Biomacromolecules; 8, 2007,
[165] Schreiner P. R., Wittkopp A., H-Bonding Additives
153-160.
Act Like Lewis Acid Catalysts, Org Lett; 4, 2002, 217-220.
[156] Connor E. F., Nyce G. W., Myers M., Moeck A.,
[166] Jakab G., Tancon C., Zhang Z., Lippert K. M.,
Hedrick J. L., First Example of N-Heterocyclic Carbenes as
Schreiner P. R., (Thio)urea Organocatalyst Equilibrium
Catalysts for Living Polymerization: Organocatalytic Ring-
Acidities in DMSO, Org Lett; 14, 2012, 1724-1727.
Opening Polymerization of Cyclic Esters, J Am Chem Soc;
124, 2002, 914-915. [167] Sohtome Y., Tanatani A., Hashimoto Y., Nagasawa
K., Development of bis-thiourea-type organocatalyst for
[157] Dove A. P., Pratt R. C., Lohmeijer B. G. G., Culkin D.
asymmetric Baylis-Hillman reaction, Tetrahedron Lett;
A., Hagberg E. C., Nyce G. W., Waymouth R. M., Hedrick
45, 2004, 5589-5592.
J. L., N-Heterocyclic carbenes: Effective organic catalysts
for living polymerization, Polymer; 47, 2006, 4018-4025. [168] Pratt R. C., Lohmeijer B. G. G., Long D. A., Lundberg
P. N. P., Dove A. P., Li H., Wade C. G., Waymouth R. M.,
[158] Enders D., Niemeier O., Henseler A.,
Hedrick J. L., Exploration, Optimization, and Application
Organocatalysis by N-Heterocyclic Carbenes, Chem Rev
of Supramolecular Thiourea−Amine Catalysts for the
(Washington, DC, U S); 107, 2007, 5606-5655.
Synthesis of Lactide (Co)polymers, Macromol; 39, 2006,
[159] Ashton P. R., Calcagno P., Spencer N., Harris K. D. 7863-7871.
M., Philp D., Using Polarization Effects to Alter Chemical
[169] Lippert K. M., Hof K., Gerbig D., Ley D., Hausmann
Reactivity: A Simple Host Which Enhances Amine
H., Guenther S., Schreiner P. R., Hydrogen-Bonding
Nucleophilicity, Org Lett; 2, 2000, 1365-1368.
Thiourea Organocatalysts: The Privileged 3,5-
[160] Kobayashi S., Kikuchi H., Uyama H., Lipase- Bis(trifluoromethyl)phenyl Group, Eur J Org Chem; 2012,
catalyzed ring-opening polymerization of 1,3-dioxan-2- 2012, 5919-5927.
one, Macromol Rapid Commun; 18, 1997, 575-579.
[170] Blain M., Jean-Gerard L., Auvergne R., Benazet D.,
[161] Bisht K. S., Svirkin Y. Y., Henderson L. A., Gross R. Caillol S., Andrioletti B., Rational investigations in the
A., Kaplan D. L., Swift G., Lipase-Catalyzed Ring-Opening ring opening of cyclic carbonates by amines, Green
Polymerization of Trimethylene Carbonate, Chem; 16, 2014, 4286-4291.
Macromolecules; 30, 1997, 7735-7742.
[171] Blain M., Yau H., Jean-Gerard L., Auvergne R.,
[162] Zhang L., Pratt R. C., Nederberg F., Horn H. W., Rice Benazet D., Schreiner P. R., Caillol S., Andrioletti B., Urea-
J. E., Waymouth R. M., Wade C. G., Hedrick J. L., Acyclic and Thiourea-Catalyzed Aminolysis of Carbonates,
Guanidines as Organic Catalysts for Living Polymerization ChemSusChem; 2016, Ahead of Print.
of Lactide, Macromolecules (Washington, DC, U S); 43,
[172] Ochiai B., Satoh Y., Endo T., Nucleophilic
2010, 1660-1664.
polyaddition in water based on chemo-selective reaction

24
of cyclic carbonate with amine, Green Chem; 7, 2005, [181] Buergel T., Fedtke M., Epoxy resins with cyclic
765-767. carbonate structures: model studies for amine curing,
Polym Bull (Berlin); 30, 1993, 61-68.
[173] Proempers G., Keul H., Hoecker H., Polyurethanes
with pendant hydroxy groups: Polycondensation of D- [182] Lu Q.-W., Hoye T. R., Macosko C. W., Reactivity of
mannitol-1,2:5,6-dicarbonate with diamines, Des common functional groups with urethanes: Models for
Monomers Polym; 8, 2005, 547-569. reactive compatibilization of thermoplastic polyurethane
blends, Journal of Polymer Science Part A: Polymer
[174] Carre C., Bonnet L., Averous L., Original biobased
Chemistry; 40, 2002, 2310-2328.
nonisocyanate polyurethanes: solvent- and catalyst-free
synthesis, thermal properties and rheological behaviour, [183] Clements J. H., Reactive Applications of Cyclic
RSC Adv; 4, 2014, 54018-54025. Alkylene Carbonates, Ind Eng Chem Res; 42, 2003, 663-
674.
[175] Maisonneuve L., More A. S., Foltran S., Alfos C.,
Robert F., Landais Y., Tassaing T., Grau E., Cramail H., [184] Beniah G., Liu K., Heath W. H., Miller M. D., Scheidt
Novel green fatty acid-based bis-cyclic carbonates for K. A., Torkelson J. M., Novel thermoplastic
the synthesis of isocyanate-free poly(hydroxyurethane polyhydroxyurethane elastomers as effective damping
amide)s, RSC Adv; 4, 2014, 25795-25803. materials over broad temperature ranges, European
Polymer Journal; 2016,
[176] Fleischer M., Blattmann H., Mulhaupt R., Glycerol-,
pentaerythritol- and trimethylolpropane-based [185] Cornille A., Michaud G., Simon F., Fouquay S.,
polyurethanes and their cellulose carbonate composites Auvergne R., Boutevin B., Caillol S., Promising
prepared via the non-isocyanate route with catalytic mechanical and adhesive properties of isocyanate-free
carbon dioxide fixation, Green Chemistry; 15, 2013, 934- poly(hydroxyurethane), Eur Polym J; 2016,
942.
[186] Dolci E., Michaud G., Simon F., Boutevin B.,
[177] Caplow M., Kinetics of carbamate formation and Fouquay S., Caillol S., Remendable thermosetting
breakdown, J Amer Chem Soc; 90, 1968, 6795-6803. polymers for isocyanate-free adhesives: a preliminary
study, Polym Chem; 6, 2015, 7851-7861.
[178] Astarita G., Marrucci G., Gioia F., Influence of
carbonation ratio and total amine concentration on [187] Grignard B., Thomassin J. M., Gennen S., Poussard
carbon dioxide absorption in aqueous L., Bonnaud L., Raquez J. M., Dubois P., Tran M. P., Park
monoethanolamine solutions, Chem Eng Sci; 19, 1964, C. B., Jerome C., Detrembleur C., CO2-blown
95-103. microcellular non-isocyanate polyurethane (NIPU)
foams: from bio- and CO2-sourced monomers to
[179] Blain M., Jean-Gérard L., Benazet D., Boutevin B.,
potentially thermal insulating materials, Green Chem;
Andrioletti B., Caillol S., Synthesis of aminotelechelic
18, 2016, 2206-2215.
prepolymers to circumvent the carbonation of amines in
epoxy coating, Macromol Mater Eng; 301, 2016, 682- [188] Poussard L., Mariage J., Grignard B., Detrembleur
693. C., Jérôme C., Calberg C., Heinrichs B., De Winter J.,
Gerbaux P., Raquez J. M., Bonnaud L., Dubois P., Non-
[180] Huntsman, Technical, Bulletin, Jeffsol alkylene
Isocyanate Polyurethanes from Carbonated Soybean Oil
carbonates synthesis of hydroxyalkyl urethanes, 2005
Using Monomeric or Oligomeric Diamines To Achieve
Thermosets or Thermoplastics, Macromolecules; 49,
2016, 2162-2171.

25
[189] Gennen S., Grignard B., Thomassin J. M., Gilbert B., type nonisocyanate polyurethane coatings, Macromol
Vertruyen B., Jerome C., Detrembleur C., Symp; 187, 2002, 325-332.
Polyhydroxyurethane hydrogels: Synthesis and
[197] Rokicki G., Lewandowski M., Epoxy resins modified
characterizations, European Polymer Journal; 2016,
by carbon dioxide, Angew Makromol Chem; 148, 1987,
Accepted manuscript.
53-66.
[190] Fortman D. J., Brutman J. P., Cramer C. J., Hillmyer
[198] Figovsky O. L., Hybrid nonisocyanate polyurethane
M. A., Dichtel W. R., Mechanically Activated, Catalyst-
network polymers and composites formed therefrom,
Free Polyhydroxyurethane Vitrimers, J Am Chem Soc;
US6120905 A, 2000.
137, 2015, 14019-14022.

[199] Carré C., Zoccheddu H., Delalande S., Pichon P.,

[191] Rix E., Grau E., Chollet G., Cramail H., Synthesis of
Avérous L., Synthesis and characterization of advanced
fatty acid-based non-isocyanate polyurethanes, NIPUs, in
biobased thermoplastic nonisocyanate polyurethanes,
bulk and mini-emulsion, European Polymer Journal;
with controlled aromatic-aliphatic architectures,
2016, Accepted manuscript.
European Polymer Journal; 2016, Accepted manuscrit.
[192] Matsumoto K., Kokai A., Endo T., Synthesis and
[200] Figovsky O., Shapovalov L., Birukova O., Leykin A.,
properties of novel poly(hydroxyurethane) from
Modification of epoxy adhesives by hydroxyurethane
difunctional alicyclic carbonate and m-xylylenediamine
components on the basis of renewable raw materials,
and its possibility as gas barrier materials, Polymer
Polym Sci, Ser D; 6, 2013, 271-274.
Bulletin; 73, 2015, 677-686.

[201] Assumption H. J., Mathias L. J.,

[193] Blain M., Cornille A., Boutevin B., Auvergne R.,
Photopolymerization of urethane dimethacrylates
Andrioletti B., Caillol S., Hydrogen bonds prevent
synthesized via a non-isocyanate route, Polymer; 44,
obtaining high molar masses PHUs, J Appl Polym Sci;
2003, 5131-5136.
2016, Submitted mansucript.

[202] Figovsky O., Shapovalov L., Buslov F., Ultraviolet

[194] Figovsky O. L., Hybrid nonisocyanate polyurethane
and thermostable non-isocyanate polyurethane
network polymers and composites formed therefrom,
coatings, Surf Coat Int, Part B; 88, 2005, 67-71.
WO9965969A1, 1999.

[195] Figovsky O., Shapovalov L., Blank N., Buslov F.,

Synthesis of polyaminofunctional hydroxyurethane
oligomers and crosslinkers for coatings and sealants,
EP1070733A1, 2001.

[196] Figovsky O. L., Shapovalov L. D., Features of

reaction amino-cyclocarbonate for production of new

26
Graphical Abstract

27
Captions

Scheme 1: Synthesis of polyurethane in a two-step process

Scheme 2: NIPU routes

Scheme 3: Mechanism of cyclic carbonate/amine reaction

Scheme 4: Reactivity of various amines toward ether-CC5 at room temperature [134]

Scheme 5: Different catalytic mechanisms of cyclic carbonate aminolysis

Scheme 6: Possible reactions between 5-membered cyclic carbonate and amine: (1) classic
aminolysis, (2) carbonation of amine, (3) CO2-in-situ formation, (4) urea formation by trans-
urethanization, (5) amidification reaction and (6) oxazolidinone formation by dehydration

Scheme 7: Outlooks of synthesis routes for PHUs at room temperature and their industrial
applications

Scheme 8: Diglycerol effect on the PHU chains mobility

Scheme 9: Synthesis of PHU foam by reaction between cyclic carbonates, di-amines, blowing
agent (MH 15) and catalyzed with thiourea

Scheme 10: Methods to synthesize H-NIPUs from (A) the crosslinking of partially carbonated
epoxide monomers; the crosslinking of PHU prepolymers with carbonate (B) or amine (B’)
end groups; or (C) the crosslinking of hydroxyurethane modifiers (HUM).

Scheme 11: Synthesis of mono- and bis-urethane methacrylate

Figure 1: Properties of polyurethane range [1]

Figure 2: Increasing of electrophilicity of cyclic carbonate in presence of protic solvent

Figure 3: Time-conversion curves in the reaction with (A) CC5 or CC6 carrier of different
substituents (Aliphatic, Ether or Ester) and hexylamine at 50°C, 1 mol.L-1 in DMO-d6 [82] and
(B) CC5 carrier of different substituents and hexylamine at 70°C, 1 mol.L -1 in DMSO-d6 [79]

Figure 4: Structure of TBD and thiourea catalysts

28
Sylvain Caillol was born in 1974 in France. He received his M. Sc. Degree in Chemistry from the Engineering School of
Chemistry of Montpellier in 1998. Then he received his PhD degree in Polymer Science in 2001 from the University of
Bordeaux. Subsequently he joined Rhodia group and headed the Polymer Department in the Research Center of
Aubervilliers. In 2007 he joined CNRS in the University of Montpellier where he started a new research topic dedicated to
Green Chemistry and Specialty Polymers. He is Deputy Director of Carnot Institute “Chimie Balard”. Co-authors of several
articles, patents and books, he won the Innovative Techniques for Environment award.

29