RSC Advances

View Article Online

REVIEW View Journal

Non-isocyanate polyurethanes: from chemistry to

applications
Cite this: DOI: 10.1039/c2ra21938g
Mukesh S. Kathalewar, Padmanabh B. Joshi, Anagha S. Sabnis* and Vinod C. Malshe
Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G

Conventional polyurethanes involve the use of isocyanates, which require hazardous and toxic phosgene for
their manufacture. These monomers cannot be manufactured without elaborate safety devices and huge
investment. Isocyanates are also considerably toxic and moisture sensitive. Growing global awareness of the
need to protect our environment and continually strive to ensure the safety, health and well-being of those in
Downloaded by Stanford University on 21 February 2013

Received 24th August 2012,
Accepted 28th November 2012
DOI: 10.1039/c2ra21938g
www.rsc.org/advances
the industry and consumers has created a demand for environment-friendly products. The cyclic carbonate–
primary amine addition reaction which results in hydroxyurethanes is a unique reaction and has been
extensively studied over the last few years. This chemistry is now attracting research interest due to its potential
application in the preparation of ‘‘green’’, non-porous, moisture-insensitive, isocyanate free polyurethanes. This
review focuses on catalysis, the mechanism involved in the formation of Non-Isocyanate Polyurethanes (NIPU)
from five-membered cyclic carbonates and the reaction kinetics for their synthesis. The higher homologues of
the cyclic carbonate family, the six-membered cyclic carbonates, are similar to, but more reactive than, the five-
membered cyclic carbonates and can also serve as a source for production of isocyanate free polyurethanes. This
review also summarizes various application of NIPU in coatings, composites, construction and biochemical fields.

Introduction order to eliminate environmental and health hazards, while

Coatings have achieved widespread use in a variety of
applications and are continuously under development in
Department of Polymer & Surface Engineering, Institute of Chemical Technology,
Mumbai-400 019, India. E-mail: as.sabnis@ictmumbai.edu.in; Fax: (+91) 022-3361
1020; Tel: (+91) 022-3361 2416
keeping performance levels as high as possible.1 Two
component coatings are widely used and use various chemis-
tries. Of these chemistries with wide applications, polyur-
ethane (PUR) materials based on isocyanate–hydroxyl
chemistry (Scheme 1) have increased significantly in compar-
ison with other thermosetting polymer materials. These

Mukesh S. Kathalewar, born in Padmanabh B. Joshi, born in

1987, has completed a Master’s
degree in Technology in the field
of Surface Coating Technology
from the Institute of Chemical
Technology, Mumbai. He
worked on ‘‘Studies in Non-
Isocynate Polyurethanes’’ for
his Master’s thesis under the
guidance of Dr A. Sabnis. He
was recently awarded a junior
research fellowship and has
joined Dr Sabnis’s research
Mukesh S. Kathalewar group as a PhD candidate. His
current areas of research include utilization of bio-based materials
for coating application, recycling of polymeric waste for synthesis
of novel monomers and polymers etc. He is also interested in the
field of UV curable coatings, fire protective coatings and emulsion
polymers.
1989 in Maharashtra, India,
completed his Bachelor in
Technology degree in the field
of Surface Coating Technology
in 2010 from the Institute of
Chemical Technology, Mumbai.
Currently he is pursuing a PhD
degree in Chemistry at the
University of Cincinnati,
Cincinnati, Ohio, USA. His cur-
rent areas of research are synth-
esis of conjugated polymers and
Padmanabh B. Joshi synthesis of conjugated polymer
nanoparticles applied for fluorescence bio-imaging. He is also
investigating areas of materials science, such as synthesis of
mesoporous silica based nanomaterials, metal enhanced fluores-
cence and metal enhanced singlet oxygen production from
photosensitizer.

This journal is ß The Royal Society of Chemistry 2013 RSC Adv.

 View Article Online

Review RSC Advances

Scheme 2 Schematic illustration of the reaction between isocyanates and

Scheme 1 Reaction between isocyanates and hydroxyl groups. water.

Non-isocyanate polyurethanes (NIPU)

conventional polyurethanes possess high elasticity, abrasion
resistance and other outstanding properties, but suffer from
some grave problems.2,3
Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G
In 1957, Dyer and Scott reported the use of ethylene carbonate
for the preparation of polymeric urethanes.8 They found that
bis(2-hydroxyethyl carbamate)s, obtained from ethylene carbo-

Toxicity of isocyanates
Isocyanates are synthesized from an even more toxic pre-
decessor, phosgene, which causes environmental hazards.
Exposure to isocyanates4 can result in health effects, such as
skin irritation and long-term asthma.5
Downloaded by Stanford University on 21 February 2013
nate and primary diamines, tend to lose ethylene glycol when
subjected to vacuum distillation with an alcohol at 150 uC in
the presence of barium oxide or zinc borate as catalysts
(Scheme 3). Here, the alcohol group might be part of the bis(2-
hydroxyethyl carbamate) or part of a diol. They also obtained

polyurethane from bis(2-hydroxyethyl carbamate), prepared

Moisture-sensitivity
During the formation and storage processes of moisture
curing PUR coatings, the reaction between isocyanate and
water is troublesome. In such systems, until the coatings are
applied to the surface, careful isolation of these materials from
water becomes extremely important. Otherwise, the polyiso-
cyanate component and water would undergo an irreversible
reaction, forming a urea and CO2 resulting in a hardened,
unusable product (Scheme 2).3,6
Inferior hydrolytic stability
Conventional polyurethanes have an inherent weakness in the
back bone due to their molecular structure. The polymer
structure has hydrolytically unstable bonds that makes it
vulnerable to environmental degradation. This inherent
weakness in weatherability and poor chemical resistance has
become a serious challenge for their long term survival.2,6,7
from ethylene carbonate and 1,6-diaminohexane. Attempts to
apply this synthesis to the preparation of N-substituted
polyurethanes by starting with secondary diamines were
unsuccessful. In addition, they prepared N-substituted poly-
urethanes from amino alcohols, i.e. 1,10-aminodecanol or
4-aminomethylbenzyl alcohol, and ethylene carbonate via the
formation of intermediates (Scheme 3). Rokicki et al. also
prepared polyurethanes via a similar transurethanization
reaction of bis(2-hydroxyethyl carbamate)s, obtained from
ethylene carbonate and 1,4-diaminobutane or 1,6-diaminohex-
ane, with 1,6- hexanediol or 1,10-decanediol in the presence of
tin catalysts.9 They characterized the polyurethanes and found
that the polymers, besides their urethane groups, showed urea
groups as well.10,11
Another route for the preparation of urethanes is through
the transesterification reaction of urea and ethyl alcohol. Ethyl
urethane (C2H5)OCONH2 is an industrial solvent prepared by
this method and is commercially available. Based on this
observation, Malshe12 suggested using this chemistry to

Anagha S. Sabnis, born in 1975, Vinod C. Malshe, born in 1947,

received her PhD in Paint Technology
from University Department of
Chemical Technology, University of
Mumbai, in 2006. She worked in a
reputed MNC for 2 and a half years,
before joining the same institute as
Assistant Professor of Paint
Technology in the Department of
Polymer & Surface Engineering. She
has worked in the field of coatings,
adhesives and sealants. Presently her
research group consists of 1 PhD and
Anagha S. Sabnis 14 master students. Her research
interests include polymer synthesis from renewable resources, water
based binders, coatings, chemical recycling of polymer waste for coating
and allied applications etc.
received his MSc (Tech) and PhD
(Tech) from Bombay University,
India. As professor of Paint
Technology at the Department of
Polymer & Surface Engineering,
University Institute of Chemical
Technology (UICT/UDCT), Mumbai,
he supervised 18 PhD and 12
Master’s students. He has several
international research publications
and patents to his credit. Before
joining academia, he worked at
Vinod C. Malshe various senior levels in reputed
industries for 18 years. He is also on the editorial board of some
polymer and coating related international journals. Since his retirement
in 2007, he works as an independent consultant for several paint and
polymer industries.

RSC Adv. This journal is ß The Royal Society of Chemistry 2013


RSC Advances
Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G
Scheme 3 Preparation of hydroxyurethanes from carbonates.
Downloaded by Stanford University on 21 February 2013
prepare diols that could be cured with conventional technol-
ogies, since in most curing reactions the isocyanates are used
as chain extenders and produce urethane or biureate linkages
in the backbone. Mandlecha attempted the synthesis of diols
from ethanolamine, ethylene glycol and urea. He observed that
carbon dioxide is the first dicarboxylic acid. Its diester is
dimethyl carbonate; its half ester half amide is urethane. Since
it is a diacid, its products do appear as polycarbonate and half
ester and half amides appear as PURs. He synthesized a series
of diols by the reaction of urea and monoethanolamine and
urea and ethylene glycol, producing high viscosity diols that
could be crosslinked with melamine formaldehyde or diiso-
cyanates, producing hard and flexible coatings (Scheme 4(a)).
Thus, coatings with urethane like properties could be
Scheme 4 (a) Reactions of ethanolamine–urea and ethylene glycol–urea. (b)
Formation of other products from reaction of urea and ethylene glycol.
This journal is ß The Royal Society of Chemistry 2013
View Article Online
Review
produced either without any use of diisocyanates or with very
little use of diisocyanates, reducing the risk of using
diisocyanates considerably.13 However, such reactions are also
prone to give undesired products, such as carbamates,
ethylene urea, ethylene carbonate, 2-oxazolidone etc.
(Scheme 4(b)).14–16
The reaction of cyclic carbonate and amine is traditionally
known to produce hydroxyurethanes and is nowadays seen as
the best possible alternative for PUR synthesis.17 The five and
six membered cyclic carbonates undergo addition reactions
with amines resulting in the formation of hydroxyurethanes.
Most often, the reaction results in two isomers, each contain-
ing a urethane and a hydroxyl group, wherein one has a
secondary b-hydroxyl group, while the other has a methylol
group. These hydroxyl groups are capable of forming
intermolecular hydrogen bonds with the urethane group.
(Scheme 5).2,18,19
The intramolecular hydrogen bond blocks the carbonyl
carbon resulting in low susceptibility of the whole urethane
group to hydrolysis and hence improved hydrolytic stability,
well above that of conventional PURs, could be achieved.
Moreover, materials containing intramolecular hydrogen
bonds display chemical resistance 1.5–2 times greater than
materials having similar chemical structure without such
bonds.2 NIPUs exhibit improved thermal stability because
there are no thermally labile biuret and allophanate groups
incorporated in the PUR backbone. Further, NIPU synthesis is
not sensitive to moisture and hence application of the coating
is not as tedious as that of conventional PUR.20 With
increasingly strict regulations and the need for more envir-
onmentally-friendly technology for polymer synthesis,
researchers all over the world are now exploring the utilization
of cyclic carbonate–amine chemistry to prepare high perfor-
mance polymers for coatings, adhesives, foams etc. Use of
cyclic carbonates for coatings which serve the dual purposes of
carbon dioxide capture and environmental advantages should,
therefore, be an important area of research. The purpose of
this review is to provide researchers engaged in this field with
comprehensive information in one place. In this review, we
discuss various routes for PUR synthesis from cyclic carbo-
nates, catalysis for this reaction, kinetics of this reaction and
its applications in various fields.
Synthesis of NIPUs
Most of the published work on NIPU preparation is based on
cyclic carbonate oligomers/polymers. The general method for
preparation of NIPU comprises the synthesis of cyclic
carbonates, followed by their reaction with amines or
polyamine compounds.
Stage I: Synthesis of cyclic carbonate oligomers
Cyclic carbonates are the primary reactants in the synthesis of
NIPU and can be prepared by various methods. Among these,
chemical fixation of CO2 over corresponding epoxy precursors
has been extensively studied. The epoxy groups can be readily
RSC Adv.

Review
Scheme 5 Reaction of cyclic carbonate and amine.
Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G
modified with the addition of CO2 over the epoxide ring at
elevated temperature and in the presence of a catalyst
(Scheme 6). The cyclic carbonate moiety thus prepared opens
up in favorable reaction conditions and can be utilized to
Downloaded by Stanford University on 21 February 2013
synthesize linear or cross-linked NIPU networks depending on
the cyclic carbonate functionality of the oligomer.21 Oxirane to
cyclic carbonate conversion also utilizes CO2 as a sustainable
solvent which is non-flammable, has low toxicity, is an
inexpensive by-product of most industries and is abundant.
It also acts as an aprotic solvent in the reaction system.22
Stage II: Preparation of NIPU or hybrid-NIPU (HNIPU)
Cyclic carbonate containing oligomers form NIPU with amines
or polyamines via a simple ring opening addition reaction.
This type of addition reaction proceeds very slowly at room
temperature and is less exothermic than the epoxy–amine
reactions. Higher temperatures are considered to be more
effective. The aliphatic amines/polyamines are expected to give
better reactivity with cyclic carbonates compared to aromatic
ones.23 The polyamines should contain at least two primary
amine groups in order to form a polymer network with a
multifunctional cyclic carbonate oligomer or polymer, while
secondary and tertiary amine groups are not preferred for this
particular reaction. Ethylenediamine, hexamethylenediamine,
tris(2-aminoethyl)amine and polyamines such as polyoxypro-
pylene diamines, polyoxypropylene triamine etc. could be
used.3,24,25
Depending upon the structure of the backbone and type of
cross-linker used for the reaction, the properties of the
polyurethane network vary. If the cyclocarbonate oligomer
used has only cyclocarbonate functionality, then it is said to be
NIPU, whereas if the cyclocarbonate backbone containing
epoxy, hydroxyl and other functional groups, this gives the
polyurethanes which are termed HNIPU. The overall properties
Scheme 6 Synthesis of cyclocarbonate oligomers (R = long chain oligomeric
unit).
RSC Adv.
View Article Online
RSC Advances
of these two types of polymer are different due to different
backbone structures.18–20 The amine functional hydroxyur-
ethanes can be prepared using excess amine or diamine, in
which two amine groups have different reactivities, and can be
employed as crosslinkers or diluent for adhesives and
paints.26,27 Preparation of carbonate functional oligomers
from excess of a bis-carbonate of a bis-glycidyl ether of
neopentyl glycol and 1,4-cyclohexanediamethanol with poly-
oxyalkylene diamines has also been studied in the past.28
Reaction mechanism, catalysis and kinetics
Stage I: Synthesis of cyclic carbonate oligomers
Various types of reaction mechanisms and catalysts are
proposed for the synthesis of cyclic carbonates. The most
commonly used method is the ring opening and simultaneous
chemical insertion of CO2 into oxirane groups.29 This reaction
is highly facile and can be conducted at both atmospheric and
elevated pressure with high yields. The addition of CO2 to
oxiranes is generally carried out in the presence of a catalytic
system that can initiate the reaction by activating either the
epoxide or carbon dioxide, or both at the same time. The
oxirane is typically activated by interaction of the oxygen atom
with a Lewis acid, followed by a nucleophilic attack, which
causes the opening of oxirane ring. Most catalytic systems that
have been investigated for this reaction contain Lewis acid
sites for the electrophilic activation of oxiranes and/or carbon
dioxide and Lewis base sites acting as nucleophiles.30
Triphenyl phosphine,31 nickel phosphine complexes,32 qua-
ternary ammonium compound and zinc chloride,33 guani-
dines, amines, quaternary phosphonium compounds such as
ethyltriphenyl phosphonium bromide, tetraphenyl phospho-
nium chloride, methoxymethyl triphenyl phosphonium chlor-
ide etc.34 have previously been studied as catalysts. In addition,
some well-defined homogeneous metal complexes have been
reported to be highly active and selective catalysts. These
include aluminum salen,35 discrete zinc phenoxides, b-dimin-
ate zinc alkoxides and chromium salen catalysts, and
especially binary or bifunctional catalyst systems based on
cobalt(III) complexes are reported to be very efficient catalysts
at lower temperature.36,37 An organo tin based tetralkylpho-
sphonium halide complex was also used to achieve about 90–
100% conversion.38 Other catalysts such as KBr, LiBr,39 NaI40
etc., being insoluble or only partially soluble, resulted in very
This journal is ß The Royal Society of Chemistry 2013

RSC Advances
low to medium conversions,4,41 but in the presence of a crown
ether, such as 18-crown-6, KI acts as very efficient catalyst.42 Of
various other catalysts investigated for the reaction, the most
commonly used catalyst is tetraalkylammonium halide.
Tetrabutylammonium bromide (TBAB) at 5% molar concen-
tration with respect to epoxy content has been reported to give
maximum conversion to cyclic carbonates. It is also observed
that the catalytic activity of such quaternary ammonium salts
increases when the nucleophilicity of the halide anion and
Lewis acidity of the cation increases. The proposed mechan-
ism for cyclic carbonate formation is shown in Scheme 7.
Here, the rate determining step is the nucleophilic attack of
Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G
the halide anion on the oxirane ring. The reactivity of oxiranes
is also dependent on the type of substituents (R) attached to
the oxirane ring. As the bulkiness of substituents (R) on the
oxirane ring decreases or the electron withdrawing ability of R
increases, the reactivity of the oxirane increases. The oxiranes
and the cyclic carbonates are also observed to show the same
Downloaded by Stanford University on 21 February 2013
stereochemistry, as the SN2 type of inversion occurs during the
conversion.43 Kinetic analysis of the reaction shows that the
reaction rate can be expressed by the empirical equation eqn
(1):
{d½epoxide
~k½epoxide½catalystm
dt
where ‘‘m’’ depends on the Lewis acidity of the catalyst and
molecular weight of the epoxide polymer.44
Homogeneous TBAB catalyst gives good conversion to cyclic
carbonates, but requires tedious process of extraction of the
catalyst.45,46 The silica supported quaternary ammonium salt
is reported to give more efficient cyclic carbonate synthesis
under supercritical carbon dioxide conditions, where CO2 acts
both as a reagent and a solvent.21 Higher carbonate yield and
faster epoxy conversion with respect to those of homogenous
catalysts at atmospheric CO2 pressure could also be achieved
with silica supported catalysts.47 The Si–OH on the silica
surface acts as a weak acid to activate the epoxide, which
undergoes simultaneous nucleophilic attack by the halide
Scheme 7 Typical mechanism of cyclic carbonate formation using quaternary
ammonium salts.
This journal is ß The Royal Society of Chemistry 2013
View Article Online
Review
anion.48 In general, the silica supported ammonium salts have
higher catalytic activities than low molecular weight catalysts
under the same reaction conditions, probably due to the
synergistic effect between silica gel and quaternary ammo-
nium salts for the activation of CO2. The other advantage of
using silica-supported quaternary ammonium salts is that
these act as heterogeneous catalysts and can be easily
recovered by a simple filtration and reused more than four
times with slight loss of their catalytic activity.21 Recently, a
catalytic system of tetranuclear zinc cluster and tetrabutylam-
monium iodide for the synthesis of cyclic carbonates by
solvent free CO2 coupling under atmospheric pressure and
temperature was investigated, with the particular advantage
that the zinc cluster catalytic system showed high catalytic
activity and tolerance to impurities, including water and
oxygen.49
To overcome the problem of catalyst separation, various
solid catalysts, such as basic metal oxide,50,51 calcined
hydrotalcites52 and ion-exchange resins,53–55 have been devel-
oped. However, these heterogeneous systems are restricted
due to the formation of side products, as well as co-solvent or
co-catalyst requirements, low activity and high cost. However,
lanthanide oxychloride, especially SmOCl, is reported to show
(1) excellent activity and selectivity for the reaction of supercritical
CO2 and propylene oxide.56
In recent years, ionic liquid (IL) based heterogeneous
catalysts have attracted significant attention for the synthesis
of cyclic carbonates, as they give the advantages of both
homogeneous ILs and heterogeneous catalysts. Previously,
quaternary ammonium salts, alkali halides and imidazolium
alkyl halides immobilized on silica 55 or polymer supports 57,58
have been extensively explored for IL-based heterogeneous
catalysts with respect to the cycloaddition reaction. Carboxylic
acid functionalized imidazolium based ILs,59 modified amino
acid IL,60 silica-supported IL,61 chitosan supported ILs,
carboxymethyl cellulose supported ILs 62 etc. have been
studied effectively for cyclic carbonate synthesis. Recently, a
highly efficient catalytic synthesis of cyclic carbonates using
polymer supported diol functionalized ionic liquid was
reported. 63 The presence of a vicinal hydroxyl group on an
ionic liquid cation moiety has been observed to accelerate the
reaction in the forward direction, due to its strong chelating
ability, through hydrogen bonding with the oxygen atom of
epoxide, enabling the ring opening even more effectively than
ILs containing monohydroxyl groups.
Compared to heating by thermal energy, such as in an oil
bath, microwave irradiation is an effective heating mode
which affords a marked decrease in activation energy due to its
non-thermal effect. The rapid and solvent free synthesis of
cyclic carbonates from CO2 and epoxides under microwave
irradiation with controlled temperature and pressure has also
been reported.64 Pseudo-first order kinetics of the reaction
also suggested that the observed reaction acceleration under
microwave irradiation was mainly due to the non-thermal
effects of microwave, which lead to a decrease in activation
energy.
RSC Adv.

Review
Stage II: Synthesis of NIPU and HNIPU polymer
During the process of formation of NIPU, simultaneous
nucleophilic attack of amine over cyclocarbonate takes places
and is followed by a deprotonation reaction. In the first stage,
amine attacks the carboxyl group in cyclic carbonates,
resulting in the formation of a tetrahedral intermediate. The
reactions are observed to be slow at room temperature due to
the relatively stable nature of cyclic carbonates compared to
their oxirane counterparts.4 In the second stage, deprotona-
tion of the intermediate occurs through attack of another
amine, resulting in the removal of hydrogen ions. The carbon-
oxygen bond is then broken, which is favored by the strong
Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G
electron-withdrawing effect of nitrogen atoms.
Simultaneously, the newly generated alkyl-oxygen ion com-
bines with hydrogen ions, resulting in rapid formation of the
product.65 Such polyaddition reactions of cyclic carbonate and
amine generally give two isomers of hydroxyurethanes
Downloaded by Stanford University on 21 February 2013
(Scheme 8). The hydroxyurethane containing secondary
alcohol is formed predominantly whereas that containing
primary alcohol is formed in a small quantity. Moreover, the
selectivity of hydroxyurethane containing secondary alcohol
and that containing primary alcohol is found to be indepen-
dent of the reaction temperature, but somewhat dependent on
solvents and amines.66,67
Kinetic analysis investigated for the reaction of cyclic
carbonate and hexylamine revealed the second order kinetics.
The reaction rate constant (k) values were observed to increase
with the increasing electron withdrawing character of group
attached to the cyclic carbonate ring. This also resulted in
better reactivity and selectivity.68 Increasing reaction tempera-
ture was also observed to catalyze the reaction in the forward
direction, as suggested by increasing reaction rate.69,70
However, a further increase in temperature may result in the
formation of substituted urea through attack of another amine
molecule. When compared to oxiranes, the reaction rate of
cyclic carbonate had a lower activation energy and hence was a
less exothermic reaction than the epoxy–amine reaction.71 The
rate of the reaction of cyclic carbonates with amine also
depends on the initial concentration of the amines.72,73 The
Scheme 8 Reaction mechanism of reaction between cyclic carbonate and
amine.
RSC Adv.
View Article Online
RSC Advances
ring opening reaction of cyclic carbonates by amines may also
be accelerated by activating either the monomers, that is, by
additions of weakly Lewis acidic and oxophilic additives to
increase the electrophilicity of the cyclic carbonate group or
basic additives to increase nucleophilicity of amines. In 1958,
NaH and N-acetyl-e-caprolactam were first reported to lead to
formation of hydroxyurethanes.74 Meanwhile, many authors
have worked on catalysis of this particular reaction. Lewis
acids, such as LiCl, activate the carbonyl group without
deactivation of the amine, that is, the increased electrophili-
city of the activated cyclic carbonate by the appropriate Lewis
acids is hence the most plausible factor for the enhanced
yields of high molecular weight polyhydroxyurethanes.75 The
reaction can also be effectively catalyzed by use of triethyla-
mine which reduces the activation energy of the reaction by up
to 20% compared to that of the non-catalyzed system. Various
other catalysts, including piperazine, TBAB, glacial acetic acid,
methane sulfonic acid etc., can also be used effectively.76
Role of solvent (media) in synthesis of NIPU
and HNIPU
A) Protogenic solvents
In protogenic solvents, the limiting stage determining the
reaction order is the deprotonation stage, which stipulates
that the reaction is third order overall and second order with
respect to the amine. In this case, the first stage occurs
relatively rapidly due to the increase in the positive charge on
the carbonyl carbon atom resulting from the formation of
hydrogen bonds between solvent molecules and oxygen atoms
of the ring (Fig. 1).
B) Aprotic solvent
In aprotic solvents, the rate-controlling stage of the reaction is
the nucleophilic attack of the quaternary amine at the
carbonyl carbon of the ring. In this case, the solvent molecules
are not capable of forming the hydrogen bonds which favour
the first stage. This stage is limiting and determines the
overall second order of the reaction in aprotic solvents. The
presence of an electron-releasing substituent in the alkylene
carbonates results in a decrease in the partial positive charge
on the carbonyl carbon (Fig. 2). This results in a decrease in
the reactivity of the cyclic carbonate. Electron-withdrawing
Fig. 1 Effect of protogenic solvents on cyclic carbonate.
This journal is ß The Royal Society of Chemistry 2013

RSC Advances
Fig. 2 Decrease in the carbonyl carbon positive charge.
Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G
substituents, which increase the electrophilicity of the
carbonyl carbon, favour aminolysis at a higher rate.4
In aqueous conditions, the cyclic carbonates react with
amines at a relatively slower rate. In addition, the side
Downloaded by Stanford University on 21 February 2013
reactions, such as hydrolysis of cyclic carbonates, also need
to be considered while formulating water based systems. A
study investigating glycerol carbonate and aliphatic amines in
aqueous media revealed that higher temperature and the
presence of a base catalyst resulted in extensive hydrolysis of
glycerol carbonate. Moreover, the long chain amines provided
enough resistance to hydrolysis. At optimized conditions, two
isomers of hydroxyurethanes were obtained whose conversions
were dependent on the reaction temperature and ratio of
amine added.77
NIPU from various sources
1) NIPU from cyclic carbonate functional polymers
A primary interest of using cyclic carbonates is motivated by
the reaction of cyclic carbonates with amines yielding
hydroxyurethanes without use of isocyanates.41 Various low
and moderate molecular weight polyurethanes are used for
producing synthetic fibers, adhesives, paint-and-varnish mate-
rials, plastics, elastomers, foams, etc. Several methods are used
to synthesize five-membered cyclic carbonate compounds,
including reaction of alkali metal hydrogen carbonates with
oxiranes,78 transesterification of 1,2-glycols with ethylene
carbonate,79 dimethyl carbonate,80,81 reaction of oxiranes with
butyrolactone38 etc. However, the direct reaction of an epoxy
with carbon dioxide is most facile.
Vinyl ethylene carbonate (VEC) is one such cyclic carbonate
containing monomer which can introduce an intact carbonate
group in a vinyl polymer. VEC is prepared by the high pressure
addition of carbon dioxide into epoxy butene, a product of
butadiene epoxidation. (Table 1, entry 1). It can be copolymer-
ized with different acrylate monomers, such as methyl
methacrylate, ethyl acrylate, butyl acrylate and styrene, to
yield a copolymer with pendant cyclic carbonate groups.72,82
Another monomer is vinylene carbonate (Table 1, entry 2)
which is prepared from ethylene carbonate by a sequence of
chlorination and dehydrochlorination.. The addition of the
diamine to the cyclocarbonate would yield the urethane
containing compounds, which can be further modified and
incorporated into the coating formulation with unsaturation
This journal is ß The Royal Society of Chemistry 2013
View Article Online
Review
present on the backbone.83,84 Other example of cyclic
carbonate functional monomer is glycerol carbonate vinyl
ether (Table 1, entry 3) which can be prepared from glycidyl
vinyl ether using three different methods: reaction with CO2,
reaction with butyrolactone, and reaction with sodium
hydrogen carbonate.83,85
Some other examples of cyclocarbonate functional mono-
mers that can be used for the synthesis of the polyurethane
include propylene carbonate acrylate (PCA) (Table 1, entry 4),
propylene carbonate methacrylate (PCMA) (Table 1, entry 5),79
trimethylol propane tris(glycerol carbonate) ether (Table 1,
entry 7), TGIC carbonate (Table 1, entry 6)38 etc. Multi-alkylene
carbonates can also be prepared from epoxy resins via CO2
insertion. An example is the insertion of 3 moles of CO2 into
Heloxy Modifier 84 (Shell), a trifunctional epoxy-terminated
polyoxypropylene based on glycerol.79 The result is the
trifunctional alkylene carbonate shown in Table 1 (entry 8).
These materials are not yet commercially available. Table 1
shows general structures of some of the cyclic carbonate
functional monomers and oligomers.
These cyclic carbonates can also be synthesized by phosge-
nation in which hydroxyl containing compounds are phosge-
nated under excess pyridine (Scheme 9), but this route is now
replaced by other methods, due to the high toxicity and
corrosive nature of phosgene.86 Cyclic carbonates can also be
synthesized by reacting dimethyl carbonate with bis-hydroxyl
compounds containing hydroxyl groups at adjacent positions
in the presence of a metal oxide catalyst, such as MgO, CaO etc.
(Scheme 10).87,88
Glycerol carbonate (GC) is one of the most attractive
derivatives of glycerol which can be prepared from glycerol
via phosgenation or transesterification with dialkyl carbonates
such as dimethyl carbonate (DMC). This process represents a
genuine green synthesis, where the reaction of a renewable
material (glycerol) and a non-toxic compound (DMC)89–91 is
performed catalytically and in the absence of added solvents.
Various catalysts have been studied for this reaction, including
alkaline base catalyst, triethylamine81 metal oxides, hydro-
talcite,88 zeolites, enzyme based catalyst 92 etc. GC can also be
prepared by reaction of glycerol with urea, carbon dioxide, and
oxygen, or by reaction of carbon dioxide with glycidol. GC can
be reacted with anhydrides, acyl chlorides, isocyanates, and
similar. GC is modified via esterification with maleic
anhydride to generate an acid functional unsaturated cyclic
carbonate compound, which can be used as a monomer for
polymer synthesis using multiple functionality (Table 1, entry
9).79
Other methods for synthesis of cyclic carbonates include
chemical reactions of halohydrins, halogenated carbonates
and substituted propargyl alcohols (Scheme 11).18,87
In addition to mono-functional cyclic carbonates, bi-func-
tional cyclic carbonate oligomers are suitable for chemical
crosslinking in coatings and can serve as base resin, modifiers
or cross-linkers. These can be prepared through addition or
condensation reactions of cyclic carbonate containing com-
pounds with other functional oligomers or compounds. Bis-
cyclic carbonate derivatives can be synthesized by esterifica-
tion reactions from glycerol carbonate and dicarboxylic acid or
its derivatives. Five-membered dicyclic carbonate bis[(2-oxo-
RSC Adv.
 View Article Online

Review RSC Advances

Table 1 General structures of different cyclic carbonate functional compounds

Entry Name Structure Ref.

1 Vinyl ethylene carbonate 72,82

2 Vinylene carbonate 83,84

Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G

3 Glycerol carbonate vinyl ether 83,85

Downloaded by Stanford University on 21 February 2013

4 Propylene carbonate acrylate 79

5 Propylene carbonate methacrylate 79

6 triglycidyl isocyanurate (TGIC) carbonate 38

RSC Adv. This journal is ß The Royal Society of Chemistry 2013

 View Article Online

RSC Advances Review

Table 1 (Continued)

Entry Name Structure Ref.

7 Trimethylol propane tris(glycerol carbonate) ether 38

Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G

8 Multifunctional alkylene carbonate 79

Downloaded by Stanford University on 21 February 2013

9 Acid functional unsaturated cyclic carbonate 79

1,3-dioxolan-4-yl)methyl] benzene-1,4-dicarboxylate was pre-
pared by esterification of the carboxylic acid groups of
benzene-1,4-dicarboxylic acid with alcohol functionality of 4-
(hydroxymethyl)-1,3-dioxolan-2-one. However, the presence of
an ester linkage in the backbone makes them more sensitive to
hydrolysis reaction.93
Thioethers with bis-cyclic carbonates prepared by a one step
reaction by thiol-ene coupling of dithiol and glycerol carbonate
derivatives are also reported in the literature. This ‘‘click-
chemistry’’ reaction is particularly advantageous, since it
requires neither solvent nor photoinitiator and is quantitative
in stoichiometric conditions. Various bis-cyclic carbonates
prepared from 4-(3-butenyl)-1,3-dioxolan-2-one,94 4-ethenyl-
1,3-dioxolan-2-one95 and 4-[(prop-2-en-1-yloxy)methyl]-1,3-
dioxolan-2-one (Scheme 12) have been prepared.
Polyhydroxyurethanes synthesized by step growth poly addi-
tion reaction of these bis-cyclocarbonate oligomers contain
neither hydrolysis sensitive ester bonds nor UV sensitive

Scheme 9 Phosgenation reaction for cyclocarbonate synthesis. Scheme 10 Cyclocarbonate synthesis using dimethyl carbonate.

This journal is ß The Royal Society of Chemistry 2013 RSC Adv.


Review
Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G
Downloaded by Stanford University on 21 February 2013
Scheme 11 Carbonate synthesis by other methods.
aromatic groups and exhibit low glass transition temperature
(Tg) which could be used in exterior coatings application.
2) Synthesis of NIPU from epoxy resins
Epoxy resins are one of the most versatile classes of polymers
with diverse applications such as coatings, primer, adhesives,
composites etc. due to their excellent performance properties.
The most commonly used epoxy is the diglycidyl ether of
bisphenol-A (BPA) which possesses oxirane functionality at the
Scheme 12 Thioethers containing bis-cyclic carbonates.
RSC Adv.
View Article Online
RSC Advances
terminals. These oxirane functionalities can undergo the
addition of CO2 to yield corresponding bis-cyclic carbonate
functional oligomers (Scheme 13). The bis-cyclic carbonate of
BPA based epoxy was first reported by Rokicki et al. in 1989.96
Many studies have reported on the synthesis, catalysis and
application of this product. The cyclic carbonated epoxy resins
can be further modified or cured with amine functional
compounds to prepare high performance coatings.97 Other
epoxy based resins such as epoxy novalac resin (Scheme 14),
generally used for industrial coatings, can also be used to
prepare NIPU coatings.98,99 These products are expected to
possess excellent overall properties for coating and adhesive
applications. However, a limitation is poor exterior durability,
primarily resulting from direct absorption of UV radiation by
the aromatic ether groups, which ultimately leads to photo-
oxidative degradation. In addition, toxicity and exposure of
BPA is also a concern and has been a controversial issue
among scientists and various organizations.1 Recently, the
government of Canada has listed BPA amongst the ‘‘toxic’’
chemicals for humans and the environment.
Polyester based NIPU coatings can also be prepared.
Polyester resin prepared from adipic acid, hexanediol and
trimethylol propane was modified with epichlorohydrin to
incorporate epoxy functionality at the terminal position of
polymer chain. Epoxidized polyester was further modified as
cyclic carbonate containing polyester. This resin was then
thermally cured with isophorone diamine to produce high
performance coatings.100
A novel carbonate-modified bis(4-glycidyloxy phenyl) phenyl
phosphine oxide (CBGPPO) has been reported to prepare
phosphine oxide based polyurethane/silica nanocomposites.
Surface of the silica particles were modified with silane
coupling agent, (4-((3-(trimethoxysilyl)propoxy)methyl)-1,3-
dioxolan-2-one) (Si-CPS) to improve the compatibility between
silica particles and organic part, which was synthesized
successfully by the carbonate modification reaction of (3-
glycidyloxypropyl) trimethoxysilane (GPTMS). The cyclic car-
bonate resins, prepared from corresponding epoxy precursors,
were used to prepare nanocomposite formulations with 0–6
wt% silica content and 0–30 wt% CBGPPO (Scheme 15).
Incorporation of silica and CBGPPO into thermally cured
nanocomposite coatings was observed to increase modulus
and hardness of the coating, making the material more brittle.
It was also observed that the thermal stability of hybrid
coatings was enhanced with the addition of silica and
CBGPPO.101
3) Synthesis of NIPU from renewable sources
With increasing awareness of the environment, strict regula-
tions and restrictions on using many chemicals, researchers
and industries are forced to explore alternatives. Renewable
resources are naturally occurring sources which are abundant
and eco-friendly. Utilization of these resources is now
desirable and is being extensively studied all over the
world.102,103 Epoxidized soyabean oil (ESO) is available
commercially at a low price and is used as a plasticizer in
the PVC industry. ESO can be effectively converted to
carbonate soyabean oil (CSBO) containing five-membered
cyclic carbonates in high yields. CSBO could easily react with
This journal is ß The Royal Society of Chemistry 2013

RSC Advances
Scheme 13 Synthesis of cyclocarbonated epoxy resin.
Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G
Downloaded by Stanford University on 21 February 2013
Scheme 14 Synthesis of carbonated epoxy novalac resin.
amines, like ethylenediamine, hexamethylenediamine etc., to
give the corresponding NIPU networks (Fig. 3). NIPU can be
prepared with high tensile strength and other mechanical
properties which could be varied by the type of amine and
cyclocarbonate oligomer used.104
The latest study by Javani et al. revealed that aromatic
amines/diamines could be employed as hardeners for NIPU
systems. They used m-xylylenediamine, p-xylylenediamine and
aliphatic/cycloaliphatic diamines for curing reactions of cyclic
carbonated soyabean oil. The aromatic nature of the xylylene-
diamine reagent resulted in increased tensile strength with
inferior elongation compared to the aliphatic diamine.23
Recently, catalytic conversion of epoxide groups with carbon
dioxide was used to prepare carbonated linseed oil.105 In
addition to the homogeneous TBAB catalyst, the silica-
supported alkylpyridinium iodide SiO2–(I) was employed
Scheme 15 Synthesis of Si-CPS particles and CBGPPO.
This journal is ß The Royal Society of Chemistry 2013
View Article Online
Review
successfully to catalyze this carbon dioxide conversion reac-
tion and to enable facile catalyst recovery by filtration, thus
eliminating solvent extraction. In comparison to soya-based
(CSBO), the carbonate content of carbonated linseed oil
(CLSO) is substantially higher. Mixing together CSBO and
CLSO enabled variation of carbonate content in order to
explore the influence of curing agents and the carbonate
content on the thermal and mechanical properties of NIPU.
With increasing crosslink density, stiffness and Tg increased
significantly. Tg can be increased by using a cycloaliphatic
curing agent, isophorone diamine, for curing purpose.106 In
this case, Tg increased from 20 to 60 uC, while stiffness
increased by three orders of magnitude at the expense of
elongation at break. While most conventional CSBO-based
systems are rather soft and flexible, this approach indicates
that NIPU can be developed to meet the demands of
engineering applications with higher dimensional stability
and stiffness.
A disadvantage of these oil based NIPUs is that the cure
reaction is sometimes accompanied by cleavage of the ester
Fig. 3 General structure of CSBO.
RSC Adv.

Review
Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G
Downloaded by Stanford University on 21 February 2013
Scheme 16 Hydroxyurethanes from limonene.
groups, thus reducing network density and lowering tensile
strength. Hence, cyclic carbonate compounds without ester
linkages are preferred.107 The difunctional limonene dioxide,
originating from limonene, one of the forms of terpenes, is
used commercially as a reactive diluent for epoxy resin and as
a solvent (Scheme 16). Terpenes represent highly unsaturated,
ester-free renewable resources which are readily available on a
large scale and can provide much higher CO2 fixation. These
rigid monomers can improve the stiffness and heat distortion
temperature of NIPU. Due to high carbonate content and rigid
structure; the curing of limonene carbonate with polyfunc-
tional amines affords rigid and brittle NIPUs. This is reflected
by high Young’s modulus, high Tg and low elongation at
break.108
4) NIPU in nanotechnology
Nanostructured systems could be employed with NIPU
technology for superior performance. NIPU-SiO2 nanocompo-
sites are reported to give significant improvements in rigidity,
toughness and transparence. Cyclic carbonate functional SiO2
nanoparticles (Fig. 4) can be prepared from tetraethylorthosi-
licate and cyclic carbonated glycidoxy silanes via sol–gel
Fig. 4 Cyclic carbonate functional silica particles.
RSC Adv.
View Article Online
RSC Advances
Scheme 17 Synthesis of urethane precursor.
processes. These particles could be used as crosslinkers to
improve adhesion and reduce water absorption.109
NIPU technology can also be used for preparation of reactive
organic precursors. Synthesis of urethane containing organic
silane precursor from 3-aminopropyl trimethoxysilane
(APTMS) and cyclic carbonated glycidoxypropyl trimethoxy
silane (C-GPTMS) with triethylamine (TEA) as a catalyst is
reported. This precursor contains six hydrolysable methoxy
groups which could facilitate sol–gel processing. Organo-
inorganic hybrid sol–gel coatings were prepared using this
precursor, tetraethylorthosilicate and dimethoxy silicate and
were used for surface protection of aluminum alloys
(Scheme 17).110 The authors have also reported synthesis of
bis-urethane bis-silane precursor from C-GPTMS and 1,3-
propanediamne for the same application.111
NIPU from six-membered cyclic carbonates
Six-membered cyclic carbonates (6CC) are very similar to five-
membered cyclic carbonates and can be used efficiently for
polymer synthesis by various methods. These can be synthe-
sized through several different routes. Synthesis of 6CC such
as trimethylene carbonate is traditionally achieved by reacting
1,3-propanediol with phosgene or its derivatives. Although
cyclic carbonates can also be obtained by direct coupling of
CO2 with oxetanes at elevated temperature and pressure using
organometallic catalyst, the synthesis route of transesterifica-
tion of 1,3-diols with dialkyl carbonates is preferred, due to its
environmentally benign procedure.112 In this two-step synth-
esis, oligomers are generally formed. As the temperature is
increased, depolymerization of linear polycarbonates produces
the cyclic monomer which can be easily distilled off under
vacuum. Metallic base catalysts, stannous 2-ethylhexanoate,
chlorides, oxides and carbonates113 have been successfully
used for such reactions in the past.114 Trimethylol propane can
also be converted to 6CC with pendant functional groups via a
lipase mediated reaction between DMC without any cata-
lyst.115 The 6CC derivative prepared from trimethylol propane
This journal is ß The Royal Society of Chemistry 2013

RSC Advances
Table 2 Structures of 6CC containing compounds
Fig. No. Structure Ref.
1 116
2 116
Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G
Downloaded by Stanford University on 21 February 2013
3 117
4 116
5 118
6 119
7 120
8 121
This journal is ß The Royal Society of Chemistry 2013
View Article Online
Review
can be further modified to incorporate a desired structural
moiety (Table 2, entry 1–8) for specific applications. Table 2
summarizes some such products reported in the literature.
6CCs undergo ring-opening polymerization (ROP) to give
the corresponding linear polycarbonates without side reac-
tions and volume shrinkage, especially under anionic condi-
tions. These are preferred for ROP to five-membered
carbonates, as they are less thermodynamically stable than
their ring-opened polymers and thus retain CO2 during the
polymerization process.122,123 Under cationic conditions,
however, the polymerization is accompanied by partial/no
elimination of carbon dioxide to afford polycarbonates with an
ether unit.124–126 Five-membered cyclic carbonates do not
polymerize to yield polycarbonates, due to their stable five-
membered rings, while polyethercarbonates are formed by
partial decarboxylation and loss of CO2 in the presence of a
catalyst, such as metal alkoxides, metal acetylacetones and
metal alkyls.127 However, they efficiently react with amines to
give the corresponding hydroxyurethanes as discussed earlier.
Cyclic carbonates having larger ring sizes than five are
expected to show higher reactivity with amines and react
smoothly to give the corresponding hydroxyurethanes, hence
six- and seven-membered cyclic carbonates show much higher
polymerization rates than five-membered ones.128 Five-mem-
bered cyclic carbonates react relatively slowly with amines
particularly at ambient temperature while annealing causes
yellowing of the polymers. The molecular weights of the
obtained polyhydroxyurethanes are also relatively low com-
pared to the commercial polyurethanes obtained from di-
isocyanates and diols. These drawbacks have limited the
worldwide usefulness and expansion of the polyhydroxyur-
ethanes.129
The comparative reaction kinetics of five- and six-mem-
bered cyclic carbonates has also been investigated and is
available in the literature. The equivalent reaction of the six-
membered cyclic carbonates, 5-(2-propenyl)-1,3-dioxan-2-one,
and five-membered cyclic carbonate, 4-(3-butenyl)-1,3-dioxo-
lan-2-one with hexylamine and benzylamine (Scheme 18)
carried out in N,N-dimethylacetamide at 30, 50, and 70 uC
without catalysts has been reported.130 The study revealed that
Scheme 18 Reaction of five- and six-membered cyclic carbonate.
RSC Adv.
 View Article Online

Review RSC Advances

6CCs resulted in corresponding hydroxyurethane with high

conversions at 30–50 uC, while five-membered cyclic carbonate
showed less than 50% conversions under similar conditions.
The reactivity of benzylamine was also found to be much lower
than hexylamine, probably due to lower basicity and steric
hindrance by the phenyl group (pKa of hexylamine and
benzylamine at 25 uC are 10.56 and 9.33 respectively). The
activation energy for the reaction of the 6CCs with hexylamine
was also smaller than that of the five-membered cyclic
carbonates. The low conversion of the five-membered cyclic
carbonate was also observed to be affected by the presence of a
donating solvent N,N-dimethylacetamide.
Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G

The reaction rate constants (k) values for these particular

reactions could be estimated by the following equation eqn (2):

2d[C]/dt = k[C][A] (2)

Downloaded by Stanford University on 21 February 2013

where [C] and [A] represent the concentrations of the cyclic

carbonate and amine, respectively.
Scheme 19 Syntheis of 5-ethyl-5-(((2-oxo-1,3-dioxolan-4-yl)methoxy) methyl)-
1/[C] 2 1/[C]o = kt at [C] = [A] (3) 1,3-dioxan-2-one (BC56).

This linear relationship suggested that the reactions

seemed to follow second-order kinetics with respect to the
concentrations of the cyclic carbonate and amine. The k value
of 6CCs was observed to be 29 to 62 times larger than that of
five-membered reactants, which supports the observations
discussed above.130
Similar trends were observed in the ring-opening polyaddi-
tion of bis(cyclic carbonate)s. 1,2-Bis[3-(1,3-dioxan-2-one-5-yl)-
propylthio]ethane (6BCC) and 1,2-bis[4-(1,3-dioxan-2-one-4-yl)-
butylthio]ethane (5BCC) (Fig. 5) with 4,9-dioxadodecane-1,12-
diamine have been polymerized. The reaction-rate constants
and Mn of the obtained polymer of the six-membered cyclic
carbonate were observed to be larger than those of the five-
membered one. It was suggested that the higher ring-strain of
the six-membered cyclic carbonate contributed to its higher
reactivity.131
Different reactivities of five-membered and six-membered
cyclic carbonates toward primary amines can also be utilized
for various purposes. This special property enables a coupler
containing both a five- and six-membered moiety to be used
for a selective linking of two functional amines within one
molecule and to form a bis(functional) compound—5-ethyl-5-
(((2-oxo-1,3-dioxolan-4-yl)methoxy) methyl)-1,3-dioxan-2-one
(BC56) prepared from ethyl chloroformate and 2-allyl-2-
propyl-1,3-propanediol (Scheme 19). On the other hand, both
five- and six-membered cyclic carbonates react with primary
amines to prepare hydroxyl functional polyurethanes.

Fig. 5 Structures of 6BCC and 5BCC. Scheme 20 Preparation of ionic, hydrophobic and hydrophilic coupler.

RSC Adv. This journal is ß The Royal Society of Chemistry 2013


RSC Advances
Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G
Scheme 21 New routes for synthesis of polyhydroxyurethanes.
Downloaded by Stanford University on 21 February 2013
Polymers with hydrophilic and hydrophobic alternating
diamine building blocks in the backbone can also be prepared
by adding different diamines in a two step process
(Scheme 20).132
Other non-conventional routes for NIPU
synthesis
Another typical synthetic route to polyurethane is the ROP of
cyclic urethane 133,134 The cationic ROP of trimethylene
urethane and tetramethylene urethane in a melt at 100 uC
yields poly(trimethylene urethane) and poly(tetramethylene
urethane) with a regular microstructure (Scheme 21(A)).135,136
As a new route to polyurethane, the copolymerization of 2,2-
dimethyltrimethylene carbonate with tetramethylene urea
results in the copolymer containing a urethane bond shown
in Scheme 21(B).137 The novel synthesis of thermoresponsive
polyurethane from 2-methylaziridine and supercritical carbon
dioxide to give a polymer with a high content of urethane units
and unique temperature-sensitive phase transitions in
water138,139 was recently reported (Scheme 21(C)).
Properties of non-isocyanate polyurethane
coatings
NIPU based coatings are generally two pack, low volatile
organic compound (VOC) coatings, non-porous, moisture
insensitive and safe to handle. The coatings possess greater
hydrolytic stability, adhesion, abrasive and chemical resis-
tance compared to conventional PU systems. Based on various
types of cross-linkers being used, the basic properties can be
varied. The stoichiometric carbonate-to-amine ratio produces
polymer networks of the highest density, glass transition
temperatures, hardness and tensile strengths. Non stoichio-
metric carbonate-to-amine ratios could result in lower values
This journal is ß The Royal Society of Chemistry 2013
View Article Online
Review
Table 3 Overall performance properties of HNIPU and conventional PUR
Properties Conventional PUR Hybrid NIPU
Solids (%) 76–100 85–100
Pot Life 4–6 h 4–6 h
Cure time 7 days at 18–22 uC 4 days at 18–20 uC
Pencil Hardness H–2H H–2H
Impact (Kg/cm) 40–50 50–60
Adhesion Mark 1–2 1
Coefficient of
Chemical Resistance:
H2SO4, 10% at 60 uC 0.75–0.80 0.90–0.95
NaOH, 10% at 60 uC 0.80–0.85 0.95–1.0
H2O, at 60 uC 0.85–0.90 0.95–1.0
of properties, except for elongation at break, which could be
highest for samples prepared with an excess of diamine. The
molecular weight of diamines also affects the properties in
different ways. Hardness and tensile strength are highest for
those with short chain diamines, such as ethylene diamine,
and lowest for long chain diamines, like hexamethylene
diamine, due to differences in cross-linking density and
hydrogen bonding.140,141 However, NIPU systems are not
suitable for room temperature curing, due to slow reaction
rates of cyclic carbonates compared to those of hydroxyl and
isocyanate reactions, hence curing at elevated temperature is
preferred. This limits the application of these systems to
obvious room temperature coatings such as floor, furniture,
maintenance of automotive and industrial adhesives. Table 3
shows the comparative performance of the conventional PUR
and the HNIPU coating system.142,143 The mechanical and
chemical performance was evaluated for coatings with
approximately similar film thickness. As can be seen, the
HNIPU coatings give very good mechanical and chemical
performance comparable to those of conventional PUR.
Advantages of NIPU over conventional PUR
The conventional method of producing linear and network
PUR is based on reaction of polyols and toxic isocyanates,
which are produced from an even more dangerous compo-
nent, phosgene. NIPU networks are obtained by a synthesis
route that uses diols, polyols, carbon dioxide and diamines,
which are far more environmental-friendly materials than
isocyanates and phosgene. This synthesis is also a step in the
direction of fixing excessive CO2 in coatings, already an area of
extensive research. Due to their unique molecular composi-
tion, NIPUs are transformed into a material with practically no
pores and, once formed, are not sensitive to the moisture on
surfaces. Hence, the care necessary when using diisocyanates
to avoid formation of carbon dioxide bubbles leading to
porosity is not required. Even during cure, the great care
required while using diisocyanates to exclude moisture from
atmosphere and the solvents is not necessary. Chemical
resistance of the NIPU coatings is also 30–50% greater than
that of conventional PUR coatings. The overall permeability is
RSC Adv.
 View Article Online

Review RSC Advances

Fig. 6 Structure of urethane glycol.

also reduced to a large extent due to its nonporous nature and

is 3–5 times less than that of conventional PUR.4,7
Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G

Applications of NIPU
As PUR has manifold applications in the coatings industry,
non-isocyanate based polyurethanes can also find various
Downloaded by Stanford University on 21 February 2013

applications in the coatings and polymer industry. NIPU

systems could be employed for thermosetting coatings, UV
stable coatings,144 monolithic floorings145 etc. The most
interesting way of increasing thermal stability of NIPU is
using difunctional hydroxyalkyl urethanes glycols (Fig. 6).
These glycols possess the potential to be used as diols in
relevant polymer chemistries.144,146,147
It is also possible to employ aminosilanes and cyclic
carbonates for preparing thermostable compounds. These
coatings can be used in nonporous monolithic coatings,
coverings and linings for corrosion protection and wear
protection of concrete, metallic and wood surfaces where
outstanding initial gloss, color retention, very good resistance
to chemical and/or marine environments is required.148 The
isocyanate-free coating also has an extended period of
corrosion protection, due to its non-porous structure which
assures effective protection against aggressive media and also
gives better durability than conventional PURs.143
Under exposure to light, a NIPU coating might gradually
turn yellow, which makes them unsuitable for transparent
applications. UV stable coatings can be prepared from acrylic
polymers containing cyclic carbonate groups with superior
mechanical properties.149 Low/zero VOC coatings with super-
ior properties can be obtained using waterborne polyurethane
dispersions by non-isocyanate chemistry, thus eliminating the
exposure hazards of working with isocyanate raw materials.
These PUR dispersions can also function as highly efficient
pigment dispersing resins by virtue of the presence of
hydroxyl, carboxyl and urethane functionality.150,151
Multifunctional alkylene carbonates prepared from GC and
the multifunctional isocyanate polymeric diphenylmethane
diisocyanate (MDI) in the presence of potassium acetate are
useful as blow promoters in the preparation of polymeric
foams or can be reacted with aliphatic diamines to prepare
polyurethane resins (Scheme 22).29
The significant difference in the reactivity of the aliphatic
amine versus the cycloaliphatic amine with alkylene carbo-
nates can be utilized to generate urethane adducts
(Scheme 23) with terminal amine groups, as only the aliphatic
Scheme 22 NIPU synthesis from multifunctional alkylene carbonate.
amine participates in reaction. This adduct can be reacted
with epoxy-urethane resins to form useful urethane coatings
without the need for isocyanates. 29
NIPU technology can also be employed in hydrolysis-stable
and gasoline-stable sealants for protection of electronic
devices and their components in aircraft and rocket construc-
tion and for civil engineering applications; glues with high
adhesion strength and longevity which can be used for joining
all types of materials, e.g., metals, ceramics, glass, etc.;
reinforced and highly-filled polymers for civil and chemical
engineering applications, and printing and finishing of
textiles.4,152 Recently, a UV curable PUR resin prepared by
NIPU chemistry utilizing long chain polyetheramine and cyclic
carbonate of bisphenol based epoxy resin was used for
hydrophilic textile treatment.153
NIPU based products can also be used as adhesive and
sealants, due to their excellent adhesive properties.154,155
Multifunctional methacrylates bearing urethane groups are
widely used in varnishes, inks and adhesives. Whilst they are
mostly used in radiation-curable formulations, these raw
materials also find uses in other systems. Urethane dimetha-
crylates as cross-linkers in anaerobic adhesives, urethane
monoacrylates as co-monomer in polyacrylics for laminating
adhesives and urethane di(meth)acrylates as flexibilizer in
protective coatings are some potential applications.156 Dendro-
aminosilane hardeners could also be used in NIPU sealant
preparation, which improve the thermal properties. High
adhesion to steel and glass (up to 47 MPa) and high impact
resistance can also be obtained on the basis of organosilane
pentacyclo-carbonate.157
Polymer nanocomposites (PNC), based on matrix polymer
and nano-scale inorganic constituents offer an alternative to

RSC Adv. This journal is ß The Royal Society of Chemistry 2013


RSC Advances
Scheme 23 Synthesis of urethane adduct.
Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G
conventionally filled polymers and composites. Due to their
nanometer phase dimensions, the nanocomposites exhibit
new and improved properties without sacrificing impact
resistance. A very interesting way of introducing nanoparticles
Downloaded by Stanford University on 21 February 2013
is to use compounds that can form nano-particles "in situ".
The use of organosilanes makes the possible. For example,
after hardening by cross-linking, NIPU network may be used as
a matrix of composite materials to serve as structural
components.154
NIPU network can be used as matrix for enzyme immobi-
lization. Low density polyethylene films co-grafted with
vinylene carbonate and N-vinyl-N-methylacetamide and matrix
for the immobilization of enzyme alkaline phosphates
prepared and immobilized either by direct fixation or by
inserting spacers is reported. When water soluble alkyldia-
mine such as ethylene diamine, diaminobutane, diethylene-
triamine, and hexamethylene diamine are used as the spacers
between matrix and enzyme, the surface concentration of
active enzyme coupled on the matrix is increased. Using this
technique enzyme immobilization can be performed success-
fully.158
Conclusion
The chemical industry is facing increasing demand for
environmentally benign and safe processes and products.
Ways are being investigated to reduce carbon dioxide
accumulation to avoid global warming. Production of iso-
cyanate-free polymers attracts increasing attention and has
great potential to avoid the use of toxic and environmentally
hazardous materials such as isocyanates and phosgene,
manufacturing of which is a capital intensive process. NIPU
materials open a window for the developing world by simple
reaction of epoxides with carbon dioxide. It also leaves the
option of using a large number of aromatic diamines as
components of structure that have been commercially avail-
able for the dyes and pigment industry.
New generation PURs based on isocyanate-free chemistry
can be used as replacement for conventional PURs and
successful implementation can be performed in different
fields of application. The design of molecular structure of
cyclic carbonates and their oligomers is essential for improv-
This journal is ß The Royal Society of Chemistry 2013
View Article Online
Review
ing the performance of NIPUs. Recent developments in
preparation of cyclic carbonates and their polymers hold
promise. Six-membered cyclic carbonates will provide great
opportunities in production of isocyanate-free polyurethanes.
A variety of cyclic carbonates bearing various functional
groups can be prepared and polymerized with tailor-made
properties for use in large volume industrial applications, as
well as in general and high-end materials. Reaction of
unsaturated components of polymer material with hydrogen
peroxide and subsequently with carbon dioxide is a very
promising green solution to the various problems of isocya-
nate and amine synthesis. This would lead to green coatings
that do not use hazardous phosgene and isocyanates, but rely
on simple, harmless molecules such as carbon dioxide and
hydrogen peroxide. The range of possible applications of these
monomers from renewable resources is likely to be expanded
as a result of the increasing interest of both industry and
academia.
Opportunities for research
Opportunities for research in this subject are enormous.
Catalysts for curing at room temperature are a challenge that
appears attainable. Nature produces several polyols and
hydroxylated monomers and polymers such as sugar, xylitol,
manitol, glucose, starch, cellulose and lignin. A starch
derivative abundantly manufactured is sorbitol. Possibilities
exist to convert part of the hydroxyl groups into carbonates to
generate sites for cross-linking. This could lead to a new
dimension of green chemistry. Researchers all around the
world may conduct extensive research in this area to find the
commercial applications of these systems for actual imple-
mentation.
References
1 S. Paul, Surface Coatings: Science and Technology, Second
Ed., Wiley & Sons, Australia1985.
2 P. Datir, PaintIndia, 2007, 57, 71.
3 V. C. Malshe andM. A. Sikchi, Basics of Paint Technology
Part-I, Antar Prakash Centre for Yoga, Uttarakhand,
India2008.
RSC Adv.

Review
4 O. Figovsky and L. Shapovalov, Paint Coating Industry,
June 2005.
5 D. J. David and H. B. Staley, ‘‘Analytical Chemistry for
Polyurethanes’’, XVI (III) Wiley Interscience with John
Wiley & Sons, New York, 1969.
6 M. LonescuChemistry and Technology of Polyol for
Polyurethanes, Rapra Technology Ltd. UK2005.
7 S. Sarkar, Special Chem, Sept.2007.
8 E. Dyer and H. Scott, J. Am. Chem. Soc., 1957, 79, 672.
9 G. Rokicki and A. Piotrowska, Polymer, 2002, 43(10), 2927.
10 V. Mikheev and L. Zainullina, Russian Journal of Applied
Chemistry, 1999, 72(8), 1454.
11 L. Ubaghs, N. Fricke, H. Keul and H. Hocker, Macromol.
Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G
Rapid Commun., 2004, 25(3), 517.
12 V. C. Malshe, Paintindia, 1992, 42(1), 7.
13 M. Mandlecha, Synthesis and characterization of Monomers
for Polymers and Membranes, Ph.D Thesis, University of
Mumbai, 1999.
14 B. M. Bhanage, S. Fujita, Y. Ikushima and M. Arai, Green
Downloaded by Stanford University on 21 February 2013
Chem., 2003, 5, 429.
15 B. Ochiai and T. Utsuno, J. Polym. Sci., Part A: Polym.
Chem., 2013, 51(3), 525.
16 G. Rokicki and A. Piotrowska, Polymer, 2002, 43, 2927.
17 J. Whelan, J. Cotter and J. Robert, US 3072613, 1963.
18 J. Guan, Y. Song, Y. Lin, X. Yin, M. Zuo, Y. Zhao, X. Tao
and Q. Zheng, Ind. Eng. Chem. Res., 2011, 50(11), 6517.
19 H. Yaocheng, L. Liyun, R. Xu and T. Bien, Progress in
Chemistry, 2011, 23(6), 1181.
20 L. Ubaghs, Isocyantes-free synthesis of (functional)
Polyureas, Polyurethanes and Urethane-containing
Copolymers, Ph.D Thesis, Institut für Technische und
Makromolekulare Chemie, Germany, 2005.
21 J. Wang, D. Kong, J. Chen, F. Cai and L. He, J. Mol. Catal.
A: Chem., 2006, 249, 143.
22 E. J. Beckman, J. Supercrit. Fluids, 2004, 28, 121.
23 I. Javani, D. Hong and Z. Petrovic, J. Appl. Polym. Sci.,
2012, DOI: 10.1002/app.38215.
24 B. Ochiai, S. Inoue and T. Endo, J. Polym. Sci., Part A:
Polym. Chem., 2005, 48, 6613.
25 A. Blessler, W. Smith and C. John, US Patent, US3084140,
1963.
26 E. Dieter, J. Christoph, B. Gerhard and W. Gerd, US Patent,
US4758615, 1988.
27 R. Leonid Roger, US Patent, US5175231, 1992.
28 C. Wheeler and M. Edward Howard, US Patent,
US5340889, 1994.
29 J. H. Clements, Ind. Eng. Chem. Res., 2003, 42(4), 663.
30 P. Pescarmona and M. Taherimehr, Catal. Sci. Technol.,
2012, 2, 2169.
31 J. Michael, WO/1984/03701, 1984.
32 R. Pasquale, US Patent, US3748345, 1971.
33 P. Monia, European Patent EP 2055699, A1, 2009.
34 S. Frank, H. Rolf, M. Bert and Z. Jurgen, US Patent,
US5153333, 1992.
35 M. North, ARKIVOC, 2012, 1, 610.
36 X. Lu and D. Darensbourg, Chem. Soc. Rev., 2012, 41, 1462.
37 D. Darenbourg and S. Wilson, Green Chem., 2012, 14,
2665.
38 A. Baba, T. Nozoki and H. Matsuda, Bull. Chem. Soc. Jpn.,
1987, 60(4), 1552.
39 K. M. Doll and S. Z. Erhan, Green Chem., 2005, 7, 849.
RSC Adv.
View Article Online
RSC Advances
40 N. Kihara and T. Endo, J. Polym. Sci., Part A: Polym. Chem.,
1993, 31, 2765.
41 G. Rokichi and C. Wojciechowski, J. Appl. Polym. Sci.,
1990, 41, 647.
42 G. Rokicki, W. Kuran and B. Marciniak, Monatsh. Chem.,
1984, 115, 205.
43 T. Iwasaki, N. Kihara and T. Endo, Bull. Chem. Soc. Jpn.,
2000, 73, 713.
44 T. Sakai, N. Kihara and T. Endo, Macromolecules, 1995, 28,
4701.
45 M. Kim, S. Jeon, D. Park and J. Lee, Journal of Industrial
and Engineering Chemistry, 1998, 4(2), 122.
46 Z. Li, Y. Zhao, S. Yan, X. Wang and M. Kang, Catal. Lett.,
2008, 123(3–4), 246.
47 K. Motokura, S. Itagaki, Y. Iwasawa, A. Miyuji and T. Baba,
Green Chem., 2009, 11, 1876.
48 T. Takahashi, T. Watahiki, S. Kitazume, H. Yasuda and
T. Sakakura, Chem. Commun., 2006, 1664.
49 Y. Yang, Y. Hayashi, Y. Fujii, T. Nagano, Y. Kita,
T. Ohshima, J. Okuda and K. Mashima, Green Chem.,
2012, 14, 509.
50 B. Bhanage, S. Fujita, Y. Ikushima and M. Arai, Appl.
Catal., A, 2001, 219(1–4), 259.
51 K. Yamaguchi, K. Ebitani, T. Yoshida, H. Yoshida and
K. Kaneda, J. Am. Chem. Soc., 1999, 121(18), 4526.
52 B. Bhanage, S. Fujita, Y. Ikushima, K. Toriia and M. Arai,
Green Chem., 2003, 5, 71.
53 Y. Du, F. Cai, D. Kong and L. He, Green Chem., 2005, 7,
518.
54 J. Jiang, F. Gao, R. Hua and X. Qui, J. Org. Chem., 2005, 70,
381.
55 H. Shim, S. Udaykumar, J. Yu, I. Kim and D. Park, Catal.
Today, 2009, 148, 350.
56 H. Yasuda, L. He and T. Sakakura, J. Catal., 2002, 209,
547.
57 H. Zhou, Y. Wang, W. Zhang, J. Qu and X. Lu, Green
Chem., 2011, 13, 644.
58 D. Park, J. Moon, H. Jang and K. Kim, React. Kinet. Catal.
Lett., 2001, 72(1), 83.
59 L. Han, H. Choi, B. Liu and D. Park, Green Chem., 2011,
13, 1023.
60 Q. Gong, H. Luo, J. Cao, Y. Shang, H. Zhang, W. Wang and
X. Zhou, Australian Journal of Chemistry, 2012, 65(4), 381.
61 M. Lee, H. Shim, M. Dharman, K. Kim, S. Park and
D. Park, Korean J. Chem. Eng., 2008, 25(5), 1004.
62 K. Roshan, G. Mathai, J. Kim, J. Tharun, G. Park and
D. Park, Green Chem., 2012, 14, 2933.
63 R. Watile, K. Deshmukh, K. Dhake and B. Bhanage, Catal.
Sci. Technol., 2012, 2, 1051.
64 Y. Ono, Catal. Today, 1997, 35, 15–25.
65 X. Wang, Polyester based hybrid organic coatings, Ph. D.
Thesis, University of Akron, 2012.
66 H. Tomita, F. Sanda and T. Endo, J. Polym. Sci., Part A:
Polym. Chem., 2001, 39(6), 851.
67 B. Nohra, L. Candy, J. F. Blanco, Y. Raoul and
Z. Mouloungui, J. Am. Oil Chem. Soc., 2012, 89, 1125.
68 H. Tomita, F. Sanda and T. Endo, J. Polym. Sci., Part A:
Polym. Chem., 2001, 39(21), 3678.
69 M. Burgel and M. Fedtke, Polym. Bull., 1993, 30, 61.
70 A. Steblyanko, W. Choi, F. Sanda and T. Endo, J. Polym.
Sci., Part A: Polym. Chem., 2000, 38(13), 2375.
This journal is ß The Royal Society of Chemistry 2013

RSC Advances
71 T. Burgel and M. Fedtke, Polym. Bull., 1991, 27, 171.
72 D. C. Webster and A. L. Crain, Prog. Org. Coat., 2000, 40,
275.
73 M. M. Baizer, J. R Clark and E. Smith, J. Org. Chem., 1957,
22, 1706.
74 A. K. Schneider, J. Am. Chem. Soc., 1958, 80, 6409.
75 B. Ochiai, S. Inoue and T. Endo, J. Polym. Sci., Part A:
Polym. Chem., 2005, 43, 6282.
76 C. D. Diakoumakos and A. L. Kotzev, Macromol. Symp.,
2004, 216, 37.
77 B. Nohra, L. Candy, J. Blanco, Y. Raoul and
Z. Mouloungui, J. Am. Oil Chem. Soc., 2012, 89(6), 1125.
78 K. Kossev, N. Koseva and K. Troev, Reaction Kinetics
Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G
Mechanisms and Catalysis, 2004, 79(1), 11.
79 M. Climent, A. Corma, P. D. Frutos, S. Iborra, M. Noy,
A. Velty and P. Concepcion, J. Catal., 2010, 269, 140.
80 R. O. Jose, G. Olga, M. Belen, P. Amaia, R. Camilo,
L. Leire, T. Jesus and C. Maria, Appl. Catal., A, 2009, 366,
315.
Downloaded by Stanford University on 21 February 2013
81 O. Jose, G. Olga, R. Camilo and M. Belen, Green Chem.,
2012, 14, 3368.
82 W. W. Prichard, US Patent, US2511942, 1950.
83 D. C. Webster, Prog. Org. Coat., 2003, 47, 77.
84 J. M. Judge and C. Price, J. Polym. Sci., 1959, 41, 435.
85 T. Nishikumbo, A. Kameyama and M. Sasano, J. Polym.
Sci., Part A: Polym. Chem., 1998, 32, 301.
86 P. G. Parzuchowski, J. K. Maddalena, J. Ryszkowska and
G. Rokichi, J. Appl. Polym. Sci., 2006, 102, 2904.
87 A. Shaikh and S. Sivaram, Chem. Rev., 1956, 96, 951.
88 A. Takagaki, K. Iwatani, S. Nishimura and K. Ebitani,
Green Chem., 2010, 12, 578.
89 T. Sakakura, J. Choi and H. Yasuda, Chem. Rev., 2007, 107,
2365.
90 S. Benyahya, M. Desroches, R. Auvergne, S. Carlotti,
S. Caillol and B. Boutevin, Polym. Chem., 2011, 2, 2661.
91 Y. Ono, Catal. Today, 1997, 35, 15.
92 S. Pyo and R. Hatti-Kaul, Adv. Synth. Catal., 2012, 354(5),
797.
93 Q. Li, W. Zhang, N. Zhao, W. Wei and Y. Sun, Catal.
Today, 2006, 115, 111.
94 H. Tomita, F. Sanda and T. Endo, J. Polym. Sci., Part A:
Polym. Chem., 2001, 39(23), 4091.
95 C. Tang, H. Nulwala, K. Damodaran, P. Kaur and
D. Luebke, J. Polym. Sci., Part A: Polym. Chem., 2011,
49(9), 2024.
96 G. Rokicki and J. Czajkowska, Polimery, 1989, 34, 141.
97 O. Figovsky and L. Shapolvalov, US Patent,
US20040192803, 2003.
98 O. Figovsky and L. Shapovalov, US Patent, US7232877-B2,
2007.
99 M. Kim, S. Jeon, D. Park and J. Lee, Journal of Industrial
Engineering & Chemistry, 1998, 4(2), 122.
100 X. Wang and M. D. Soucek, Preparation of Nonisocyanate
Polyurethane Coatings, American Coatings Show, USA,
2010.
101 Z. Hosgor, N. Apohan, S. Karatas, Y. Menceloglu and
A. Gungor, Prog. Org. Coat., 2010, 69(4), 366.
102 K. M. Doll and S. Z. Erhan, J. Agric. Food Chem., 2005, 53,
9608.
103 M. Desroches, M. Escouvois, R. Auvergne, S. Caillol and
B. Boutevin, Polym. Rev., 2012, 52(1), 38.
This journal is ß The Royal Society of Chemistry 2013
View Article Online
Review
104 I. Javni, D. P. Hong and Z. S. Petrovic, J. Appl. Polym. Sci.,
2008, 108, 3867.
105 M. Bahr and R. Mulhaupt, Green Chem., 2012, 14, 483.
106 A. Boyer, E. Cloutet, T. Tassaining, B. Gadenne, C. Alfos
and H. Cramail, Green Chem., 2010, 12, 2205.
107 M. Bahr, A. Bitto and R. Mulhaupt, Green Chem., 2012, 14,
1447.
108 Book of abstracts 5th Workshop on Fats oils as renewable
feedstock for the chemical industry, Karlsruhe, Germany,
March 18–20, 2012.
109 O. Turuinc, N. Apohan, M. V. Kahraman and
Y. Menceloglu, Journal of Sol–Gel Science & Technology,
2008, 47, 290.
110 M. Kathalewar, D. Balgude, N. Shinde and A. Sabnis,
Paints & Coatings News, 2011, 7(7), 83.
111 M. Kathalewar and A. Sabnis, International Journal of
Scientific & Engineering Research, 2012, 3(3).
112 A. Albertsson and M. Sjoeling, J. Macromol. Sci., Part A:
Pure Appl. Chem., 1992, 29, 43.
113 B. Nohra, L. Candy, J. Blanco, Y. Raoul and
Z. Mouloungui, European Journal of Lipid Science &
Technology, 2012, DOI: 10.1002/ejit.201200082.
114 J. Mindemark, ‘‘Functional cyclic carbonate monomers
and polycarbonates’’, Thesis, Uppsala Universitet, 2012,
16.
115 S. Pyo, P. Persson, S. Lundmark and R. Kaul, Green Chem.,
2011, 13, 976.
116 S. Kuhling, H. Keul, H. Hocker, H. J. Buysch and N. Schon,
Makromol. Chem., 1991, 192, 1193.
117 W. Chen, H. C. Yang, R. Wang, R. Cheng, F. H. Meng, W.
X. Wei and Z. Y. Zhong, Macromolecules, 2010, 43, 201.
118 X. L. Hu, X. S. Chen, H. B. Cheng and X. B. Jing, J. Polym.
Sci., Part A: Polym. Chem., 2009, 47, 161.
119 T. F. Al-Azemi and K. S. Bisht, J. Polym. Sci., Part A: Polym.
Chem., 2002, 40, 1267.
120 X. L. Hu, X. S. Chen, Z. G. Xie, S. Liu and X. B. Jing, J.
Polym. Sci., Part A: Polym. Chem., 2007, 45, 5518.
121 C. H. Lu, Q. Shi, X. S. Chen, T. C. Lu, Z. G. Xie, X. L. Hu,
J. Ma and X. B. Jing, J. Polym. Sci., Part A: Polym. Chem.,
2007, 45, 3204.
122 M. Toyoharu, S. Mie, S. Fumio and T. Endo,
Macromolecules, 2005, 38, 7944.
123 H. R. Kricheldorf and B. Weegen-Schulz, Polymer, 1995,
36(26), 4997.
124 N. Nobukatsu, F. Sanda and T. Endo, J. Polym. Sci., Part A:
Polym. Chem., 2001, 39, 1305.
125 P. Brignou, J. Carpentier and S. Guillaume,
Macromolecules, 2011, 44, 5127.
126 J. Matsuo, F. Sanda and T. Endo, Macromol. Chem. Phys.,
1998, 199, 97.
127 S. Pyo, P. Persson, M. Mollaahmad, K. Sorensen,
S. Lundmark and R. Hatti-Kaul, Pure and Applied
Chemistry, March 1, 2012.
128 L. Vogdanis, B. Martens, H. Uchtmann, F. Hensel and
W. Heitz, Makromol. Chem., 1990, 191, 465.
129 H. Tomita, H. Hidaka, F. Sanda and T. Endo, Journal of the
Adhesion Society of Japan, 2000, 36(7), 259.
130 H. Tomita, F. Sanda and T. Endo, J. Polym. Sci., Part A:
Polym. Chem., 2001, 39, 162.
131 H. Tomita, F. Sanda and T. Endo, J. Polym. Sci., Part A:
Polym. Chem., 2001, 39, 860.
RSC Adv.

Review
132 Y. He, H. Keul and M. Moller, React. Funct. Polym., 2011,
71, 175.
133 H. Hall, J. Am. Chem. Soc., 1958, 80, 6412.
134 H. Hall and A. Schneider, J. Am. Chem. Soc., 1958, 80,
6409.
135 S. Neffgen, H. Keul and H. Höcker, Macromolecules, 1997,
30, 1289.
136 J. Kusan, H. Keul and H. Höcker, Macromolecules, 2001,
34, 389.
137 F. Schmitz, H. Keul and H. Höcker, Polymer, 1998, 39,
3179.
138 O. Ihata, Y. Kayaki and T. Ikariya, Angew. Chem., Int. Ed.,
2004, 43, 717.
Published on 04 December 2012 on http://pubs.rsc.org | doi:10.1039/C2RA21938G
139 S. Matsumura, Y. Soeda and K. Toshima, Appl. Microbiol.
Biotechnol., 2006, 70, 12.
140 O. Figovsky and L. Shapovalov, Macromol. Symp., 2002,
187, 325.
141 B. Tamami, S. Sohn and G. L. Wilkes, J. Appl. Polym. Sci.,
2004, 92, 883.
Downloaded by Stanford University on 21 February 2013
142 Polymate Ltd., International Nanotechnology Research
Center, ‘‘Hybrid Nonisocyanate Polyurethane Materials
(NIPU)’’..
143 Green Polyurethanes Floor Coatings ‘‘Next Generation in
Poly/Epoxy Floor Paint Coatings (Non-Isocyanate)’’..
144 O. Figovsky, L. Shapovalov and D. Beilin, Surf. Coat. Int.,
Part B, 2005, 88(1), 67.
145 O. Figovsky, L. Shapovalov and D. Beilin, Monolithic
Flooring Based on nonisocyanate polyurethanes, Polymate
Ltd.- Israeli Research Center, Israel2005.
146 W. Blank, US patent, US4820830, 1989.
147 P. Forgione and B. Singh, US Patent, US5089617, 1992.
148 ‘‘High gloss non isocyanate polyacryl anhydride’’ DuPont
Industrial Coatings, 2002.
RSC Adv.
View Article Online
RSC Advances
149 W. Ho, A. Capino, M. A. Croyle, J. M. Reuter and R.
F. Tomko, US Patent, US7345120-B2, 2008.
150 V. J. Tramontano, M. E. Thomas and R. D. Coughlin,
‘‘Synthesis and coating properties of novel waterborne
polyurethane dispersions’’, Kings Industries, Inc.,
Speciality Chemicals, Science Road, Norwalk.
151 W. J. Blank, ‘‘Formulating Polyurethane Dispersions’’,
Kings Industries Inc., Norwalk CT.
152 O. Figovsky, L. Shapovalov and D. Beilin, ‘‘Monolithic
Flooring Based on nonisocyanate polyurethanes’’,
Polymate Ltd.- Israeli Research Center, Israel, 2005.
153 J. Hwang, S. Wang, P. Chen, C. Huang, J. Yeh and
K. Chen, J. Polym. Res., 2012, 19, 9900.
154 O. Figovsky and L. Shapovalov, ‘‘Non isocyanate polyur-
ethanes for adhesives and coatings, Polymers and
adhesives in microelectronics and photonics’’, First
International IEEE Conference, Germany, 2001.
155 O. Figovsky and L. Shapovalov, ‘‘Cyclocarbonate based
polymers including Nonisocyanate polyurethane adhe-
sives and coatings’’, Encyclopedia of Surface Colloid
Science, Second EditionTaylor & Francis Group, 2001.
156 V. Holen, V. Stone and H. V. Bergen, ‘‘New Routes to
Urethane Acrylates, Cytec Surface Specialties’’, RadTech
Europe, Conference & Exhibition, Belgium2005.
157 O. L. Figovsky and L. Shapovalov, ‘‘Nonisocyanate
Polyurethanes for Adhesives and Coatings’’, 1st
International Conference on Polymers and Adhesives in
Microelectronics and Photonics, Potsdam Germany,
October 21–24, 2001.
158 G. Chen, V. Does and A. Bantjes, J. Appl. Polym. Sci., 1993,
47, 25.
This journal is ß The Royal Society of Chemistry 2013