Review

pubs.acs.org/CR

On the Versatility of Urethane/Urea Bonds: Reversibility, Blocked

Isocyanate, and Non-isocyanate Polyurethane
Etienne Delebecq,† Jean-Pierre Pascault,‡,§ Bernard Boutevin,† and François Ganachaud*,†,‡,§
†
Institut Charles Gerhardt, UMR 5253 CNRS, Ingénierie et Architectures Macromoléculaires, Ecole Nationale Supérieure de Chimie
de Montpellier, 8 rue de l’école normale, 34296 Montpellier, Cedex 05, France
‡
INSA-Lyon, IMP, UMR5223, F-69621, Villeurbanne, France
§
Université de Lyon, F-69622, Lyon, France

*
S Supporting Information

3.2.1. Bulk Cross-Linked PUs by Cast Molding

(CM) and Reaction Injection Molding
(RIM) 93
3.2.2. Reaction in Solution: Coatings, Sealants,
and Adhesives 93
3.2.3. Reaction with Water: Preparation of
Solid Foams 93
3.2.4. Reaction in Water: Waterborne Coatings 94
3.2.5. Solvent-Free Reaction: Powder Formu-
lations 95
3.2.6. Isocyanate Chemistry in Self-Healing
Materials 95
3.3. Reversibility of Urethane Bonds and Trans-
carbamoylation during the Processing of
CONTENTS Polyurethanes 95
3.3.1. Example 1: Reversibility and Rheological
1. Introduction 81 Behavior 95
2. Background on the Isocyanate Chemistry 82 3.3.2. Example 2: Reversibility To in Situ
2.1. Structure and Reactivity of Monoisocyanates 82 Compatibilize Polymer Blends 96
2.2. Urethanes and Ureas 82 3.3.3. Example 3: Reversibility To Generate
2.2.1. Preparation of Urethanes, Ureas, and “Reprocessable” Cross-Linked Polymers 96
Thiourethanes 82 3.4. Reversibility as a Means of Recycling Polyur-
2.2.2. Mechanism and Reaction Parameters 82 ethanes 97
2.2.3. “Transreactions” and Reversibility 85 4. Model Reversible Urea/Urethane Bonds: The
2.3. Dimer, Trimer, and Polymer 86 Case of Blocked Isocyanates 97
2.3.1. Preparation 86 4.1. Introduction 97
2.3.2. Reversibility 87 4.2. Overall Mechanisms for Reactions of
2.4. Allophanate and Biuret 87 Blocked Isocyanates 98
2.4.1. Formation 87 4.2.1. Elimination−Addition Mechanism 98
2.4.2. Rate of Formation 87 4.2.2. Addition−Elimination Mechanism 98
2.4.3. Reversibility 88 4.2.3. More Complex Mechanisms 98
2.5. Oxazolidone 89 4.3. Recording the Deblocking Reaction 98
2.6. The Reactivity of Diisocyanates and Poly- 4.3.1. A Point about the Measurement of the
isocyanates 89 “Deblocking Temperature” 99
2.7. “Polymeric Isocyanates” 90 4.3.2. Techniques 99
2.8. Conclusion 91 4.2.3. Operating Conditions 101
3. Implications of the Urethane/Urea Bond Reversi- 4.3.4. Presence of Chemical Additives 101
bility in Preparing Polyurethane Materials 91 4.3.5. Catalysis Action 102
3.1. Synthesis of Polyurethane Materials 92 4.3.6. Conclusion 103
3.1.1. Polymerization and Phase Transitions 92 4.4. Chemical Structure−Reactivity Relationship
3.1.2. Thermoplastic versus Thermoset Poly- of Blocked Isocyanates 103
mers 92
3.2. Processing of Polyurethane Materials 93
Received: May 14, 2012
Published: October 19, 2012

© 2012 American Chemical Society 80 dx.doi.org/10.1021/cr300195n | Chem. Rev. 2013, 113, 80−118
Chemical Reviews Review

4.4.1. Alcohols and Phenols 103 reactivity and the large yield of reaction one achieves, even in
4.4.2. Amines 104 viscous systems or at low temperatures. One major drawback is
4.4.3. Oximes 104 the inherent toxicity of isocyanate molecules, which in the
4.4.4. Other N-Based Compounds: Amides, context of REACh becomes more and more problematic.1
Imides and Imidazole, Pyrazole, and Sure enough, the chemistry of isocyanate is complex since it
Triazole 104 entails a variety of reactions with other simple functions, such
4.5. Improving Industrial Systems 104 as alcohol or amine, but also self-additions and trans-
4.5.1. Conventional Systems 104 condensations. Prior reviews from this journal already described
4.5.2. Chemical Tricks 105 to a large extent the wide spectrum of reactions that this simple
4.5.3. Dual Networks 106 function could generate.2,3 Among the most recent literature
4.5.4. Blocking Reaction of Amine Groups 106 survey on polyurethanes, the widely cited review article of Krol
4.6. Blocked Isocyanates as Initiators for Other already scanned a wide spectrum of all old and modern aspects
Reactions 106 to prepare these materials.4 A series of comprehensive
4.6.1. Urea Linkage as a Source of Amine 106 papers5−7 proposed mainly a patent compilation of an
4.6.2. Urethane Promoting Ring-Opening Pol- industrial trend picture, the generation of “blocked isocyanates”
ymerization of 1,3-Benzoxazine 107 that notably changed the method of formulation of PU
5. “New” Trends: Toward Non-isocyanate-Based materials, allowing, for example, one-component or waterborne
Polyurethanes 107 polyurethane formulations to be commercialized. From the
5.1. Phosgene-Free Isocyanate Precursors 107 application point of view, the major parameter of the system is
5.2. Phosgene-Free Isocyanate-Free Precursors 107 the temperature at which reactive functions are regenerated, in
5.2.1. Carboxamide/Alcohol Polycondensation 107 other words, the deblocking temperature of adduct. The rate
5.2.2. Dicarbonate/Amine Condensation 107 and extent of regenerating isocyanate however depends on
5.2.3. The Specific Case of Cyclocarbonate/ many factors: the chemical function containing the active
Amine Addition 108 hydrogen, the isocyanate and blocking molecule structures, the
5.3. Conclusion 112 solvent properties, the presence of a catalyst, and the reaction
6. Final Conclusion: Isocyanate-Free versus Non- temperature. Also, the presence of an external molecule able to
isocyanate Solutions in View of an Industrial consume regenerated isocyanate functions severely shifts the
Context 112 equilibrium towards the adduct deprotection (vide inf ra).
Associated Content 113 This review proposes to extend this approach of the
Supporting Information 113 reversibility of isocyanate-based bond to all products of this
Author Information 113 chemistry, namely, urethane, urea, uretdione, biuret, allopha-
Corresponding Author 113 nate, and isocyanurate. From this arbitrary starting point,
Notes 113 different factors leading for instance to the choice or the design
Biographies 113 of a system of isocyanate and blocking molecule or to the
Acknowledgments 114 reprocessing of polyurethane materials are proposed. Also, to
Symbols and Abbreviations 114 respond to the problem of toxicity of the isocyanate precursors,
References 114 which could entail problems at the end of life of the materials
(owing in part to its reprocessability), recent pathways that
(re)discovered elegant, straightforward chemistry to avoid the
1. INTRODUCTION use or presence of isocyanate functions in ready-to-process
Discovered by Wurtz in 1848, the isocyanates revealed their materials are also reported here.
chemistry from systematic study during the nineteenth century, In writing this review, equally dedicated to academic and
for example, by Curtius or Hofmann. The discovery of industrial researchers, one obviously had to set some limits.
polyurethanes (PU), via the reaction of a polyester diol with First, we exclusively focused on the academic literature; patents
a diisocyanate, by Bayer and his co-workers in 1937, made the are hardly touched upon. If selection makes this review more
diisocyanates one of the major chemicals produced in the restrictive, clarity shall be improved since the open literature
world. Currently, the global isocyanate market grows by 5% per generally compares close systems to conclude about the
year, stimulated primarily by the polyurethane output influence of various parameters. In the same idea, emphasis
expansion. The strength of the polyurethane market surely will be placed on the most industrially used isocyanates; specific
comes from the fact that a large variety of products can be isocyanates with sulfonyl, chlorosulfonyl, phosphorus, or
prepared from essentially simple precursors, namely, toluene carbonyl functions attached to the isocyanic group will not be
diisocyanate (TDI) and methylene diphenyl isocyanate (MDI), considered here (these were however described in the old
used for the manufacture of flexible and rigid polyurethane reviews). Finally, we did not try to cover a specific range of time
products, respectively. Depending on whether linear or cross- of publication, but selected what we believe were (and still are)
linked networks are prepared, thermoplastic elastomers and the most relevant articles to the subjects treated here.
thermoset resins (including foams) are sold every day as major In a first part, we recall some background on isocyanate
components from paints to binders to materials for the chemistry, including the structures and reactivity of mono- and
aeronautic industry, for instance. The large range of mechanical diisocyanates, the description of reactions leading to urethane
properties that can be reached within such materials arise and urea groups, and the preparation of autocondensed
mainly from two physical chemical processes, that is, phase functions, for example, allophanate, biuret, or oxazolidone. In
separation between hard and soft segments and hydrogen a second part, the chemistry of polyurethanes is approached on
bonding between carbamate (or urethane) bonds. Another the starting precept of the reversibility: both thermoplastic and
important advantage of isocyanate chemistry is its very deep thermosetting polymer syntheses are reviewed, insisting on the
81 dx.doi.org/10.1021/cr300195n | Chem. Rev. 2013, 113, 80−118
Chemical Reviews
specific use of transcarbamoylation reactions to process the
materials. In the third part, the blocked isocyanate chemistry is
reviewed by discussing the addition between isocyanate group
and reactive hydrogen containing compounds and the thermal
reversibility of the formed products to finally describe the most
widespread classes of blocking molecules. Finally, new trends in
the isocyanate/polyurethane chemistry complete this review
before comparing, in a conclusive discussion, isocyanate-free or
non-isocyanate systems in the prospects of industrial outcomes.
2. BACKGROUND ON THE ISOCYANATE CHEMISTRY
2.1. Structure and Reactivity of Monoisocyanates
The isocyanate group is a strained linear structure with two
cumulated double bonds NC and CO. As in the case of
other heterocumulenes, the isocyanate group reactivity is based
on the polarization induced by the high electronegativities of
nitrogen and oxygen atoms, which delocalize the electron
density toward the nitrogen and oxygen atoms, as shown in
Scheme 1.
Scheme 1. Resonance Structures of the Isocyanate Group
Surprisingly, the electron density distribution, as well as the
geometry, of the isocyanate group is still unknown. Caraculacu8
has reviewed the major results in the field of theoretical
calculations and observed that the only point on which the
different authors agree is that the carbon atom possesses the
minimum electron density; the charge magnitudes, the
distances, and even the angle values differ from one author to
another. These considerations have important consequences in
understanding the isocyanate reactivity and the mechanism of
urethane/urea bond formation.
Sacher9 found out that in the phenyl isocyanate molecule the
NCO group is perpendicular to the benzene ring plane,
whereas Bondarenko et al.10 claimed a completely planar
structure for the whole phenylisocyanate molecule. Scheme 2
Scheme 2. Geometry and Electron Density of Phenyl
Isocyanate According to Sacher
shows the electron density, the distances, and the angles for this
molecule according to Sacher. These differences are essential
since they determine the reaction mechanism by specifying (i)
the isomeric cis/trans structure; (ii) which of the double bonds,
NC or CO, is the first affected in the initial stage of
reaction, and (iii) whether the lone electron pair on the
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Review
nitrogen atom is less available because of interactions with the
aromatic ring.
Generally speaking, if steric factors are neglected, any
electron-withdrawing groups attached on the NCO moiety
increase the positive charge on the carbon atom and so enhance
the reactivity. This leads to the following reactivity
classification:11 ClSO2NCO > RSO2NCO (R = alkyl, aryl) >
OP(NCO)3 > aryl-NCO (p-NO2C6H4− > p-ClC6H4− > p-
CH3C6H4− > p-CH3OC6H4−) > alkyl-NCO.
2.2. Urethanes and Ureas
2.2.1. Preparation of Urethanes, Ureas, and Thiour-
ethanes. According to the resonance forms presented in
Scheme 1, isocyanate easily reacts with active nucleophilic
reagents XH; the nucleophilic center X attacks the electrophilic
carbon of isocyanate.
The most important reactions involving isocyanate are
additions on alcohol, thiol, or amine: the isocyanate group
reacts with a hydroxyl group to yield urethane (Scheme 3a),
Scheme 3. Common Reactions Used in Polyurethane
Chemistry
with a thiol to produce thiourethane (Scheme 3b), and with an
amine to give urea bonds (Scheme 3c). The thiol group reacts
with isocyanates in the same way as its oxygen analog, with
much less reactivity.3,12 The reaction with water generates
unstable carbamic acid, which decomposes into gaseous carbon
dioxide and a primary amine, a common way to produce a wide
range of PU materials with different densities, for example, from
moisture-curing coatings to urethane foams (Scheme 3d). The
propensity of inorganic acids, such as HCl or H3PO4 used
during the monomer synthesis,13 to slow isocyanate reactivity is
known from industry. Unfortunately, we could not find any
mention of it in the literature nor a mechanistic scheme to
explain the chemistry involved.
2.2.2. Mechanism and Reaction Parameters.
2.2.2.1. Autocatalytic Model. Seminal works have been carried
out to study the reaction mechanism and establish the kinetic
equations. Generally speaking, it is accepted that the
nucleophilic center of XH is first added to the electrophilic
carbon of the isocyanate group (Scheme 4); then hydrogen
atom is transferred to nitrogen.
From this mechanism, the following second-order kinetics of
the final product formation is deduced (eq 1).
−d[RNCO]
v= = k[RNCO][R′XH]
dt (1)
where [RNCO] and [R′XH] represent the concentration at
reaction time t of isocyanate and nucleophile groups,
respectively.
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Chemical Reviews
Scheme 4. General Mechanism of Isocyanate/Nucleophile Reaction
Scheme 5. Autocatalytic Mechanism by Hydrogen Bonding (a) between Isocyanate and Urethane/Urea or (b) between
Isocyanate and RXH (X = O, S, NH)
This model is generally only verified for low-to-medium
degrees of conversion. As the conversion increases, the
isocyanate group is activated by the formation of a hydrogen
bond in which the urethane (or urea) moiety (Scheme 5a) or
even the nucleophile (Scheme 5b) acts as a basic catalyst.14
Sato15,16 was the first to develop a kinetic equation taking
into account the autocatalytic effect of alcohol and urethane
groups. Based on the above mechanism, the formation rate is
expressed as:
d[NCO] k k [RNCO][R′XH][RNHCOXR′]
− = 1 3
dt k 2 + k 3[RNHCOXR′]
k1′k 3′[RNCO][R′XH]2
+ hydrogen bonding complex with the isocyanate; then a
k 2′ + k 3′[R′XH] (2)
Aromatic isocyanates are highly reactive, and thus, the rate
constant k2 and k2′ are much higher than k3[RNHCOXR′] and
k3′ [RXH], respectively. The rate of reaction (eq 2) becomes
d[NCO]
− = K1[RNCO][R′XH][RNHCOXR′]
dt
+ K 2[RNCO][R′XH]2 (3)
where
k1k 3 k1′k 3′
K1 = and K2 =
k2 k 2′
Global kinetic models that consider these autocatalytic
contributions were successfully applied for describing both
the noncatalyzed and catalysis-mediated isocyanate/alcohol and
isocyanate/water reactions. These models include second-order
kinetics during the initial stages of the reaction and
subsequently describe autocatalytic third-order kinetics arising
from the formation of hydrogen bonds.17,18 Majoros et al.19−21
synthesized aromatic and aliphatic polyurethane prepolymers
by high throughput experiments and checked that the order of
reaction in nucleophile is 2.
2.2.2.2. Concentration and Solvent Effects. As explained
above, the reactivity toward the NCO group is not constant but
strongly depends on the possible association state of the
reactants. The concentration of these complexes, such as
dimeric or trimeric alcohol or alcohol−isocyanate or alcohol−
solvent complexes, not only depends on the concentration of
the reactants but also is determined by the characteristics of the
83
Review
solvent: polarity, hydrogen bonding ability, and dielectric
constant.
Many groups studied the association states of the reactants
mainly in the case of alcohol−isocyanate reaction, particularly
Baker,22−27 Entelis et al.,28,29 Ephraim, 30 Oberth and
Bruenner31 and Saunders and Frisch.32 Different parameters
(hydrogen bonding, dielectric constant, or basicities of species)
were proposed to explain such effects with more or less
incomplete data explanation.
Chang33 gathered all the kinetic data and proposed a general
ion-pair mechanism based on the electron donation capability
of the reactants measured by the electron donor number, DN,
as defined by Gutmann.34 First, the monomeric alcohol forms a
molecule S (i.e., any molecule present in the reaction medium,
e.g., solvent, alcohol) solvates the active hydrogen in the
complex to form an ion pair, which undergoes urethane attack
more easily (Scheme 6).
Scheme 6. Uncatalyzed Urethane Formation Mechanism
According to Scheme 6, the rate greatly depends upon the
solvation power (equilibrium b). The electron donor character
of the reactant S controls the reaction rate according to two
roles: (i) it can catalyze the reaction by activating the
isocyanate/alcohol complex or (ii) it inhibits the reaction by
forming a hydrogen bonding complex with the oxygen of
alcohol. The inhibition effect is due to the reduction of the
concentration of the alcohol/isocyanate complex and of
monomeric alcohol, which entails catalytic activity.
When the reaction is carried out in alkanes, the low DN value
(lower than for alcohols) gives no interaction with the
reactants. Here, solvent is considered as a diluent, which first
increases the monomeric alcohol concentration and second
decreases the alcohol/isocyanate complex concentration. Thus,
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Chemical Reviews Review

Table 1. Solvent Physical Properties and Apparent Second-Order Rate Constants Observed for Butanol−Phenyl Isocyanate
Reaction at 25 °C31,34,35
kobs × 103 L/(mol·min)
[butanol]/[phenyl isocyanate]
entry aprotic solvent hydrogen bonding index, γa donor number, DN dielectric constant, ε 0.15 M/0.15 Mb 0.229 M/0.229 Mb
1 cyclohexane 0 0 2.02 39
2 chlorobenzene 1.5 −0.4 5.71 8.0
3 benzene 0 0.1 2.28 5.8
4 nitrobenzene 2.8 4.4 36.1 1.8 4.8
5 ethyl acetate 8.4 17.1 6.4 0.18 0.18
6 acetonitrile 6.3 14.1 38.8 0.15
7 dioxane 9.7 14.8 2.21 0.08
8 DMF 12.3 26.6 36.7 276
9 DMSO 7.7 29.8 48.9 1410
a
Measured as an IR frequency shift in deuterated methanol (see refs 36 and 37 for details). bFor reactions carried out in bulk ([butanol]/[phenyl
isocyanate] = 5 M/5 M), the rate constant was determined at 40 × 10−3 L/(mol·min)

performing the reaction in alkane medium gives two antagonist
effects leading to no significant variation of the reaction rate
compared with bulk reactions (Table 1, line 1). The common
aprotic polar solvents that form hydrogen bonds decrease the
monomeric alcohol (the active species) and the isocyanate/
alcohol complex concentration; the reaction rate is reduced
(Table 1, rows 2−7). On the other hand, some aprotic solvents,
for example, DMSO and DMF, have higher solvation power
than alcohol (higher DN), which increases the solvated ion pair
concentration, counteracting the lower complex concentration
to produce a huge catalytic effect (Table 1, rows 8 and 9).
Chlorobenzene, benzene, nitrobenzene, ethyl acetate, acetoni-
trile, and dioxane have a certain solvation power but lower than
the monomeric alcohol; the overall effect of these solvents is an
inhibition effect.
In the third step (Scheme 6c), the high dielectric constant of
the solvent (ε) helps to dissociate the O−H bond. The
independence of ε from the reaction rate indicates that OH
dissociation is not the controlling step.
2.2.2.3. Catalysis. Tertiary amines and organometallic
compounds, such as salts of tin or iron, present catalytic
activity for the reaction between isocyanate and compounds
bearing a labile hydrogen atom.
The catalysis role of tertiary amine is easily explained by the
mechanism described in Scheme 6. Amine plays a similar role
as the solvent molecules, and thus the catalytic activity strongly
depends on the donor number. With very high donor value in
the range of 30−50, the addition of a small amount of tertiary
amine does not affect the concentration of the isocyanate/
alcohol complex, but its high DN value leads to strong solvation
effect. Table 2 presents an example of rate constants measured
Table 2. Relative Rate Constants for the Methanol/Phenyl
Isocyanate (0.24 M/0.24 M) Reaction in Di-n-butyl Ether, in
Presence of 0.03 M Amine Based Catalysts at 20 °C33,38
tertiary amine DN34 relative rate constant
uncatalyzed 1 Entelis suggested earlier.55 In the Bloodworth’s mechanism, the
quinoline 30.4 6 cycle of catalysis involves N-coordination of the isocyanate with
pyridine 36.7 11
tributyl amine a 54
triethylamine 50.7 134
DABCO a 1206
a
Not given.
84
for a model isocyanate−alcohol reaction catalyzed by tertiary
amines. For amine catalysis, the most widespread industrial
catalyst is 2,2′-diazabicyclo[2.2.2]octane or DABCO. It is
important to note that their relative reactivity depends on
catalyst concentration (Table 3).
Table 3. Relative Rate Constants of Catalysts in an
Isocyanate−Hydroxyl Reaction49a
catalyst concentration (%) relative rate constant
uncatalyzed 1
DABCO 0.1 130
0.2 260
0.3 330
DBTDL 0.1 210
0.5 670
DBTDL + DABCO 0.1 + 0.2 1000
a
Reactants not given in the publication.
Generally speaking, metal-based catalysts act as Lewis acids
toward alcohol or isocyanate to initiate the reaction. It has been
shown that numerous organometallic compounds, such as
organo-lead,39 -tin,17 -zirconium,40,41 -magnesium,42 -bismuth,
and -iron43,44 are effective catalysts for the isocyanate−hydroxyl
reaction. The tin compounds, among which those represented
by the general formula Bu2SnX2 (X is an anion) exhibit
remarkable catalytic activity, for example, the dibutyltin
dilaurate, DBTL. Mercury compounds combine two industrially
remarkable properties: they initially retard the reaction (good
latency) and thereafter, when the reaction commences, they
provide a high conversion in short time reaction.45−48 Current
investigations are carried out to replace these highly toxic
compounds, so far with mixed results.
Concerning metal-based catalysis, recent kinetic data40,50−53
tend to prove that the isocyanate activation by tin alkoxide
originally proposed by Bloodworth and Davies54 is more
relevant than alcohol activation by coordinating with tin as
the tin alkoxide previously formed by alcoholysis of the starting
tin compound as shown in Scheme 7A. Transfer of the alkoxide
anion onto the coordinated isocyanate affords an N-stannylur-
ethane, which then undergoes alcoholysis to give the urethane
and the original tin alkoxide. For a mixture of aliphatic and
aromatic alcohols, catalysis choice orientates the reaction
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Chemical Reviews
Scheme 7. Catalysis of Isocyanate/Alcohol Reaction (A) by Organotin According to Bloodworth and Davies51 and (B) by
Carbene According to Coutelier et al.63
Scheme 8. Possible Degradation Reactions of Urethane Bond
toward either aliphatic or aromatic urethane. At room
temperature, in presence of DABCO or even in the absence
of catalyst, hexamethylene diisocyanate (HDI) reacts first with
the phenolic OH; whereas with organotin catalyst, the aliphatic
OH−HDI reaction is faster. For both catalyses, the aliphatic
urethane is always thermodynamically favored, so upon
refluxing the phenolic-based urethane rearranges to an aliphatic
urethane.56
The catalyst concentration influences the relative reactivity of
reaction (Table 3) and according to Richter et al.,57 the tin
catalyst has first to dissociate before complexing the isocyanate
group. This equilibrium is temperature sensitive and thus, the
effective concentration in catalytic active species is difficult to
ascertain. Several studies demonstrated that for both amine58 or
tin59 catalysis systems, increasing the catalyst concentration
beyond a certain level does not accelerate the reaction further.
Synergism between tin and amine catalyst systems has been
depicted by Tarasov et al.28 for addition of butanol on m-
chlorophenyl isocyanate, by Sojecki and co-worker60,61 for the
TDI-macrodiols reactions or by Frisch and Rumao49 (Table 3).
Finally, one should note the recent study on carbene as a
catalyst of isocyanate−hydroxyl reaction under mild conditions,
typically below 70 °C (Scheme 7B).62,63
2.2.3. “Transreactions” and Reversibility. The individual
stages of the reactions between isocyanates and protic
nucleophilic reagents are all reversible and, furthermore,
characterized by an intrinsic reversibility under heating
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Review
(Scheme 4). The urethane bond formed by addition of
isocyanate on alcohol presents a weak C−NH bond with an
activation energy of dissociation in the range of 100−130 kJ/
mol.64,65 In a temperature range starting from 150 °C and
above, four degradation pathways were identified (Scheme 8):
first, the urethane linkage can be broken into the initial reagents
(isocyanate and alcohol). Other pathways, leading to small
molecules such as carbon dioxide and primary and secondary
amines, eventually with olefin formation, are also possible but
occur more slowly and at higher temperature (Scheme 8b,c). In
the presence of a more nucleophilic compound, urethane can
rearrange, via transcarbamoylation, into a new urethane or urea
compound (Scheme 8d).
The main degradation pathway depends on the equilibrium
between urethane bond and the starting functional groups.
When temperature increases, the reverse reaction occurs
(Scheme 8a). Generally speaking, the more easily the urethanes
are formed, the less stable they are. Thus, according to the
reactivity classification presented before, the following decom-
position temperature order is given: alkyl-NCO/alkyl-OH (250
°C) > aryl-NCO/alkyl-OH (200 °C) > alkyl-NCO/aryl-OH
(180 °C) > aryl-NCO/aryl-OH (120 °C).67
Electronic effects on the substituents also influence both the
kinetics and pathway of the thermal decomposition: aromatic
groups tend to favor the reverse reaction (Scheme 8a), while
aliphatic ones promote urethane dissociation into primary
amine and olefin (Scheme 8b).67 Reverse reaction occurs
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Chemical Reviews
exclusively for N-mono substituted polyurethanes while N-
disubstituted ones mainly degrade through dissociation to
primary amine, olefin, and CO2.68
At a temperature as low as 120 °C, urethane linkage has been
proven to break in the presence of a nucleophilic reagent
(Scheme 8d). O-Alkyl carbamates are quite stable and
necessitate high reaction temperature or efficient catalysis.
Jousseaume et al. reported transcarbamoylation reaction of N-
hexyl O-methyl carbamate with n-octanol aided by 1% bismuth
trifluoromethanesulfonate or 1,3-dibromodistannoxane, giving
yields in the range of 70−90%.69,70 Depending on the
substituents, exchange reactions are also possible between
two urethanes (Scheme 9) in the same range of temperature as
the reverse urethane formation reaction (T ≈ 180−250 °C) or
just below.
Scheme 9. Transurethanization Reaction
Exchange reactions have been evidenced by heating up a
model compound to its melting temperature.71 Diphenyl-
methane diisocyanate was first reacted with butanediol (BDO)
and ethanol (molar ratio 2:1:1), from which purified product,
called HS2 (Scheme 10, n = 1), was analyzed by size exclusion
Scheme 10. Structure of Model Compounds Used in
Scrambling Reaction Obtained from the Reaction between
MDI, BDO, and Ethanola
a 12).
In Figure 1, molecules are labeled HS1 (for n = 0) to HS4 (for n = 3).
chromatography (Figure 1) in tetrahydrofurane (THF) before
and after reaching 220 °C. It clearly shows that in the liquid
state, the strictly monodisperse HS length distribution of the
model compound became polydisperse, with the most probable
molar mass distribution expected from a step-growth polymer-
ization. Such a “scrambling” reaction can be explained
according to two mechanisms, either by transurethanization
Figure 1. SEC curves of (a) the purified model compound (HS2 =
2MDI + 1BDO + 2ethanol) and (b) the mixture of compounds after
heating at 220 °C. Peaks 1, 3, and 4 are equivalent in molar mass to
HS1, HS3, and HS4. Reprinted with permission from ref 71.
Copyright 2003 John Wiley & Sons.
86
Review
(Scheme 9) or by a two-step process: first reverse reaction of
the urethane linkage (carbamate, -NHCOO-) above the
melting temperature of HS2 (Tm ≈ 187.6 °C) and then
reaction of thus-generated -NCO and -OH groups when the
sample cools to room temperature (Scheme 8a).
2.3. Dimer, Trimer, and Polymer
2.3.1. Preparation. In addition to the reaction of addition
between an isocyanate group and reactive hydrogen-containing
compounds, isocyanate groups also undergo homocyclization.
The Scheme 11 presents the different possibilities of isocyanate
homocyclization depending on the catalyst used.
Scheme 11. Isocyanate Self-Reactions
If aliphatic isocyanates dimerize with difficulties,72 dimers of
aromatic isocyanates are obtained by heating the monomer
with a nucleophilic catalyst. Dimerization is an equilibrium
reaction catalyzed by trialkylphosphine, substituted pyridines,
or trialkylamines.3,72 Phosphines and especially trialkyl-
phosphine are much more efficient than pyridine in catalyzing
dimer formation and must be deactivated by a stoiechiometric
amount of alkylating molecule such as benzyl chloride (Scheme
Scheme 12. Dimerization Mechanism of Aryl Isocyanate
Catalyzed by Phosphine
Trimerization of alkyl and aryl isocyanates is promoted by
catalysts such as alkali metal alkoxides.3 Tertiary amines and
certain tin compounds also catalyze the reaction, though very
slowly. The trimerization reaction is also favored by
incorporating tin(II) bis(acetylacetonate) catalyst, which yields
33% of triphenyl isocyanurate.74,75 Urethane groups are known
also to be good catalysts for isocyanurate formation.76 Recently,
Buchmeiser’s team showed that N-heterocyclic carbene
derivatives could produce 99% of phenyl isocyanate trimer
but also promotes reaction of these with diols.77
Polyisocyanates are synthesized at low temperature (from
−40° to 100 °C) by anionic chain polymerization. The
homopolymer is not thermally stable because unzipping occurs
and it forms monomers and cyclic trimers around 140 °C or
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Chemical Reviews
even at room temperature in presence of basic impurities.78 For
more details on polyisocyanates, readers are referred to the
work of Bur et al.79
Isocyanates can also be converted into carbodiimides with
elimination of carbon dioxide (Scheme 13) by prolonged
Scheme 13. Carbodiimide Formation Starting from
Isocyanates
heating at high temperature (180−200 °C).80 Transition
metals81 and especially organic compounds of main group 5,
phosphine oxides,82 and nitrogen-containing molecules (such
as amide, urea, anilide, or isocyanate derivatives)83,84 catalyze
the condensation reaction under mild conditions.
2.3.2. Reversibility. If carbodiimide formation is clearly
irreversible, homocyclization products can be split off and
regenerate isocyanate at high temperature. Querat et al.73
studied by infrared spectroscopy the dissociation of 2,4-TDI
dimer without catalyst. They reported first-order kinetics up to
80% conversion at 160 °C and observed a relatively high
activation energy (Ea = 142 kJ/mol). Without catalyst, the free
isocyanate regeneration, which depends on the parent
isocyanates, occurs only at high temperature. The uretdiones
of 2,4-TDI, isophorone diisocyanate (IPDI), and HDI (for
structures, see Scheme 21) decompose without catalyst at 150,
160, and 200 °C, respectively.7,85 The presence of the
remaining catalyst lowers the dissociation temperature. In
presence of tributylphosphine, Saunders2 reported that TDI
dimers are 10% dissociated at 10 °C, 25% dissociated at 25 °C
and totally dissociated at 80 °C in benzene solution.
Although the isocyanates can be regenerated from their
dimers by heating at moderate temperature, a higher temper-
ature (>250 °C) leads to isocyanurates via trimerization. While
usually considered thermally stable,86 isocyanurate degradation
has been observed by infrared spectroscopy, thermogravimetric
analysis,87 and 1H and 13C nuclear magnetic resonance
(NMR).88 Kordomenos et al.89,90 studied by infrared spectros-
copy the degradation kinetics of model isocyanurate synthe-
sized by homocyclization of phenylisocyanate. A temperature
above 417 °C is required to observe a degradation rate through
volatilization superior to 0.3 h−1 (Table 4); this temperature
Table 4. Kinetic Parameters for the Degradation Reaction of
Butyl Phenyl Carbamate and Various Isocyanurates
Ea TD (°C) at
(kJ·mol−1) A (h−1) k = 0.3 h−1
butyl phenylcarbamate 161.8 7.38 × 1012 277
isocyanurate of 252.2 3.69 × 1016 417
phenylisocyanate
poly(aromatic 184.1 8.46 × 1010 441
isocyanurate)
poly(aliphatic 246.7 2.12 × 1016 410
isocyanurate)
must be compared with 277 °C for butyl phenylcarbamate 1
(Scheme 14). For isocyanurate-based polymer, synthesized
through self-reactions between mono- and diisocyanate, they
reported a higher stability for aromatic than aliphatic
isocyanurate, which is explained by the strong char formation
during aromatic isocyanurate degradation, which retains volatile
Review
Scheme 14. Butyl Phenylcarbamate
products. For these reasons, isocyanurates are sometimes
considered fire-resistant additives.
2.4. Allophanate and Biuret
2.4.1. Formation. Urethane and urea adducts are active
compounds thanks to the hydrogen atom linked to the nitrogen
atom. Because they are less reactive than hydroxyl or amine
compounds, the reactions occur especially when isocyanates are
introduced in excess. By the reaction of isocyanate with
urethane or urea group, an allophanate or biuret, respectively,
forms, as summarized in Scheme 15. Due to the electron-
withdrawing effect of the carbonyl group, urethane and urea
groups have a much lower reactivity than the secondary amine
-N-H groups; in order to promote allophanate or biuret
formation, a temperature typically greater than 110 °C or a
catalyst addition is necessary. To decrease isocyanate toxicity,
coating formulations favor high molar mass polyisocyanates
from allophanate, biuret, and isocyanurate chemistry.91
When uretdione is heated in the presence of a nucleophile,
such as an alcohol or an amine, two mechanisms were
suggested to occur, one of which generates allophanate or
biuret, respectively (see an example, Scheme 16, of allophanate
formation); the reaction proceeds either by free isocyanate
group releasing, generating new ureas, or through direct
allophanate formation. The second mechanism competes also
with linear polyurethanes formation, especially when isocyanate
is in excess, and so, the gel point is reached at lower conversion
(see section 3 of this review). Singh92 found that the reaction of
TDI dimer with alcohols at 90 °C gives principally diurethanes
with only traces of allophanates. Higher temperatures (in the
range of 125−160 °C) and a catalyst such as triethylamine or
N-methylmorpholine led to the formation of allophanate and
triphenyl isocyanates. Di-n-propylamine, di-n-butylamine, and
di-n-amylamine ruptured the dimer ring, whereas di-sec-
butylamine and dibenzylamine did not affect it.
2.4.2. Rate of Formation. Formation reactions of
urethane, uretdione, biuret, and allophanates compete between
each other. In a system containing monoalcohol, monoisocya-
nate, and water in presence of catalyst93 and in a selective
solvent, the following order of rate constants were found:
urethane ≫ biuret > allophanate. At a given temperature, the
ref equilibrium constant of biuret formation is higher by an order
89 of magnitude than the equilibrium constant of allophanate
89 formation.94 The rate of allophanate formation is much smaller
than that of urethane formation; therefore allophanates are
90 mainly formed when the overall ratio NCO/OH is higher than
1. For temperature below 60 °C, biuret and allophanate
90
formation is very slow; no trace of these functions was found
after 5 days when poly(oxypropylene)diol reacts with 4,4′-
diisocyanato-diphenylmethane systems.95
Schwetlich96 studied the alcohol−isocyanate reaction at 50
°C at NCO/OH ratio smaller than 1 and reported that the
urethane formation lies almost completely on the product side,
with or without the presence of common urethane formation
catalyst (DBTDL or DABCO). Special catalysts such as amino
alcohols, amidines, or alkoxide anions are needed to enhance
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Chemical Reviews
Scheme 15. Two Chemical Pathways Proposed for Allophanate and Biuret Formations
Scheme 16. Transreactions between Uretdione and Alcohol
allophanate and isocyanurate formation; nevertheless alcohol is
then only partly consumed.96
At high NCO/OH ratio and high temperature, Kogon97
found that the equilibrium constant of the allophanate 4
formation (Keq) equals 0.2 at 128 °C. This constant is
independent of the ratio phenyl isocyanate 2/ethylcarbanilate 3
(varying from 9 to 12) but decreases when temperature
increases (Scheme 17). When the reaction is catalyzed by
tertiary amine like N-methylmorpholine, triphenylisocyanurate
is the only final product formed via allophanate intermediates.
In bulk, Heintz98 measured an increase of allophanate
concentration with temperature. The amount of side products,
namely, the percentage of nitrogen atom involved in
allophanate bond, was quantified by 1H NMR as a function
of time and temperature for the diol−isocyanate reaction
(NCO/OH = 1.6) (Figure 2). With moderate temperature
increase from 108 to 145 °C, the amount of allophanate
increases from a negligible content (less than 1%) to over 10%
of all nitrogen-containing compounds. Both low and high
molecular species equally participate to the allophanate
formation. The presence of such trifunctional groups broadens
the molar mass distribution. In that case, isocyanurate
concentration is much less than the allophanate one.
2.4.3. Reversibility. Allophanate and biuret bonds, as
products of addition reactions between isocyanate and
compounds bearing active hydrogen, are thermally reversible
when heated. Their thermal stability is generally considered as
lower than that of the urethane bond. The decomposition rates
in halogenated solvent were reported by Kogon (Scheme 18
and Figure 3). The reaction rate increases with temperature for
allophanate and biuret groups. Allophanate is less stable than
biuret (comparison between 6 and 7 in Figure 3) and its
dissociation rate increases with temperature but also with
Scheme 17. Allophanate Formation from Phenyl Isocyanate 2 and Ethylcarbanilate 3
88
Review
Figure 2. Allophanate concentration during the reaction between a
secondary hydroxyl of poly(propylene glycol) and MDI.98
Scheme 18. Allophanate (X = O) and Biuret (X = N)
Decompositions
aromatic substitution (comparison between 5 and 6 in Figure
3).
An interesting work of Duff et al.100,101 compared the
thermal stability of the different R−NH−CO−X bonds. Such
study was performed on an isocyanurate-rich polymer, obtained
by homoaddition of 4,4′-methylene diisocyanate (MDI) in the
presence of stannous octoate, leading to aromatic N-functions
such as urea, amine, uretdione, biuret, and isocyanurate. The
thermal stability of this resin was studied by recording the
relative content of N-function by 15N cross-polarization/magic
angle spinning spectroscopy (CP/MAS NMR) from room
temperature to 500 °C (Figure 4). Upon increase of the
temperature, degradation of isocyanate, uretdione, and biuret
led to an increase of urea linkage concentration up to 230 °C.
Then, between 240 and 260 °C, urea degradation occurred
leading to amine bonds whereas isocyanurate linkage broke
from 280 °C. Since allophanate has been proven to be less
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Chemical Reviews
Figure 3. First-order rate constant for allophanate and biuret
decompositions (structures are given in Scheme 18).
Figure 4. Content of N-functions measured by 15N CP/MAS NMR
for each thermal decomposition temperature. Uretdione functions
were identified but not quantifiable.
stable than biuret, the thermal stability of isocyanate-based
bonds ensues:73,95 allophanate < biuret < urethane < urea <
isocyanurate.
Very recently, Kozakiewicz and co-workers showed on a
model allophanate molecule (obtained from phenyl isocyanate
and N-ethylurethane) that not only transurethanization but also
urethane decomposition could regenerate isocyanate functions
for further curing. They made use of these findings to introduce
functional blocking agents for efficient gelling reaction during
heat curing.102
2.5. Oxazolidone
Heating an epoxy function in the presence of an isocyanate
group leads to the formation of an oxazolidone ring, together
with the trimerization of isocyanate and the homopolymeriza-
tion of epoxy.103,104 It was found that the main reactions take
place step by step while the temperature increases: (i)
isocyanurate formation (Scheme 19a), (ii) epoxy−isocyanate
reaction leading to oxazolidone rings (Scheme 19b), and (iii)
isocyanurate decomposition by epoxy groups producing
oxazolidone rings (Scheme 19c).105 Isocyanurate rings were
found to be stable in the presence of epoxide and isocyanate
excesses, that is, reaction b is faster than c.103 A catalyst like
imidazole decreases the reaction temperature and promotes the
89
Review
Scheme 19. Epoxy Isocyanate Reactions
trimerization, but not the oxazolidone formation, while tertiary
amines favor the isocyanurate ring formation.106 Thus,
depending on the catalyst and the reactant ratio, the cross-
linking density of diepoxy/diisocyanate material can be adjusted
by varying the oxazolidone/isocyanurate ratio.
Okumoto et al.107 studied model reactions through ab initio
calculations to determine the main reactions pathways (Scheme
20). The 2-oxazolidone 9 is thought to be produced by a dual
SN2 reaction, where the catalyst (e.g., Cl−) is a nucleophile and
a leaving group on the ethylene−oxide carbon. Isocyanurate 10
is generated by the stepwise association of three isocyanate
molecules, where one of the molecules is initially linked with a
base. The six-membered ring isocyanurate is isomerized
stepwise into the isocyanate and 2-oxazolidone components.
A tetrahedral type of complex 11 between the isocyanurate and
a base-catalyzed ethylene oxide is the key intermediate for the
isomerization.
2.6. The Reactivity of Diisocyanates and Polyisocyanates
Diisocyanates are extensively used as monomers in the
manufacture of polyurethanes formed by addition reactions
(vide inf ra). The use of a diisocyanate is directly proportional to
the price of diamine supply and phosgenation; since
inexpensive aliphatic diamines are not readily available as
precursor for diisocyanates, the aromatic diisocyanates, that is,
NCO groups borne by an aromatic moiety, represent more
than 95% of the market. Among them, two products are
especially widespread, TDI and MDI. Due to its small size and
symmetry, the para-phenylenediisocyanate molecule (PPDI)
provides great reactivity difference between the first NCO to
react and the remaining one. Regarding the aliphatic molecules,
the main reactants are HDI and to a lesser extent IPDI and
bis(4-isocyanatocyclohexyl)methane (also called hydrogenated
MDI, HMDI; see Scheme 21 for the structure of this product).
m-Tetramethyl-xylylene (TMXDI) is a special molecule since it
allows preparation of solvent-free waterborne polyurethane
dispersions due to its low reactivity toward water (for a recent
review, see ref 108).
For a symmetric diisocyanate, both isocyanate groups initially
present the same reactivity (k1 = k2 = k). But, as the NCO
group itself exhibits an activating effect on the isocyanate
reactivity, the second (unreacted) isocyanate group undergoes a
substitution effect and its reactivity can be lowered (k′) by the
electronic and steric effect of created urethane or urea group
(see Scheme 22a as an example). The first isocyanate group of
2,6-TDI reacts 5.8 times faster with poly(propylene) glycol at
60 °C than the second one.109 For longer distance between
diisocyanates, the reactivity difference due to substitution is
smaller. For HMDI, the ratio between k and k′ is reported to
equal 1.4.110 It should be noted that a temperature increase
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Chemical Reviews Review

Scheme 20. Different Reactions Theoretically Able To Occur in Model Epoxy−Isocyanate Reactions in the Presence of a
Nucleophilic Catalyst

Adapted from ref 107.

Scheme 21. Names and Structures of Common Diisocyanates with Their Room Temperature State in Italicsa

a
Values in parentheses indicate the melting temperature.

lowers the reactivity differences. The reactivity ratio varies from
2.9 at room temperature to 1 at 70 °C for MDI reacting with n-
butanol.110,111
Asymmetric diisocyanates exhibit two initial different
reactivities (k1 and k2), which are again altered by the reaction
of the first isocyanate group. Thus, a reaction between an
asymmetric diisocyanate and nucleophilic compound leads to
four reaction rate constants as exemplified in the case of 2,4-
TDI in Scheme 22b. These reactivity differences strongly
complicate diisocyanate kinetics study. Table 5 shows the
reactivity ratios between isocyanate groups of 2,4-TDI reacted
with different types of alcohol. The discrepancy in the results is
attributed to the temperature increase, which decreases the
selectivity. According to the work of Burel et al.,112 the
selectivity between primary and secondary isocyanate groups of
IPDI (ksecondary/kprimary) decreases with temperature going from
31 at 25 °C to 15 at 90 °C.
90
An efficient catalysis can compensate the reactivity differ-
ences; for example, the secondary isocyanate group of IPDI is
1.6 times more reactive with n-butanol at 50 °C than the
primary NCO group. Using DBTDL, the reactivity of the
secondary NCO group is 12 times superior to the primary one;
while in the presence of DABCO, the primary NCO group is
1.2 times more reactive than the secondary one.72
2.7. “Polymeric Isocyanates”
During the course of dimer and trimer preparations, MDI and
HDI, symmetric diisocyanates with close reactivity for both
groups, give both the targeted product and oligomers of low
molar masses.113 Dimerization of MDI (12) in bulk was studied
in a wide range of temperature, in both the solid and liquid
state (Scheme 21 and Figure 5). In an effort to keep MDI
under its monomeric state, storage temperature is thus set
either at very low temperature or just above the melting point,
where the rate of formation of dimer is the lowest.114
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Chemical Reviews
Scheme 22. Consecutive Reaction Steps in the Case of Diisoocyanate/Alcohol Reaction Starting from (a) 2,6 TDI and (b) 2,4-
TDI
Table 5. Typical Example of Reactivity Ratios of an
Asymmetric Diisocyanate (2,4-TDI) against Hydroxyl
Groups, Taking the Lowest Reaction Rate as the Reference
(k′2)
diisocyanate alcohol r1 = k1/k′2a r2 = k2/k′2b r′1 = k′1/k′2
2,4-TDI n-butanol, 25 °C8 18.1 4.5
poly(propylene glycol), 15.8 2.6
60 °C109
a
NCO group in para position. bNCO group in ortho position.
Figure 5. Rate of dimer formation as a function of temperature.
Reprinted from ref 114 with permission. Copyright 2009 BASF
company.
Greater difference of reactivity between the two isocyanate
groups facilitates the control of reactions.115 In the case of the
asymmetric IPDI, the primary isocyanate group reacts
preferentially, but reaction with the secondary isocyanate
group likely occurs (r = 2−3).85 Thus, the trimerization
reaction of isophorone diisocyanate leads to species from
isocyanate trimer to tridecamer, trimer and pentamer (which
structure is given in Scheme 23) representing 71 and 19 wt %
of the full mixture, respectively.116
One should note that polymeric isocyanates strongly increase
the viscosity of solution. Another way of increasing the viscosity
consists in reacting diisocyanate with monoalcohol to favor the
Review
Scheme 23. Example of Pentamer Produced from the Self-
Addition of Isophorone Diisocyanate
4.2
2.1
formation of low molar mass allophanate species.117 High
molar mass polymer bearing several isocyanate groups can also
be prepared by copolymerizing isocyanate bearing monomers
such as 2-isocyanatoethyl methacrylate118 or 3-isopropenyl-
α,α′-dimethybenzyl isocyanate.119−121
2.8. Conclusion
The high reactivity of the isocyanate group toward any
nucleophilic compound promotes its reaction with both the
reactant and the formed product from isocyanate/nucleophile
reaction, if it is sufficiently nucleophilic. Generally speaking, the
nucleophilicity of active hydrogen compounds governs the
reactivity toward isocyanate. Table 6 presents generally
accepted relative reaction rate as a rule of thumb. All these
reactions compete among each other and all are reversible.
Moreover, for diisocyanate, the situation is even more
complicated by the intrinsic difference of reactivity between
the isocyanate groups. Thus, studying these systems and above
all kinetics from a fundamental prospect is extremely complex.
On the other hand, the flexibility of the isocyanate chemistry is
a convenient tool to stem from a wide range of compositions in
an industrial way, as shown in the following section.
3. IMPLICATIONS OF THE URETHANE/UREA BOND
REVERSIBILITY IN PREPARING POLYURETHANE
MATERIALS
The synthesis of PU is carried out by one or few of the
reactions described in Scheme 3. If the functionality of the
hydroxy-containing compounds or the isocyanate is increased
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Chemical Reviews Review

Table 6. Relative Reactivity of Active Hydrogen Compounds proportional to the difference between the solubility parame-
against Isocyanatea ters, δ, of the soft and hard blocks) and the degree of
polymerization (N). It is called reaction (or polymerization)
relative reaction
rate (noncatalyzed, induced phase separation. The role of hydrogen bonding has
hydrogen active compound formula 25 °C) extensively been discussed, and it has been demonstrated that
primary aliphatic amine R−NH2 1000 hydrogen-bonded species grow at the same time that phase
secondary aliphatic amine R2NH 200−500 separation evolves.122−124 At the end, the resulting microphase
primary aromatic amine Ar−NH2 2−3 separation morphology is composed of soft-rich and hard-rich
primary hydroxyl RCH2−OH 1 phases. Depending on the composition, the sizes of the hard
water HOH 1 domains are in the range of 10−50 Å, but also cocontinuous or
secondary hydroxyl R2CH−OH 0.3 inverted structures can be obtained. Usually the SSs are
urea R−NH−CO−NH−R 0.15 amorphous with a glass transition Tg lower than room
tertiary hydroxyl R3C−OH 0.005 temperature, and hard domains are semicrystalline with a Tg
phenolic hydroxyl Ar−OH 0.001−0.005 in the range of 50−100 °C and melting temperatures from 120
urethane R−NH−COOR 0.001 to 180 °C. As the result of phase separation, a physical network
a
Isocyanate structure was not given. Data from ref 110 were is formed.
normalized according to the rate of the water-isocyanate reaction. The other independent transformation that can take place
during network formation but also during the synthesis of a
linear polymer in bulk is vitrification. This transition occurs at
beyond 2, branched and possibly cross-linked polymers are the particular extent of reaction where the increasing glass
produced. The nature of the polyol (polyether, polyester, transition temperature, Tg, of the reacting system equals the
polycarbonate, or polyolefin) and of isocyanate components instantaneous value of the cure temperature. At this time, the
can vary widely, making PUs one of the most versatile polymers macroscopic behavior of the system changes from a liquid (for
to produce a wide variety of materials such as high performance a linear or a growing network) or rubber (for a growing
elastomers and tough thermoplastic, foams (flexible and rigid), network) to a glass. This means an increase of several decades
coatings, adhesives, sealants, or fibers. In the following, we in the value of the storage modulus. Several equations have
summarize the main steps occurring while synthesizing and been proposed to describe the increase of Tg with extent of
processing PU copolymers, before showing some examples of reaction; it may, however, simply be predicted by characterizing
the use of the reversibility in real industrial cases. the initial and final materials using differential scanning
3.1. Synthesis of Polyurethane Materials calorimetry.126
3.1.1. Polymerization and Phase Transitions. To obtain 3.1.2. Thermoplastic versus Thermoset Polymers. For
TP or cast PU elastomers, one or two diols can be reacted with linear segmented TPU, phase separation is the essential
the isocyanate. When two diols are used, the first one is a parameter for controlling the final thermomechanical behavior.
macrodiol with a molar mass in the range (5−10) × 103 These polymers offer unique possibilities for tailor-made
g·mol−1, and the second one is a short diol, typically 1,4- materials through the variation of the block lengths and
butanediol. The PU may be prepared either by the one-shot composition. They are widely used for high-performance
process (three components reacting together) or by the applications, especially when high tear and tensile strengths
prepolymer approach (a prepolymer is prepared first and or good wear and abrasion resistances are required. For some
then reacted with the short diol as the chain extender) (Scheme applications, if the soft segment or the chain extender have a
24). functionality higher than 2, the same process can be used to
During the reaction in bulk, the hard segments (HSs) synthesize cross-linked cast PU.
become incompatible with the soft segments (SSs), so that For thermosetting polymers, two structural transformations
phase separation takes place during polymer-forming urethane are likely to occur during network formation. At the end of the
or urea reactions. Small angle X-ray scattering, at a certain stage reaction, practically all constituent units are covalently bonded
of the reaction, shows the apparition of a peak that marks the into an infinite three-dimensional structure. This means that
onset of phase separation.122−125 The driving force for during the polymerization, the system evolves from a collection
microphase separation is thermodynamic in nature; it is of molecules of finite size to an infinite network, proceeding
governed by the product of the interaction parameter (χ, through the gel point at which the infinite network structure

Scheme 24. Schematic Synthesis of Linear Segmented Polyurethane

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Chemical Reviews
appears for the first time. Before the gel point, the material is a
liquid with a finite value of viscosity. As the reaction proceeds,
the viscosity increases and it tends to infinite at the sol−gel
critical transition, when a giant macromolecule percolates
through the sample. Gelation can be roughly estimated as the
time (extent of reaction) at which the elastic modulus becomes
higher than the loss modulus, or more precisely, at which the
ratio of both moduli (tan δ) becomes independent of the
frequency of the experimental run. The extent of reaction at the
gel point depends on the functionality (number of reactive
sites) of precursors: the higher the functionality, the lower the
gel conversion. After gelation, the mass fraction of the insoluble
giant structure increases continuously and so does the elastic
modulus of the sample.126 For thermosetting polymers, shaping
of the part has to be performed before the gel point where the
material is still in the liquid state. Note finally, that in the case
of PU, the boundary between thermoplastic and thermosetting
is not so clear. Particularly, linear segmented PU can be
processed as TP granules or as cast PU. In addition when some
urea links are introduced in the linear chains, the polymer
became intractable and has to be processed like a thermosetting
polymer.
3.2. Processing of Polyurethane Materials
3.2.1. Bulk Cross-Linked PUs by Cast Molding (CM)
and Reaction Injection Molding (RIM). Because isocyanate/
alcohol and isocyanate/amine reactions are very fast, give no
byproduct, and attain high degree of conversion, they are well
suited for direct polymerization of two reactive liquids, A and B,
in a mold. Part A is the isocyanate-based component, and part
B is composed of the diols plus a catalyst (or diamines)
together with usual additives like antioxidants, pigments, and so
on. PU formulations for reactive molding follow the same
strategy as the one described in Scheme 24. Two cases are
distinguished: (i) all precursors bear the same functionality of 2
and then an excess of isocyanate is used to generate
allophanate, resulting in further cross-linking; (ii) some
precursors of higher functionality are introduced, for example,
reactive oligomers like polycaprolactone with functionality
equal to 3 or 4, isocyanates, such as liquid MDI with f ≥ 2.3 or
polymeric MDI, or chain extenders like trimethylol propane,
TMP. When increased rigidity and high-temperature perform-
ance are desired, further cross-linking may be accomplished via
isocyanurate formation, using aromatic isocyanates rather than
aliphatic ones (Scheme 11). In this case, base catalysts, such as
alkoxides, quaternary ammonium, or phosphonium, promote
this reaction.
The main difference between cast molding and RIM is to be
found in the reactivity. For cast molding, the pot-life is usually
higher than 5 min, whereas for RIM it has to be less than 1 min,
which means that isocyanate is reacted either with amine or
with alcohol in presence of catalyst. RIM is similar to
thermoplastic injection molding except for the curing reaction
in the mold. Two reactive monomeric liquids, A and B, are
mixed together by impingement and injected into the mold by
the so-called “one-step” method (Scheme 24). It involves the
high-speed mixing of two or more reactive chemicals, just as
they are injected into the mold. The low-viscous mixture fills
the mold at relatively low temperatures and pressures. The
reactions must be synchronized with the process so that
gelation does not occur during the filling time. In the mold,
polymerization and usually reaction induced phase separation
93
Review
between SSs and HSs occur; the part solidifies and is then
ejected.
Contrary to RIM, a “two-step” process is often used for cast
molding. At the end of the prepolymer synthesis (Scheme 24),
the diisocyanate excess depends on the initial excess and also
on the reactivity ratio between the two isocyanate groups. As
sustainable development is the major trend for the future, the
diisocyanate molecules in excess can be a problem to solve.
There are different routes to decrease the toxicity of volatile low
molar mass diisocyanates. The first route is to increase the
boiling temperature and to decrease the vapor tension by
making adducts (as examples trimers of IPDI or adducts of
HDI + TMP). Other possibilities are to distillate the
diisocyanate excess after the synthesis of the prepolymer or
to play with the different reactivities of the diisocyanate (like
TDI 2,4 or PPDI) to prepare “diisocyanate-free” formulations
(vide inf ra).
Finally, in addition to cast and reaction injection molding,
thermoplastic polyurethanes are sometimes processed in the
melt state where the urethane bond reversibility behavior is
exacerbated (see section 3.3).
3.2.2. Reaction in Solution: Coatings, Sealants, and
Adhesives. Thanks to their excellent adhesives properties,
good weather stability, and versatility of formulation,
thermosetting PUs are currently the preferred materials for
coatings, sealants, and adhesives. The majority of conventional
formulations are solvent-borne, traditionally containing about
25% solids. Organic solvents are used to disperse the different
constituents of the formulation and to provide the low viscosity
needed for conventional application methods (spray, roller
coating, etc.). Solvent-based PU films are formed by
simultaneous cross-linking of polymer network precursors and
solvent evaporation. This is a complex process in which the
cross-linking rate and the development of the network depend
on the content, nature, and volatility of the solvent.127 Because
coating and paint producers as well as end-users wish to reduce
the volatile organic compound (VOC) emissions, progress is
being made to increase the solid contents of solvent-based
liquid coatings.128
3.2.3. Reaction with Water: Preparation of Solid
Foams. PU foams are an important commercial application
of PU chemistry. They are prepared from basically the same
raw materials as elastomers by the “one-step” method (Scheme
24) and with the use of a RIM machine. Here however, instead
of the chain extender, water is used to react with isocyanates
and form an amine and CO2, which results in foaming. The
diamine thus created can then react with isocyanate groups
giving polyurea short segments. A catalyst can be used; both
reactions are exothermic and proceed simultaneously to
generate a cross-linked network, which is blown into a cellular
structure by the heat expanded CO2 and entrapped air. A
silicone-based surfactant is also introduced as a cell control
agent. Self-assembly of the HSs leads also to the formation of
hard domains.124
The main difference between rigid and flexible foams is the
molar mass of the polyol component, less than 103 g/mol for
rigid foams and between (2 and 8) × 103 g/mol for the flexible
ones, and also the average functionality of the polyol, much
higher than 2 for rigid foams. Industrially, the catalysts not only
bring faster rates for the reaction but also influence the
selectivity and thus permit control of the balance between the
following reactions: (i) water + isocyanate producing urea
linkages and CO2 as blowing molecule; (ii) alcohol +
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Scheme 25. Model Reactions Involving Isocyanate Group in Polyurethane Foams

Table 7. Rate Constants of the Different Reactions Involved in Polyurethane Foam Synthesis Using Various Catalysts
cross-linking activityb
urethane formation or urea formation or allophanate isocyanurate
gelling activity blowing activity formation biuret formation formation
catalyst k1,a L2/(g·mol·h) k2,a L2/(g·mol·h) k3, L2/(g·mol·h) k4, L2/(g·h) k5, L2/(g·mol·h) k6, L2/(g·h) k7, L2/(g.mol.h)
triethylamine (TEA) 11.6 6.0 0.72 0.1 1.2 <0.1 0
2,2′-diazabicyclo[2.2.2] 109 14.5 0.32 0.18 2.00 <0.1 0
octane (DABCO)
trimethylamino-ethyl- 28.9 43.3 380 48 410 21 37
ethanolamine
DBTDL 144 4.8 30 17 0 0 0
a
Determined by titration method. bDetermined by high-performance liquid chromatography (HPLC).

isocyanate reactions leading to polyurethane formation; (iii)
alcohol + urethane/urea leading to a cross-linked material
through allophanate, biuret, and isocyanurate bond formation.
As an example, rate constants for the different reactions
depicted in Scheme 25 are given in Table 7.129
Organotin catalysts preferentially activate alcohols over water
due to the higher nucleophilicity of the oxygen atoms of
alcohols. Thus, DBTDL exhibits very high activity for the chain
extension through isocyanate/alcohol reaction but generates
weak urea formation and no activity at all on the biuret and
allophanate. Organotin catalysts are also preferred for polyur-
ethane synthesis in aqueous medium (see below).130 Amine
catalysts provide a higher catalytic activity toward biuret
formation compared with allophanate reaction, and depending
on their structure, they favor blowing or gelling reaction. For
instance, tertiary amines containing ether bonds with two
carbons between amine and ether, such as 2,2′-dimorpholine
diethyl ether (DMDEE), have a higher affinity to water than
alcohol that arises from their capacity to form chelates with
water molecules and, thus, to activate urea formation
preferentially to urethane formation.131 In contrast, DABCO
has extremely low steric hindrance on the nitrogen atom and
94
the unpaired electron is in a very active state to promote
urethane formation (Table 7). Isocyanate−hydroxyl reaction is
also favored over the water−isocyanate one in the presence of
zirconium chelates.40
3.2.4. Reaction in Water: Waterborne Coatings. One of
the key choices for reducing VOC emissions is the generation
of waterborne coatings. Ionizable groups (usually carboxyl
introduced by the use of dimethylol propionic acid during the
first step in Scheme 24) are first incorporated into the
polyurethane backbone and neutralized with carboxyl groups
with a tertiary amine, before being dispersed in water. Aliphatic
and cycloaliphatic isocyanates are preferred because of their low
reactivity with water and to prevent yellowing of the final film.
One difficulty is to control reactions of isocyanates with water,
which means a poor control of the stoichiometry and so of the
molar mass of the final PU. Another problem is the coalescence
of the initially stabilized polymer particles which is often
incomplete in the final film and may take a long time to reach
equilibrium. For these two reasons and to increase its thermal
stability, the film is in some cases postcured by a polyisocyanate
leading to isocyanurate (or uretdione) structures (Scheme 11).
This is accomplished by the use of a two-component, 2K,
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system, which is not the preferred solution for end-users. Some
water-soluble systems are based on bisulfite adducts of
isocyanate prepared in aqueous solution from sodium bisulfite
or sodium pyrosulfite. Bisulfite masked isocyanates are mainly
sensitive to pH variation, rather than temperature increase; at
basic pH they hydrolyze and form symmetrical ureas (Scheme
26).
Scheme 26. (a) Masking Reaction between Isocyanate and
Sodium Bisulfate and (b) Urea Formation
3.2.5. Solvent-Free Reaction: Powder Formulations.
Powder coating technology is another route to apply PU
formulations in a solvent-free and hence environmentally
friendly manner. The two-component powder (plus additives)
is first produced by an extrusion process. The formulation is
applied onto the substrate by electrospray and then the
substrate is heated above Tg (or the melting temperature, Tm)
to produce film flow and cross-linking. The requirements for a
one-pack (1K) powder coating formulation are as follows: (i)
Tg/Tm must be at least 20−30 °C above ambient conditions in
order to store and handle the powder; (ii) polymers with low
molar masses are preferred to allow enough flow above Tg/Tm
to obtain a smooth film before the beginning of cure; (iii) the
cure temperature must be placed at 40−50 °C above Tg/Tm to
achieve a convenient flow leading to film homogeneity. Typical
systems are based on saturated polyesters, α,ω-OH terminated,
cured with an isocyanate-based molecule. In a 1K-powder
system, the isocyanate functions have to be blocked up to the
final curing step. To obtain the 1K-powder coating formulation,
masked isocyanates have to be extruded at about 100 °C with
polyamine or polyalcohol oligomer without reaction. For-
mation of the polyurethane coating is then accomplished by
releasing the isocyanates upon heating and then reacting the
free isocyanate groups with the hydroxyl component.
1K formulations can be prepared in different ways. One
strategy consists of using a blocking molecule, which releases at
high temperature to regenerate an isocyanate. This strategy is
extensively described in the next section. Making use of the
difference in reactivity between free isocyanates and uretdione
rings, diisocyanate dimers can also be used as “self-blocked
isocyanates”. They offer the potential advantage that no volatile
byproducts are formed. As an example, the 2,4-TDI dimer
contains one uretdione ring, formed by dimerization of two
isocyanate groups, and two free isocyanate groups. The latter
react rapidly with the hydroxyl groups of a macrodiol at
temperatures above its melting temperature (Tm = 80 °C). In
the presence of additional −OH groups, the regenerated
isocyanate can then react to form urethanes. Experiments have
also revealed the formation of allophanate groups as reaction
products of a uretdione ring with a hydroxyl group. Application
of branching theory has shown that the system can gel due to
allophanate formation in a wide range of initial molar ratios of
NCO to OH groups.73 Formation of allophanates is favored by
DBTDL. With primary amines, the direct reaction with the
dimer is favored, but biurets are also obtained.7,85 The last
route for preparing masked isocyanates is by microencapsula-
tion. As an example, the microencapsulation of the solid 2,4-
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TDI dimer was accomplished by interfacial polycondensation at
room temperature, with ethylene diamine in cyclohexane and in
a polycaprolactone diol. The microcapsule shell is formed by
the reaction of the diamine with the isocyanate groups at the
surface of the powder. If encapsulation is efficient, reactions
between NCO and OH groups take place only after the 2,4-
TDI dimer melting.132 The difficulty of this process is the
knowledge of the exact numbers of functional −NCO groups
inside the capsules.
3.2.6. Isocyanate Chemistry in Self-Healing Materials.
Encapsulated isocyanates have been proposed for the develop-
ment of polymeric coating systems that are stimuli responsive
and possess the ability to self-heal when damaged. In this case,
the PU coating formulation contains small amounts of healing
agent in the form of microcapsules homogeneously dispersed in
the medium. Microcapsules are prepared in water according to
established procedures. Their shells are formed of a copolymer
of acrylic acid and an acrylate of a long aliphatic alcohol;
diisocyanates (HDI, IPDI, or 4,4′-MDI) are inside. Depending
on type of copolyacrylate, type of surfactant (anionic surfactant
sodium dodecylsulfate or nonionic ethoxylated nonylphenol),
temperature and rate of dispersion the microcapsule sizes were
in the range 5−100 μm. To encapsulate the di- or
polyisocyanates, different polyalkyl acrylates having sharp
melting points of 58, 65, and 92 °C were used. About 3−7
wt % of different types of microcapsules (with different shell
temperature melting points) were incorporated in a two-
component polyurethane formulation. The most attractive
feature of this system is that the factors that cause the most
damage to the coating, such as humidity, mechanical
compromise, and exposure to high temperatures, are the
same factors that initiate self-healing phenomenon.133
3.3. Reversibility of Urethane Bonds and
Transcarbamoylation during the Processing of
Polyurethanes
3.3.1. Example 1: Reversibility and Rheological
Behavior. As demonstrated in Figure 1, the thermal
degradability of polyurethanes in the melt state is inevitable
because melting of the HSs usually occurs around or beyond
the stability temperature of the urethane linkages.134 The
thermal degradation of TPUs exerts a significant effect on
rheological behavior, and thus processing conditions. They
show a sharp increase in flow, greater than expected due to
thermal effects only. The viscosity decrease is interpreted in
terms of a thermally induced molar mass decrease, and as
expected from the reversal of the urethane formation reaction,
the viscosity equilibrium is associated with a molar mass
equilibrium. To describe the flow of melt TPU, kinetic models
have been proposed in which both flow and reversible reaction
contribute to the total activation energy for the process.64,135,136
Injection molding up to 180 °C gives no change in molar
mass but increasing temperature to 220 °C divides the mass-
average molar mass (Mw) by two for commercial ester-based
PUs and by three for ether-based ones.137 The same trends
were measured during PU annealing, in which the depolyme-
rization process is detectable from 180 °C. Moreover, insoluble
gels are detected after 60 min at 190 °C.137 Yang et al. observed
on model polyurethane oligomers the existence of free
isocyanates above 150 °C.138 Free isocyanate groups react
either on decomposition products (alcohol or amine) or on the
urethane and urea linkages leading to possibly insoluble gels
formed by allophanate and biuret cross-links, respectively.
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It should be noted that the thermally induced molar mass
decrease is completely reversible. Figure 6 shows the
Figure 6. Molar mass decrease as a function of temperature. Labels
indicate the time necessary to reach equilibrium.64
equilibrium values reached as a function of temperature. The
higher the initial molar mass, the higher the number of broken
bonds.135 Bajsic and Rek139 prepared four PUs by reacting
poly(oxytetramethylene)glycol or poly(caprolactone glycol)
with HMDI or H12MDI. They recorded the first degradation
step of PU by TGA between 280 and 300 °C. By rheological
measurements, Hentschel64 confirmed that at constant temper-
ature between 180 and 220 °C, the molar mass of the
polyurethane melt exponentially drops and asymptotically
approaches a constant value.
For the commercial TPU consisting of MDI and hexanediol,
with a molar mass of 30.5 kg·mol−1 (ISOPLAST 2530 from
Dow Chemical Company), the so-called ceiling temperature
(Tcl) was determined to be 160 °C using temperature-
modulated differential scanning calorimetry (TM-DSC).
Furthermore, the TM-DSC experiments proved that the
depolymerization reaction of TPU is completely reversible
and equilibrium is attained almost instantaneously. By another
technique, Fourier transform infrared (FT-IR) spectroscopy,
and by measurement of the increase in the isocyanate
absorption band at 2270 cm−1 with increasing temperature, a
quantitative depolymerization curve was constructed. The
complete reversibility of the reaction was checked by both
the disappearance of the isocyanate absorption band after the
sample cooled to room temperature and the absence of any
absorption band characteristic of products from side irreversible
reactions of isocyanate (Scheme 8). By FT-IR spectroscopy, a
Tcl of 155 °C was derived for the polymer, quite similar to the
one given by the TM-DSC technique. Furthermore, highly
elevated temperatures were necessary for complete depolyme-
rization to come back to monomers.140
To conclude on this first case, and adopting the point of view
of the manufacturer who processes TPU, the important result is
that both the processing temperature and the residence time of
the polymer in the molten liquid state strongly affect its flow:
the viscosity is decreased and thus processing conditions are
easier, knowing that the molar mass decrease is in principle
reversible. However, if processing temperatures are too high or
for too long residence time, other thermal degradation or
nonreversible reactions known for PU (free isocyanate groups
forming carbodiimide and carbon dioxide but also dissociation
of the urethane group to amine, carbon dioxide, and olefin or
dissociation to secondary amine and carbon dioxide, formation
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Review
of cyclic oligomers, etc.) could occur, exerting a significant
effect not only on rheological behavior but also on material
properties.
The reversibility of the urethane link and the resulting low
melt viscosity of the polymer can be a difficulty while producing
PU films by extrusion blowing. One trick to overcome this lack
of film stability consists in adding silica to increase artificially
the melt viscosity.141
3.3.2. Example 2: Reversibility To in Situ Compatibi-
lize Polymer Blends. Another application of the thermal
degradability of PU in the melt state is the reactive
compatibilization of blends in which one component is a
TPU. It is well-known that the most efficient way to stabilize
the blends of two immiscible polymers is to generate graft or
block copolymers in situ during the process of melt-blending.142
Sufficiently fast interfacial reactions are necessary to generate
compatibilizers within a short processing time. With the aim to
use reversibility of urethane bonds for in situ reactive
compatibilization of blends containing at least one TPU, Lu
et al.143 have investigated reactions between urethanes and
many functional compounds. A model urethane compound was
synthesized by simply capping 4,4′-MDI with n-octanol. This
low molar mass diurethane, dioctyl 4,4-methylenebis(phenyl
carbamate) (OMO) was reacted with several small monofunc-
tional compounds. NMR and FTIR spectroscopies were used
for quantitative analyses of formed products. According to the
conversions of urethane linkages at 200 °C after 5 min, the
reactivity of the common functional groups toward urethane
linkages can be roughly ranked in decreasing order as follows:
primary amine > secondary amine ≫ hydroxyl ≈ acid ≈
anhydride ≫ epoxy. The reactions between OMO and primary
amine were also conducted at different temperatures between
170 and 200 °C and are best described with a second-order
bimolecular reaction model. In short, the two types of amines
(primary and secondary) are the most well suited function-
alities for reactively compatibilizing TPU with other functional
polymers. Anhydride, acid, and hydroxyl groups may also be
used depending on specific situations. The epoxy functionality
is not recommended, given its low reactivity toward urethane
linkages.
3.3.3. Example 3: Reversibility To Generate “Reproc-
essable” Cross-Linked Polymers. The only functional group
that was not used in the work describe above143 was isocyanate.
In the same way as Lu et al.,143 Lapprand et al.144 have studied
the reaction of the same low molar mass diurethane, OMO,
with 4,4′-MDI or trimer of isophorone diisocyanate (tIPDI).
The products of the reaction were characterized by SEC and
MALDI-TOF for molar mass determinations, and 1H and 13C
NMR for characterization of functional groups. Thanks to a
model study, it was possible to clearly identify allophanates as
new functional groups after the reaction of an excess of
isocyanates (equimolar NCO/urethane ratio) at high temper-
ature (170 and 200 °C) and after the mixture was cooled to
room temperature. Only 10% allophanates were obtained after
1 h of reaction, but one important and unexpected result was
that no isocyanurate was found as a reaction product.
Concerning the molar masses and molar mass distribution,
the reactive system was composed of residual diurethane,
monourethane, and also numerous compounds of higher molar
masses identified as grafted di- or monourethanes. These latter
are the result of complex reactions between urethane bonds and
isocyanates, which further reacted with dissociated alcohol, for
example, ending in branched molecules. Comparing the two
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Scheme 27. (1) Allophanate Formation through the Reaction of Urethane with an Isocyanate and (2) Hydrolysis of an
Isocyanate Followed by the Formation of a Urea
polyisocyanates, when tIPDI is reacted with OMO in the same
experimental conditions, less allophanates and monourethanes
were formed.
These results prove the possibility to create some cross-links
through allophanate functions by adding a polyisocyanate to a
TPU by reactive extrusion. It has been applied to the
preparation of self-cross-linkable but still thermoplastic
materials.145 Poly(ethylene adipate) glycol is reacted with an
excess of isocyanate (NCO/OH = 1.21), generating up to
about 40% of the allophanate groups as cross-linking points,
while the other part forms only branching.146 Because of the
lateral isocyanate groups, the resulting polymer can be easily
cross-linked at ambient moisture. A scheme of the strategy used
is given in Scheme 27.145
This simple modification has already been used to improve
the mechanical and thermal properties of commercial TPUs.
Details of this study are out of the scope of this review, but
basically, it is very important to maintain a nanostructure for
the final material, which means the control of the competition
between the chemical reactions and physical microorganization
of soft and hard phases. At the end, the modified and cross-
linked TPU shows better mechanical behavior (creep) at
moderate temperatures (80−100 °C) and better thermome-
chanical properties at high temperatures. Additionally the
chemical cross-links of the modified TPU are reversible, and it
can be still processed as a conventional thermoplastic
elastomer.
3.4. Reversibility as a Means of Recycling Polyurethanes
Knowing that the urethane bond is unstable above 170 °C in
the solid and molten liquid states, it can be imagined that the
chemical recycling of PU materials (thermosets or thermo-
plastics) can be effective and economical. The properties of
recycled granules can be easily readjusted during an extrusion
process. The recycling of PU has been proposed by other
methods. In the regrind technology, the obtained fines particles
of recycled PU foams (like in automotive seating) were mixed
with fresh polyol. Because the solids are so fine, a slurry is
obtained, and they can be used to replace only up to 12% of the
polyols without affecting the quality of the new PU foam.
During the foaming process, transreactions such as the ones
described previously make the material homogeneous.
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Another proposal is to depolymerize thermoplastic or
thermosetting PU by the use of water, alcohols, or amines.
Glycolysis technology has been proposed to chemically
depolymerize PU foams.147 The splitting of the polymer chains
occurs under continuous stirring and temperature control and
with the help of a catalyst. Upon completion of the reaction
step, the recycled fluid is filtered and discharged. The reclaimed
polyol can be added to or mixed with original polyol to be used
in spray foam applications, flexible foams, elastomers, and other
traditional PU applications without any loss of quality. This
process can be economically acceptable, but it requires further
development to introduce less contamination in the post-
consumer material. Concerning this last remark, it can be said
that PU based on aliphatic diisocyanates are claimed as
nontoxic amine producers during the polyurethane degradation
process.
4. MODEL REVERSIBLE UREA/URETHANE BONDS:
THE CASE OF BLOCKED ISOCYANATES
4.1. Introduction
Industrial products take advantage of the reversibility of
isocyanate-based bonds by designing special derivatives of
isocyanates that thermally dissociate to regenerate the reactive
isocyanate function at a given temperature. Below this
temperature, the isocyanate is in a blocked form that decreases
the isocyanate reactivity and toxicity. A seminal work reviewing
blocked isocyanate systems was already done in the last
century.7,148,149 Later on, Wicks et al. published an exhaustive
review with over 1700 references that covered a broad range of
industrial applications from 1980 to mid-2000.5,6 Since
discrepancy was systematically found in the deblocking
temperatures, to the point that the relative order between
general classes of blocking molecule is still difficult to assess
nowadays, these reviews attempted to present as many
examples as possible, taken mainly from patent literature, to
provide a general guidance for applications.
Though other possibilities exist, blocked isocyanate is
generally described as an adduct containing a weak bond
formed by the reaction of isocyanate with a hydrogen active
compound. Since it is an equilibrium, this reaction tends to
regenerate the isocyanate group at elevated temperature
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(elimination step). Then, the free isocyanate reacts with a
substrate containing nucleophile to form thermally more stable
bonds (addition step). The overall reaction is summarized in
Scheme 28.
Scheme 28. (a) Blocking and Deblocking Reaction of
Isocyanate and (b) Curing Reaction
Since the adduct is less (or even not) sensitive toward
nucleophilic molecules and in particular toward water, blocked
isocyanates make it possible to prepare a one-component
reactive system with long pot life and lower toxicity and to
drastically reduce or even suppress solvent use.
4.2. Overall Mechanisms for Reactions of Blocked
Isocyanates
Optimizing a controlled blocked isocyanate system goes
through a compulsory step of studying the actual thermal
behavior. However, studying mechanisms and kinetics is hard
work owing to numerous reactions that occur at the same time,
most of which are reversible.
4.2.1. Elimination−Addition Mechanism. A blocked
isocyanate is an adduct containing a weak bond formed by
the reaction with a hydrogen active compound. At high
temperature, the adduct splits off to regenerate the free
isocyanate group (elimination step), which in turns reacts with
a nucleophilic substrate (addition step). This elimination−
addition mechanism is shown in Scheme 29.
Scheme 29. Elimination−Addition Mechanism
Considering that the rate constant K−2 is negligible, the final
product formation, under steady-state hypothesis, is written as
in eq 4:
K1K 2[NuH][BI]
rate =
K −1[BH] + K 2[NuH] (4)
where [NuH], [BI], and [BH] stand for the concentration of
nucleophile, blocked isocyanate, and blocking group, respec-
tively. The eq 4 shows two limiting cases given below.
If the curing reaction is much faster than the blocking
reaction, K2[NuH] ≫ K−1[BH], then, the rate is independent
of the nucleophile content (eq 5):
rate = K1[BI]
(5)
This situation occurs for instance in the case of blocked
isocyanate reacting with an amine. The reaction is described by
an overall first-order reaction, zero-order in amine and first-
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Review
order in blocked isocyanate (for instance, between an oxime
blocked isocyanate and an amine, see ref 150).
On the opposite, supposing that the blocking molecule BH is
more reactive toward isocyanate than the NuH leads to neglect
K2[NuH] > K−1[BH]. It is important to note that, in that case,
no curing reaction occurs except if the blocking molecule is
eliminated. The rate is expressed by eq 6:
K1K 2[NuH][BI]
rate =
K −1[BH] (6)
With this system, a part of the intermediate isocyanate reverts
to starting materials, resulting in an overall slower rate of
reaction, as in the case of blocked isocyanate reacting with
alcohols.
4.2.2. Addition−Elimination Mechanism. While the
elimination−addition mechanism is mostly mentioned in the
literature, the reverse mechanism, proceeding through a
nucleophile molecule addition on the blocked isocyanate
followed by the blocking molecule elimination (as shown in
Scheme 30) has been proven to apply to some systems where
the kinetics were specifically studied.
Scheme 30. Addition−Elimination Mechanism
Because the initial stage corresponds to the nucleophile
attack on the blocked isocyanate, this mechanism can be
thought of as chemical deblocking. The rate of cured material
formation is (eq 7)
K3[NuH][BI]
rate =
K −3[TI] (7)
where [TI] is the tetrahedral intermediate concentration.
4.2.3. More Complex Mechanisms. For some systems,
both mechanisms cohabit depending on the system composi-
tion (solvent, isocyanate, blocking molecule, coreactant, etc.)
and on the temperature. At lower temperatures, the addition−
elimination pathway is favored, while at higher temperature, the
elimination−addition mechanism is prominent.151,152 Further-
more, the kinetic models presented above do not consider
many effects such as secondary reactions taking place in the
whole process (allophanate, biuret, isocyanurate, etc.).153 To
take into account these limitations, it would be advisable to use
a more general model such as model-fitting approaches or even
a model-free kinetic approach,154 of which details are given in
Supporting Information.
4.3. Recording the Deblocking Reaction
Because of the discrepancy between the analytical techniques
and for the same technique, between the sample preparations
and the analytical methods, comparison between two
deblocking temperatures from distinct publications is tricky, if
not impossible. For instance, whatever the chosen analytical
method, the dissociation temperature can be measured during
the pure dissociation reaction (without a coreactant) or during
a reaction (with coreactant), which by competing with the
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blocking equilibrium decreases the apparent dissociation
temperature. This section aims at bringing an overview of the
different aspects to take into account while measuring
deblocking temperature. The most traditional techniques are
described here, e.g. spectroscopic techniques (FTIR, NMR...),
thermal ones (DSC, TGA) or titration methods.
4.3.1. A Point about the Measurement of the
“Deblocking Temperature”. Choosing a blocked isocyanate
system requires taking into account several aspects. Obviously,
the adduct must be extremely stable at room temperature and
very reactive at high temperature. In the patents as well as in
the academic literature, a system isocyanate-blocking molecule
is commonly described by its deblocking temperature.
However, exactness would require giving a reaction rate for a
particular temperature since the deblocking reaction is
associated with a kinetic mechanism, so all the rate constants
are governed by the temperature through the Arrhenius
relationship (eq 8).
k = A e−Ea /(RT ) (8)
According to the above equation, whatever the temperature,
reaction occurs, albeit at various rates. The exponential factor
(A) is increased by a temperature increase, and for a given
temperature variation, the higher the activation energy (Ea), the
more important the change. To get an accentuated threshold
temperature between blocked and free isocyanate, one should
increase the activation energy. However a compromise is
necessary, because for economical reasons elevated dissociation
temperature does not comply with industrial requirements.
Moreover, large activation energy makes the unblocking
reaction too slow unless A is large enough to counteract Ea.
Because the pre-exponential factor is a measurement of the
effects of both the internal degrees of freedom of the reacting
species and the necessary redistribution of that energy so that
the reaction ensues, the ideal reaction should have a large
positive entropy change, such as the cleavage of a ring system to
a ring-opened system, to take advantage of the temperature
effect.
In practical applications, it is however possible to generate a
“deblocking temperature” according to the onset temperature
of dissociation. As an example, different oxime- and
caprolactam-blocked isocyanates were heated in toluene in
the presence of amine (1.2−6 equiv relative to blocked
isocyanate; Scheme 31), and aliquots were analyzed by gas
chromatography to record the rate of appearance of urea.150
Scheme 31
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The onset temperature for the different systems is taken as
the temperature at which the rate of dissociation is not nil
anymore. Caprolactam 24 blocked isocyanate 21 regenerates a
free NCO group more slowly and at higher temperature (T =
180 °C) than the other systems due to its weak activation
parameters (Figure 7). Methyl t-butyl ketoxime 23 blocked
Figure 7. Dissociation rate constants of blocked isocyanate complexes
in presence of amine as a function of temperature calculated from
activation parameters measured in toluene (data from ref 150).
cyclohexylisocyanate (T = 200 °C) presents superior activation
energy, and global reaction rate is rapidly multiplied by a
temperature increase. Tetramethylcyclobutanone ketoxime 22
blocked cyclohexylisocyanate (T = 240 °C), the highest
activation energy system, is extremely sensitive to the
temperature; the high pre-exponential factor offsets the low
value of the exponential factor.
4.3.2. Techniques. FTIR has been successfully employed
to characterize adducts and their minimum deblocking
temperatures. The NCO group strongly absorbs between
2250 and 2270 cm−1, the disappearance of this band indicates
the completion of the blocking reaction (Table 8). The CO
bond frequencies can be shifted to lower vibration frequencies
depending on the hydrogen bonding.155 Typically, the
variations of absorbance are normalized to the C−H stretching
at 2946 cm−1 to compensate the thickness changes during the
reaction course. Isocyanate conversion is then calculated as
follows (eq 9).
(ANCO /A ref )t
α=1−
(ANCO /A ref )t = 0 (9)
Although it is less employed than FTIR, UV spectroscopy
can be used to determine the NCO content. The n−π*
transition of CO absorbs at 282−283 nm. Tondeur et
al.28,52,53 studied cyclopentanol−phenylisocyanate kinetics of
reaction by calculating the conversion ratio according to eq 10:
A 282 − [NCO]0 εure
α= /
[NCO]0 (εNCO − εure) (10)
where A282 stands for absorbance at 282 nm and εNCO and εure
stand for the extinction coefficients of phenylisocyanate and
urethane, respectively.
When heat is applied to blocked isocyanate adducts, the
urethane linkage scission leads to an endothermic transition in
the DSC curve, possibly preceded by a sharp transition that
corresponds to the adduct melting. Figure 8 presents the
thermogram of the toluene 2,4-TDI dimer dissociation; the first
peaks at 162 °C is attributed to the adduct melting followed by
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Chemical Reviews
Table 8. IR Band Frequency of Common Groups Involved in the Blocking or Curing Reactions
Figure 8. DSC thermogram of the melting and the dissociation of TDI
dimer. Reprinted with permission from ref 73. Copyright 1996 John
Wiley & Sons.
the blocking molecule−isocyanate dissociation at 185 °C.
Above 200 °C, possible degradations of isocyanate group and
Figure 9. Normalized intensity of isocyanate IR band for the deblocking reaction of 3,5-dimethylpyrazole blocked HDI (a) as a function of
temperature (1 °C/min)160 and (b) during isothermal measurements.
100
Review
TDI evaporation occur. A weight loss of 95% was recorded
after the DSC scan ended at 250 °C. For a highly volatile
blocking molecule, the deblocking reaction can also be
recorded in an open pan thanks to a thermal gravimetry
analysis.
Although 1H and 13C NMR are also widely used to
characterize the blocked isocyanate and the final products,
few studies reported the kinetic recording of the deblocking
reaction. This technique gives extremely accurate results about
deblocking and side reactions but necessitates high boiling
point deuterated solvents, such as dimethylformamide (DMF)
or dimethylsulfoxide (DMSO).
The isocyanate content can also be quantitatively determined
through titration. Aliquots are withdrawn from the flask and
quenched with di-n-butylamine. The isocyanate content is
determined by back-titration with an acid, such as HCl or
H2SO4 and a color indicator (methyl red11 or bromocresol
green156). Titration method via amine quenching is widespread
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Chemical Reviews
Figure 10. ATR spectra of deblocking reaction of methyl ethyl ketoxime blocked HDI isocyanurate as a function of time at 140 °C (a) without a
cover slide and (b) with a cover removed after 40 min as indicated by the arrow. Reprinted with permission from ref 7. Copyright 2001 Elsevier.
Scheme 32. Deblocking Reaction and 1H NMR Shifts Associated with the Chemical Functions at 25 °C in DMSO
and permits the study of biuret and allophanate groups thanks
to selective degradation with butylamine.95 Indeed, Furukawa
and co-workers157 showed that aliphatic primary amine
selectively degrades allophanate and biuret and left urethane
and disubstituted urea unmodified.
Gas chromatography may also be used either to confirm the
elimination−addition mechanism by recording the presence of
dissociated reactants158 or to check the kinetic data determined
with other techniques.150,159
4.2.3. Operating Conditions. While most of patents claim
a precise “dissociation” or “deblocking” temperature, one
should keep in mind that the “deblocking temperature” does
not have any physical meaning; not only can it be measured at
different stages of the reaction, but it also depends on the
recorded physical parameter and the technique sensitivity to
detect a certain extent of the reaction. In other words, since the
reaction is equilibrated, the measurement conditions or
experimental set up greatly influence that temperature.
First, isothermal or nonisothermal conditions give clearly
diverging results in the extent of reaction. Isocyanate groups are
only partly regenerated depending on the temperature. For
nonisothermal measurement, the extent of reaction increases
with temperature until potential degradation occurs (Figure
9a). While for isothermal measurements, equilibrium is rapidly
reached (Figure 9b) whereas relatively few isocyanate groups
are freed. The reaction extent is far below the one of the
nonisothermal experiment.
Second, the equilibrium reaction can be driven toward free
isocyanate (via the deblocking reaction) through the
elimination of released blocking molecules. Evaporation turns
out to be a critical point that is influenced by the measurement
techniques. In DSC, the sample is analyzed either in a sealed
pan if the boiling point of the blocking molecule is higher than
101
Review
the temperature range or in a pan with a hole to prevent the
blocking molecule evaporation from blowing up the cell. In the
open pan, the blocking molecule evaporation will pull the
reaction toward free isocyanate formation. TGA measurements
are evidently performed in an open pan. Because this method is
based on blocking molecule evaporation, TGA is inappropriate
for blocking molecule possessing a boiling point above the
deblocking temperature. Concerning infrared analyses, the
sample can be analyzed in the solid phase as a KBr pellet or in
the liquid phase (the blocked isocyanate solution is placed
between two KBr plates73,161 or on a single KBr plate162). As an
example, the influence of blocking molecule evaporation was
perfectly shown by Wicks (Figure 10). Moreover, when the
measurement cell containing the KBr pellet is evacuated to
remove disturbing air components such as CO2 and water, the
deblocking reaction is also favored.162
4.3.4. Presence of Chemical Additives. In addition to
inherent discrepancies due to the numerous techniques and
their experimental setups, the presence of solvent or coreactant
also induces strong disparities in the deblocking temperature
for a particular system. Contrary to DSC and TGA, NMR
techniques obviously require working in a solvent. Only IR and
UV are flexible enough to tolerate measurements in the
presence or in the absence of solvent. The solvent choice affects
the deblocking reaction. As already discussed (vide supra), the
mechanism of isocyanate addition on a nucleophile is not
completely elucidated, but strong evidence supports the idea
that the solvent greatly influences the kinetics of polyurethane
synthesis. If blocked isocyanate should be synthesized in an
apolar solvent, the deblocking reaction is favored by strong
nucleophilic solvent.163
Moreover, the equilibrated deblocking reaction is also
assisted by all nucleophiles present. For instance, the NMR
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Chemical Reviews Review

signals of 3,5-dimethylpyrazole 25 (DMP) blocked isocyanate
recorded as a function of temperature demonstrate that first the
isocyanate group is regenerated, and then it reacts with water to
form a urea bond and CO2 (Scheme 32).164 But, as soon as
water is totally consumed, the free isocyanate content reaches a
constant value (Figure 11).
Figure 11. NMR signal integrations and percentage of free blocking
molecule, expressed as I5.8ppm/(I6.2ppm + I5.8ppm), and various
derivatives.
decarboxylates into an amine and carbon dioxide. CO2 is
extracted with a carbon dioxide free, dry nitrogen purge and
made to react with sodium hydroxide165 or barium hydroxide.43
The minimum temperature at which detectable turbidity from
carbonate precipitation appears is taken as the minimum
deblocking temperature. Ho et al.165 followed the kinetics of
deblocking by weighing the evolved CO2 in the U shaped tube.
The CO2 evolution methods are only qualitative and relatively
subjective.
4.3.5. Catalysis Action. The mode of catalysis is well
understood in the nucleophile−isocyanate reaction, whereas in
the deblocking reaction it is not fully comprehended. Generally
speaking the same catalysts as those used in isocyanate−
nucleophile reaction are chosen, though at higher concen-
tration. The catalytic activity is still under debate: catalyst acts
either on the deblocking mechanism or in the reaction between
free isocyanate and coreactant. In the presence of nucleophile,
the catalyst is supposed to first complex or coordinate with
hydroxyl compound to generate the active form of the catalyst
that fits between the blocking molecule and isocyanate.166
Obviously, deblocking temperature depends on the catalyst
(Figure 12) and on its concentration (Figure 13). To study the

Most of the works measured the deblocking reaction in the

presence of a nucleophile such as amines or alcohols. The
relative reactivity of all reactants makes the comparison
between the different systems and publications quite tricky.
The deblocking temperature followed by IR corresponds either
to the disappearance of the blocking molecule−isocyanate
bond73,161 or to the first appearance of the curing molecule−
isocyanate band.162 Obviously, some differences in the results
are found between the two methods: first, an undefined interval
between the disappearance of the blocked isocyanate bond and
the appearance of the curing bond leads to a mistaken Figure 12. Deblocking temperature of 1,2-pyrazole-blocked phenyl
temperature in the case of a temperature ramp experiment. isocyanate with 10 mol % catalyst determined by DSC in dry
Second, during this period, secondary reactions may artificially DMSO.41
decrease the concentration of free isocyanate and curing bond.
Finally, due to the high reactivity of amine, the presence of free
isocyanate is not likely. effect of concentration on the side reaction, Petrak et al.41
Other deblocking temperature measurements exclusively heated pyrazole blocked isocyanate 26 in the presence of
operate in the presence of nucleophile, for instance, titration. catalyst and quantified by HPLC the amount of isocyanate
In this method, the CO2 created by the deblocking reaction is hydrolysis product (diphenylurea 27, Scheme 34). Amine
analyzed. The blocked isocyanate is slowly heated in the
presence of either an anhydride (Scheme 33a) or molecular
sieves saturated with moisture (Scheme 33b), which react with
the deblocked isocyanate. In Scheme 33b, the isocyanate group
reacts with water to form an unstable carbamic acid
intermediate, which, as explained before, spontaneously

Scheme 33. (a) Isocyanate−Anhydride Reaction and (b)

Reaction between Isocyanate and Water

Figure 13. Hydrolysis reaction of 1,2-pyrazole-blocked phenyl

isocyanate as a function of Zr(acac)4 catalyst concentration.41

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Chemical Reviews Review

Scheme 34. Hydrolysis Reaction of 1,2-Pyrazole-Blocked 1:33:100. The deblocking reaction reactivity obeys the opposite
Phenyl Isocyanate in the Presence of Zr(acac)4 order: the secondary alcohol−isocyanate adduct dissociates at a
lower temperature than primary alcohol blocked isocyanate.
Although, tertiary alcohol blocked isocyanates 12 should be
more reactive, they cannot be employed as blocked NCO, since
they do not regenerate the isocyanate group but decompose
into alkenes 14, carbon dioxide, and amine 13 (Scheme 35).
catalysis is not suitable for the deblocking reactions that entails Scheme 35. Decomposition of t-Butanol Blocked
a proton transfer from the NCO nitrogen to the nitrogen of a Isocyanate2,11
blocking agent (e.g., oxime, amine, vide inf ra). In the case of
oxime-blocked isocyanate reacted with dibutylamine, DABCO
was found to have no effect on the deblocking reac-
tion;156,167,168 for the deblocking reaction of pyrazole-blocked
isocyanate, addition of a strong base like DABCO greatly
reduced the reaction rate.169
4.3.6. Conclusion. In view of the numerous techniques, Generally speaking, the carbonyl group of the blocked
methods, and parameters available to compare the “deblocking isocyanate has partial positive charge, so the bond between the
temperature” of different blocked isocyanates, care must be carbonyl carbon and the blocking molecule is labile. The lower
taken in the evaluation of a given system. Deblocking the charge difference, the lower the strength of the bond. Thus,
temperature depends on the analytical measurements, that is, decreasing the nucleophilicity of the blocking molecule reduces
the measured physical phenomenon (deblocking, curing the charge density, making the bond more labile. Consequently,
reaction or both of them), the experimental set up (heating due to the electron-withdrawing effect of the aromatic ring,
rate, gas flow, sensibility, sealed reactor cup), and the reaction phenol-blocked isocyanate deblocks at a lower temperature
conditions (presence of coreactant or solvent, product than alcohol. This effect is enhanced by all the electron-
volatility, etc.). To get an idea of the complexity of comparing withdrawing substituents on the aromatic ring, as shown in
methods, please refer to some examples quoted in the Figure 14. This system is one of the most extensively described
Supporting Information of which examination/interpretation
are out of the scope of this review. One should nevertheless
recall that single “deblocking temperature” does not have a
physical sense, because it depends on the sensibility of an
analytical method to detect some extent of the deblocking or
curing reaction. To best reflect the curing phenomenon on the
system studied, one would preferentially choose the analytical
technique close enough to the application. Industrially, the
reaction rate is indeed at least as important as the deblocking
temperature.
4.4. Chemical Structure−Reactivity Relationship of Blocked
Isocyanates
We have seen all the parameters to take into account while
studying blocking/deblocking reactions. Nevertheless, the
temperature of dissociation obviously relies in the first place
on the structure of the isocyanate and of the blocking molecule. Figure 14. Deblocking temperature of the TDI adducts presented in
Because only a few isocyanates are industrially available, the Scheme 36 measured by carbon dioxide test in 2-methoxyethyl ether
with water-saturated molecular sieves (■)172 and measured by CO2
deblocking temperature is mainly controlled through the
test with water in poly(ethylene glycol) (●).170
blocking molecule structure. This part deals with the major
classes of blocking agents and for each blocking group, the
deblocking reaction mechanism will be presented to introduce in the open literature.163,170,171 Phenols substituted by stronger
the influence of substituents (and mainly their electronic effect) electron-releasing groups such as methoxy (32) and to a lesser
on the deblocking temperature. For intensive description of extent methyl groups (33) (Scheme 36) deblock at higher
each system, the reader is redirected to the reviews of Wicks et temperature whereas electron-withdrawing substituents drop
al.5,6 the temperature of isocyanate regeneration. Thus, to a certain
4.4.1. Alcohols and Phenols. As already discussed, extent the deblocking temperature can be correlated with the
alcohols and phenol react with isocyanate group to form pKa value of the phenol-based blocking group.
urethane linkages, the thermal dissociation temperatures
roughly vary in the following order:148n-alkyl-NHCOO-n- Scheme 36. Some Phenol Derivatives Used as Blocking
alkyl ≈ 250 °C; aryl-NHCOO-n-alkyl ≈ 200 °C; n-alkyl- Agents
NHCOO-aryl ≈ 180 °C; aryl-NHCOO-aryl ≈ 120 °C.
Because their deblocking temperature is quite high, alcohols
are not commonly used, except in water-borne coating where
adducts must exhibit a very high stability. Rand39 demonstrated
that in urethane-forming reactions, the competitive rates of
tertiary, secondary, and primary alcohols approximated to
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Chemical Reviews
4.4.2. Amines. Primary amines react so fast with isocyanate
that the counter-equilibrium reaction cannot be seen (the
temperature of degradation of the complex is below the
deblocking temperature). Secondary amines (e.g., piperidine
derivatives) are very reactive nucleophilic molecules that react
easily with isocyanate without external catalysis. Because
reactivity increases with the blocking molecule nucleophilicity,
the blocking reaction rate of isocyanates with amines is always
higher than with alcohol. This high reactivity of isocyanate
toward amines should induce a very high deblocking temper-
ature of the adduct. However, in the case of aromatic amines
(e.g., aniline), an autocatalytic effect is observed; the tertiary
nitrogen atom of the blocking molecule forms a four-centered
complex through an intramolecular hydrogen bond with the
urea hydrogen (Scheme 37). This transition state, proven by
Scheme 37. Formation of a Four-Centered Transition States
during Deblocking Reaction of Aniline−MDI Adduct
NMR,173 weakens the bond between the carbonyl carbon and
the nitrogen atom of the blocking molecule. The N−H
breaking is thus the rate-determining step of the deblocking
reaction.
Nasar158 and Gnanarajan174 studied substituted aromatic
secondary amine as blocking molecule (37−41) for TDI
(Scheme 38). When the deblocking reaction is carried out in
presence of hydroxyl-terminated polybutadiene (42, Scheme
38), the recording through gel time measurements at 180 °C
gave the following reactivity order: 37 > 38 > 39.158 Similar
compounds were heated with pyromellitic dianhydride (43,
Scheme 38) by TGA and in that case, the deblocking
temperature increased as 40 > 37 > 41.174 As predicted by
the proposed mechanism (Scheme 37), the electron-with-
drawing groups (phenyl, naphthyl group attached on the
nitrogen atom, or nitro group on the aromatic ring) drain the
electrons from the nitrogen atom hindering the hydrogen
abstraction. Conversely, the electron-releasing groups such as
methyl and nitro group strengthen the electron density on
nitrogen and so enhance the autocatalytic effect.
4.4.3. Oximes. The third widespread blocking molecule is
oxime type compounds for which the deblocking reaction
follows a similar deblocking mechanism to the one reported for
Scheme 38. Substituted Aromatic Secondary Amines Used To Block TDI (left) and Chemical Additives Used as Coreactant
during the Deblocking Reaction (right)
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Review
amine-blocked isocyanates.175 Oxime-blocked isocyanates are
easily synthesized at moderate temperature in THF with
dibutyltin dilaurate as catalyst.118 Levine et al.156,167 studied the
benzophenone oxime blocked TDI 44 derivative deblocking in
presence of dibutylamine in toluene. They reported blocking
molecule elimination as the first and rate-determining step
followed by the NuH molecule addition 45 (Scheme 39).
The mechanism, similar to the deblocking reaction of amine-
blocked isocyanate, leads to the following observations: (i) the
intramolecular activated complex decreases the deblocking
temperature, compared with alcohol-blocked isocyanate; (ii)
the reaction is favored by all the electron-releasing substituents
X on the blocking molecule, contrary to the alcohol-blocked
isocyanates; these substituents increase the base strength of the
nitrogen electron lone pair as presented in Scheme 40 and
Figure 15.
4.4.4. Other N-Based Compounds: Amides, Imides
and Imidazole, Pyrazole, and Triazole. Among the N-
compounds, amide is commonly used as blocking molecule.
This type of molecule does not form a cyclic intramolecular
transition state like oximes and, consequently, behaves similarly
to the hydroxyl compound; the electron-withdrawing sub-
stituents accelerate the deblocking reaction (Scheme 41 and
Figure 16).
Pyrazole 61 is another interesting class of blocking molecule
combining excellent reactivity and good latencies. The blocking
molecule elimination goes through a five-center complex
similarly to oximes (Scheme 42). Muehlebach measured the
reactivity of these pyrazole-blocked isocyanates mixed with
trifunctional amine-terminated prepolymer (Jeffamine T403)
and reported the following reactivity order: 63 > 62 > 61. The
electron-releasing substituents decrease the deblocking temper-
ature (Scheme 42).169 Blocked MDI was systematically found
to be more reactive than blocked HDI. Other compounds
containing at least two nitrogen atoms, such as 1,2,4-triazole 60
and imidazole 57 have been proven to form the same five-
center complex facilitating the deprotonation step during the
deblocking reaction.177
4.5. Improving Industrial Systems
4.5.1. Conventional Systems. The most used blocking
molecule in coating and painting industries is ε-caprolactam
(Scheme 43). However, these blocked isocyanate-powder
coatings have to be deblocked at rather high temperature,
and they release blocking agents during the hardening process
that are undesired both ecologically and economically. A low
boiling point compound facilitates the deblocking reaction and
acts as a solvent to level off the coating during the cross-linking
reaction. However, this type of compound brings potential
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Scheme 39. Mechanism of Benzophenone Oxime Blocked Isocyanate Deblocking in the Presence of Dibutyl Amine

Scheme 40. Substituted Benzophenone Oxime

Figure 16. Deblocking temperature of amide− and imidazole−

diisocyanate adducts. Those marked with “a” were measured by
DSC;176 those marked with “b” were measured by TGA.177,178

Scheme 42. Deblocking Reaction of Pyrazole Blocked

Isocyanate through a Five-Center Complex Formation169

Figure 15. First-order rate constant for the reaction between various toxicity problems. On the other edge, a compound with higher
blocked isocyanate molecules (Scheme 40) and dibutylamine (reactant evaporation temperature remains in the film and plays the role
ratio 1:1 at 70 °C).167 of a plasticizer. Methanol blocked m-TMXDI reacts with acrylic
polyol slightly faster than the ε-caprolactam blocked m-
Scheme 41. Structures of Some N-Based Compounds Used TMXDI, which is explained by the higher diffusion and
As Blocking Molecules evaporation rate of methanol.179 The gelation times, inversely
proportional to the reactivity, increase in the following order:
methyl, ethyl, and isopropyl alcohol-blocked TMXDI in
presence of an acrylic polyol.180
4.5.2. Chemical Tricks. In a view of improving polyur-
ethane formulations, a strategy to increase the reactivity has
been proposed by Carter and Pappas.181 After the deblocking,
the blocking molecule can undergo a chemical reaction
rendering it less reactive (or even unreactive); the back
reaction is then suppressed. The oxime-blocked isocyanate
system cured with alcohol is known to be much slower than
that cured with amines because the back reaction (isocyanate−
oxime) dominates the isocyanate−alcohol curing reaction.
Ethyl acetoacetate oxime 67 was found to be a good candidate:
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Chemical Reviews
Scheme 43. ε-Caprolactam-Blocked Trimer of (A) Isophorone Diisocyanate and (B) Hexamethylene Diisocyanate
after unblocking, an intramolecular cyclization reaction
converts the free oxime 67 into a non-nucleophilic (unreactive)
product 3-methylisoxazol-5-one 68 (Scheme 44).
Scheme 44. Deblocking and Cyclization Reactions of Oxime
of Ethyl Acetoacetate Blocked Isocyanate
The insolubility of the blocked isocyanate and the curing
molecule at ambient temperature and the slow endothermic
dissolution process at higher temperature enable extension of
the stability, as shown for the mixture of pyrazole-blocked
isocyanate and amine-terminated prepolymer.169 To increase
the storage stability, some polyurethane formulations include
blocked amines as coreactants in addition to blocked
isocyanates. Suitable amines are ketimines and enamines,
which react with moisture to regenerate amine functions.182
Finally, an interesting study showed that oxime-blocked
isocyanates induce cross-linking by generating amines and
hydrazines under UV radiation.183,184
4.5.3. Dual Networks. Tassel et al.185 synthesized a new
blocking agent, 2-formyloxyethyl methacrylate (69, Scheme
45), bearing two functions: a labile hydrogen and a
methacrylate double bond, which can homopolymerize leading
to polyurethane and polyacrylate interpenetrated networks. In
the same way, polyurethane−urea/polyvinyl simultaneous
interpenetrating polymer networks were prepared starting
Scheme 45. Blocking Agent Acting As a Comonomer after
Deblocking Reaction
106
Review
from a mixture of isocyanate prepolymer blocked with N-
(11′-dimethyl-3-oxobutyl) acrylamide oxime, chain extender,
vinyl monomers, and catalysts.186,187 Vinyl isocyanate mono-
mers such as isocyanate ethyl methacrylate or m-isopropenyl-
benzyl isocyanate are also available and were copolymerized
with methyl methacrylate or ethyl acrylate. They allow acrylate
polymer to be cross-linked by isocyanate groups or acrylate−
urethane interpenetrated networks.118,188
Due to the processing window (between the preparation and
flow of the powder and the cross-linking reaction), the use of
powder coatings at temperatures lower than about 130 °C is
limited, a fact that precludes their use on heat-sensitive
substrates like many plastic substrates. Efforts to develop
radiation-curable powder coatings are ongoing. UV-cross-linked
polyurethane acrylates (PUA) are very attractive materials that
combine fairly good mechanical performances (flexibility,
abrasion resistance, and toughness), high chemical resistance,
and adhesion properties. For their synthesis, the chain extender
of the second step in Scheme 24 is replaced by hydroxyl ethyl
(meth)acrylate, HE(M)A leading to α−ω (meth)acrylates,
which are able to react by free radical polymerization. But up to
now, due to the presence of inhomogeneities in cross-linking
density, the mechanical properties such as elongation at break
are less than the ones of the corresponding PU.189 Very
recently, some authors proposed to functionalize the blocking
agent with self-reacting groups, such as trimethoxysilane or
(meth)acrylate functions, to promote an anchoring of the
blocking molecules during the curing.102
4.5.4. Blocking Reaction of Amine Groups. To increase
the pot-life of cast molding formulations, another strategy used
masked amines, such as methylene dianiline (MDA) sodium
chloride complex dispersed in dioctyl phthalate. MDA is
commonly used to cure urethane prepolymers based on
diisocyanate, TDI, or MDI and polyether polyols. At room
temperature, the MDA/NaCl salt is virtually nonreactive,
whereas when heated to 115−160 °C, the complex unblocks
and the freed MDA rapidly cures the prepolymer to lead to the
final polyurethane.190,191 Another way to mask amines is
through aldimine groups, which regenerate amines and
aldehydes by hydrolysis.192 Interestingly, blocking the amine
group rather than the isocyanate function enables polyureas as
one-pot formulations.
4.6. Blocked Isocyanates as Initiators for Other Reactions
4.6.1. Urea Linkage as a Source of Amine. Although a
complex mechanism occurs, dicyandiamide is one of the most
popular cross-linkers for epoxy resin in industrial applica-
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Chemical Reviews
tions.193 To lower the reaction temperature, this reaction is
generally promoted by tertiary amines and imidazoles. A way to
improve the latency exploits blocked isocyanates to generate in
situ amines (Scheme 46). Upon heating, substituted ureas 70
Scheme 46. In situ Generation of Catalyst for Dicyandiamide
Epoxy Reaction
dissociate into isocyanate 72 and dimethylamine 71. The latter
reacts with an epoxy group to give a tertiary amine 73, which
catalyzes the reaction of dicyandiamide with epoxy groups. The
isocyanate moiety reacts with another epoxy unit, forming an
1,3-oxazolidin-2-one.193 A similar approach was used to
generate a tertiary amine catalyst from blocked isocyanate to
promote the epoxy isocyanate reaction.106
4.6.2. Urethane Promoting Ring-Opening Polymer-
ization of 1,3-Benzoxazine. 1,3-Benzoxazines are cyclic
N,O-acetal-type monomers that polymerize by ring-opening at
T > 180 °C without catalyst to give the corresponding phenolic
or phenoxy polymers (Scheme 47).194,195 Lower curing
temperature is highly needed, and attempts to reduce the
curing temperature have been carried out, with different
degrees of success, by using various catalysts, such as acidic
or basic compounds as well as metal-containing catalysts.
Among them, phenol has proven to be efficient, and urethane
reversibility has been used to create in situ the active molecule.
Phenol activates benzoxazine by protonation, the produced
species undergoes a ring-opening reaction. Then, the imminium
moiety reacts readily and irreversibly with phenoxides (Scheme
48a). Moreover, Sudo196 claimed that the isocyanate moiety
also induces polymerization by stabilizing the propagating
zwitterionic species and avoiding suppression of the reverse
reaction possibility (Scheme 48b).
Scheme 47. Monomer N-Methylbenzoxazine 75 and
Phenolic and Phenoxy Structures of Poly(benzoxazine) 76
5. “NEW” TRENDS: TOWARD
NON-ISOCYANATE-BASED POLYURETHANES
Recently, several reactions, essentially based on transcarbamoy-
lation, attracted researchers interest due to the possibility to
form polyurethanes without isocyanate monomers in the
formulations, which complies with the new environment and
safety requirements. Nowadays industrially, the transcarbamoy-
107
Review
lation is commonly used for synthesizing polyurethane from
polyol and urethane diol.197 Other strategies consist in
preparing precursors without facing the hazards of phosgene
handling. Here, we have classified these new systems according
to whether they release isocyanate during the polymerization.
One should however never forget that, due to the reversibility
of urethane linkage, isocyanate functions may reappear in the
material at a later stage, by, for example, thermal treatment.
5.1. Phosgene-Free Isocyanate Precursors
Klinger et al.198 showed that, by heating between 50 and 70 °C
during 24 h, the acylazide groups in a polymer undergo a
Curtius rearrangement (Scheme 49) and thereby generate
isocyanato groups in situ and N2.
Another convenient method (Scheme 50) for the trans-
formation of amines into first blocked isocyanates and then free
isocyanates employs N,N′-carbonyldiimidazole.
The blocking reaction of an isocyanate function with
maleimide derivatives is not feasible for reactivity purposes.
One key to nevertheless prepare these products consists in the
reaction of the maleic anhydride with (substituted) urea(s) and
cyclization with water release (Scheme 51).200
Such derivatives were shown to deblock at relatively low
temperature (about 100 °C in DMF) and react readily with
primary alcohols to generate N-carbanylmaleamates. Other
authors reported succcinimide or maleimide derivatives of HDI
in the same range of temperature (110 and 130 °C,
respectively).176,201
5.2. Phosgene-Free Isocyanate-Free Precursors
5.2.1. Carboxamide/Alcohol Polycondensation. From
tetramethylene urea and phenyl chloroformate, Ubagh
synthesized N-(hydroxyalkyl)-2-oxo-1,3-diazepan-1-carboxa-
mide 81 as a polycondensation monomer to lead to
polyurethane.202,203 Below 100 °C, the equilibrium (Scheme
52) is completely shifted to the left; and thus, the O-phenyl
urethane is considered as an activated urethane and the 1,3-
diazepan-2-one ring as an intramolecular blocked isocyanate. In
the presence of amino alcohol, the urea ring remains intact
because the nucleophilic amino group reacts selectively with the
electrophilic carbon of the O-phenyl group. Then, this
monomer is polymerized in the presence of catalyst such as
DABCO at 150 °C to form poly(urea-urethane) 82 (Scheme
53).
Another reaction involves carbonylbiscaprolactam 83 (CBC,
Allinco from DSM) with a nucleophile to provide caprolactam-
blocked diisocyanate as an isocyanate- and phosgene-free
route.204 Depending on the nucleophile, the temperature, and
the catalyst, two reactions were identified: ring-opening (RO)
and ring elimination (RE) mechanisms (Scheme 54). Whereas
secondary amines do not react at high temperature or in
presence of catalyst, the reaction of CBC with primary amines
proceeds exclusively by the RE mechanism. At 70 °C, the
mono-RE mechanism is quantitative without catalyst to form
caprolactam-blocked isocyanate.205,206 At higher temperature,
RO competes with RE mechanism, and a mixture of blocked
isocyanate and urea is then obtained at 170 °C. Primary and
secondary alcohols and phenols react with CBC by ring-
opening and ring elimination depending on the conditions
(temperature and catalyst) to afford carbonate, urea ester, and
urethanes without isocyanate intermediates. Metal alcoholate
catalysts favor the RO pathway.
5.2.2. Dicarbonate/Amine Condensation. A promising
approach toward phosgene-free polyurethane is the carbonate−
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Chemical Reviews
Scheme 48. Mechanism for the Promoting Effect of Urethanes on the Polymerization of Benzoxazine
Scheme 49. Curtius Rearrangement
amine reaction that leads to β-hydroxyurethane. Depending on
the reaction conditions and nucleophile hardness, dimethylcar-
bonate (DMC) acts either as a carboxymethylating or as a
methylating agent of amines. In the absence of base, aliphatic
amines such as benzylamine 84 react with DMC 85 to give
both alkylation (86) and carboxylation (87) products without
any selectivity (Scheme 55).208
Due to the lower nucleophilicity of aromatic amines, these do
not react at 90 °C in the absence of a base. Basic catalysts, such
as the organic superbase guanidine 1,5,7-triazabicyclododecene
(TBD, see Figure 17), increase the rate and the selectivity of
aliphatic amine−carbonate reaction.209 Urethane bonds are
formed by dicarbonate−aliphatic or aromatic amine reaction
catalyzed by bases such as sodium methoxide at 90 °C. The
best results for the carboxymethylation of aniline with
dimethylcarbonate in terms of selectivity (urethane/N-methyl
derivative) are achieved with zinc or tin catalysts.210
Uncatalyzed urethane formation can also be performed under
high pressure (8 kbar).211 Very recently, Tang et al. showed
that a superbase catalyst conventionally used in ring-opening
polymerization (ROP) of various cyclic monomers (including
cyclocarbonates), namely, TBD, promotes transurethanization
reaction between dicarbamates and diamine functionalized
molecules to generate bio-based, isocyanate-free polyurethane
of similar structuration and mechanical properties as conven-
tional TPUs.209
Scheme 50. Formation of Isocyanate from Amine and Carbodiimidazole199
108
Review
Scheme 51. Formation of Maleimide-Blocked Isocyanate by
a Phosgene-Free Reaction and Further Deblocking
Reaction199
5.2.3. The Specific Case of Cyclocarbonate/Amine
Addition. As early as 1957, Groszos et al.212 patented PU
preparation using a non-isocyanate route based on the reaction
between cyclocarbonate and polyamine urea. Recently, this
synthesis strategy has attracted more and more interest since no
volatile compounds are released during the reaction. Cyclic bio-
based alkylenes are reactive intermediates known for more than
50 years,213 but since the 1990s, seminal work has been done to
explore the high reactivity of five-membered alkylene carbonate.
Primary or secondary amine has long been shown to open the
cyclocarbonate at room temperature without catalyst.213−215
Using diamine and bicyclocarbonate allows synthesis of original
polymers that could not be obtained by common isocyanate−
alcohol addition, for instance, amorphous polyhydroxyur-
ethane.216 A very recent review proposes practical aspects of
NIPU preparation and applications.217
5.2.3.1. Synthesis of Pentacyclocarbonate. Several meth-
ods were used to synthesize five-membered cyclic carbonates as
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Chemical Reviews
Scheme 52. Equilibrium between Activated Urethane/Intramolecular Blocked Isocyanate and the Mono- or Diisocyanate forms
Scheme 53. Synthesis of Poly(urea-urethane) from 81
Scheme 54. Reaction Pathway of CBC 83 with Nucleophiles
Scheme 55. Reaction of Benzylamine with DMC in the Absence of Base
Figure 17. Synthesis of isocyanate-free polyurethane via the
transurethanization between dicarbamates and diamino-terminated
polymers catalyzed by organic superbase guanidine 1,5,7-triazabicy-
clododecene.
109
Review
summarized in Scheme 56. These include the reaction between
an epoxy group and β-butyrolactone218 and the reaction
between carbon dioxide and 1,2-diols in presence of
catalysts.219 A recent approach involves the formation of a
cyclocarbonate from a ketal formed from ethan-1,2-diol and
cyclohexanone in the presence of supercritical CO2.220 Reaction
between urea and alcohol is another method for the synthesis
of cyclocarbonates in presence of catalysts.221,222 Phosgenation
of polyols is interesting due to a high yield in cyclocarbonate
but the high toxicity of phosgene is the main drawback.223−225
The transesterification of 1,2-diols with ethylene carbonate
leads to cyclocarbonates by a group exchange reaction in
presence of catalyst.226 Finally, the most common method
remains the addition of carbon dioxide on cyclic ethers,227−229
for which the catalysts and synthetic methods were nicely
described by Daresbourg.230
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Chemical Reviews
Scheme 56. Synthetic Routes to Five-Membered Cyclocarbonates
Various techniques are likely available to synthesize
dicyclocarbonates: (i) reaction of diglycidyl ether of bisphenol
A (BADGE) and CO2 in presence of sodium iodide and
triphenylphosphane at 100 °C;231 (ii) transesterification of
polyols such as 3,4-O-isopropylidene-D-mannitol with ethylene
carbonate with yields around 65%;232 (iii) highly selective
reactions of n-(tert-butoxycarbonyl)imidazole233 or triphos-
gene234 onto various tetrol; (iv) carbonated methyl lineolate
obtained from the bis-epoxy precursor using CO2.227 The most
reported technique consists of the esterification of carboxylic
acid groups of benzene-1,4-dicarboxylic acid with the alcohol
function of commercial 4-(hydroxymethyl)-1,3-dioxolan-2-one
90 (Scheme 57).235 This method was also reported by others to
Scheme 57. Synthesis of Dicyclocarbonate Using Glycerin
Carbonate
lead to different cyclocarbonates, symmetric or asymmet-
ric.216,236 The same product was also obtained by Steblyanko
from CO2 and diglycidyl terephthalate, previously synthesized
from 2-oxiranylmethanol and terephthaloyl dichloride.237 Very
recently, this method, in combination with ROP of the same
cyclocarbonate, was applied to prepare cyclocarbonate-termi-
nated polycarbonates.238
Carbon dioxide was also added to other glycidyl ethers to
synthesize polyfunctional cyclocarbonates.227 Koen-Raadt
reported the preparation of tris(2-oxo-1,3-dioxolanyl-4-
methyl)isocyanurate by reaction of triglycidyl isocyanurate
110
Review
with carbon dioxide.239 Note that a tristar poly(ethylene glycol)
terminated by cyclocarbonate 92 is commercialized by the
company Macromer Ltd., Russia, under the trade name
Laprolate L.803 (Scheme 58).240
Scheme 58. Chemical Structure of Laprolate L.803
5.2.3.2. Cyclocarbonate/Amine Reaction. 5.2.3.2.1. Iso-
mers. Endo et al.237,241 studied a model reaction between
monofunctional cyclic carbonate 93 and benzylamine 94
(Scheme 59). After 20 h, no aminolysis product (N-
benzylbenzamide 97 in Scheme 59) but two isomers of ring-
opening reaction were found. The secondary hydroxyl
containing compound (96 in Scheme 59) predominates in
the medium (96/95 = 4.4:1); theoretical calculations confirmed
the stability of 96 (ΔHf = −9.77 kcal/mol) over 97 (ΔHf =
−8.10 kcal/mol).
The ratio between secondary and primary hydroxyl
compound is determined by substituents introduced at the α-
methylene of the bicyclocarbonate 98: a more electron-
withdrawing group draws the reaction toward secondary
hydroxyl containing product 99 (Scheme 60).242 Chemical
structure and molar mass govern the amine reactivity:
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Chemical Reviews
Scheme 59. Ring-Opening Model Reaction of Cyclocarbonate by Amine237
aromaticity, α- and β-electron-withdrawing substituents, and
high molar mass lower the reactivity.240
Scheme 60. Polyhydroxyurethane Synthesis
5.2.3.2.2. Reactivity. Kotzev240 studied in 2004 the reaction
between the Laprolate and various amines, which structures are
given in Scheme 61. The reactivity decrease for bulk reaction is
explained by the amine concentration dropping off as the molar
Scheme 61. Scale of Reactivity of Various Amines toward a Model Pentacyclocarbonate
111
Review
mass of the molecules increases; catalyst or higher temperature
are then required. Typically with diethylene triamine (DETA),
8 days at room temperature is required for a quantitative
reaction, whereas using a catalyst and working at 60 °C, 4 days
is enough. This shows that the carbonate/amine reaction is less
efficient than the isocyanate/alcohol one and should rather be
compared with the epoxy−amine reaction in a higher range of
temperature. Kotzev proposed, as shown in Scheme 61, a scale
of reactivity that summarizes perfectly this trend.
5.2.3.2.3. Larger Cycles. Endo223−225 has prepared and
compared the reactivity of C5 and C6 cyclic carbonates,
prepared from epoxy/CO2 and malonate/triphosgene reaction,
respectively. The C6 cycle is about 20 times more reactive at 30
°C and 10 times more at 70 °C, than C5 while reacting them
with 4,9-dioxadodecane-1,12-diamine. Guillaume et al. have
prepared various cyclocarbonates in C7 starting from levunilic
and itaconic acids but engaged these molecules exclusively in
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Chemical Reviews
ring-opening metathesis polymerization (ROMP) to prepare
polycarbonates.243
5.2.3.3. Polymer Synthesis and Properties. Kihara and Endo
synthesized linear polyhydroxyurethanes from reaction between
diamines and dicyclocarbonates obtained from epoxy mole-
cules.231 Burgel and Fedtke also prepared linear polyhydroxyur-
ethanes from dicyclocarbonates and diamines.244 Finally, Lee et
al.245 designed new linear polyhydroxyurethanes by poly-
addition between dicyclocarbonates and various amines.
Dicyclocarbonates were obtained from bisphenol S of diglycidyl
ether monomer and carbon dioxide.245 The work was also
extended to polymers functionalized with bicyclocarbonate,
which react with polyamines to yield cross-linked polyhydrox-
yurethanes.246 Various types of catalysts such as acid (glacial
acid acetic, methanesulfonic acid), base (triethylamine,
piperazine, tetrabutyl ammonium bromide), or metal (metatin
type catalyst) increase the reaction rate.240
Because the molar mass obtained by this process is usually
below 10,000 g/mol and ultimately less than 20,000 g/mol, this
reaction is essentially used to synthesize prepolymer247 or to
cross-link cyclocarbonate bearing polymer248 or for chain
extension of preformed polymers. The Tg of this material
ranges between −30 and 100 °C, depending on the chemical
structure of reactants. Neither volatile nor nonvolatile by-
products are produced by the reaction between cyclocarbonates
and amines resulting in pore-free polyurethanes. The influence
of hydroxyl functions on thermal properties of poly-
(hydroxyurethane) (PHU) is remarkable. Indeed, the intra-
molecular hydrogen bonding between the alcohol and urethane
functions (Scheme 62) seems to be responsible for lowering
Scheme 62. Hydrogen Bonding in a Hydroxyurethane
Function249
the susceptibility of the backbone to hydrolysis resulting in
substantial increase of the chemical resistance.249 The chemical
resistance of materials containing intramolecular hydrogen
bonds is 1.5−2 times superior to materials with a similar
chemical structure without such bonds.250 Tomita has shown
that the water absorption percentages and thermal decom-
position temperatures of the film cast from synthesized PHU
were reduced by 30% and from 32 to 88 °C higher,
respectively, than those from commercial PU.223−225
5.2.3.4. Bio-Based Materials from this Chemistry. As a
current trend, researchers tend to go further by producing
nonisocyanate PU from renewable resources. In that frame,
vegetable oils as feedstocks for polymeric materials attract
increasing attention, because they tend to be very inexpensive
and available in large quantities. They are used either as a
source of polyol251 or as polycyclocarbonate obtained from
epoxidized oils.252,253 As an example, Boyer et al.254 synthesized
internal carbonated fatty acid diester and terminal carbonated
fatty acid diester from sunflower oil. Interestingly, carbonate
and dialkyl carbonates can be prepared from bio-based
products, such as dianhydrohexitol,255 leading to green,
biosourced polyurethane.
112
Review
5.3. Conclusion
The carbonate/amine reaction produces polyurethane materials
overcoming the use of toxic isocyanates. However, catalyst
addition is required to enhance the reaction rate and the
selectivity. Cyclocarbonates, especially five-membered cyclo-
carbonates, drew additional interest compared with carbonates
since no volatile compounds are released during the polymer
formation. The obtained products from these cyclic carbonates
bear a hydroxyl group at the β-carbon atom of the urethane
moiety, which brings improved properties such as pore-free PU.
The thermal stability of nonisocyanate PU is also claimed to be
improved compared with conventional PU. However, this
parameter has only been checked through thermogravimetric
analyses; the molar mass stability when heating should also be
verified. Indeed, the reversibility of the β-hydroxyurethane
bond would produce isocyanate and an excess of OH groups,
which upon recondensation could induce a strong molar mass
decrease. An opposite possibility would be exclusive exchange
reactions without depolymerization; if that occurs, it would be
possible to prepare malleable materials from permanent organic
networks, as proposed recently for conventional epoxy−acide
chemistry.256
6. FINAL CONCLUSION: ISOCYANATE-FREE VERSUS
NONISOCYANATE SOLUTIONS IN VIEW OF AN
INDUSTRIAL CONTEXT
As stated in the Introduction, urethane/urea bonds have proven
their versatility. One clear advantage of the NCO chemistry is
the high reactivity of this function, even at room temperature.
This allows fast curing of cast-molded materials or coatings, as
well as a facility to prepare solid foam (chemical reaction rate
competes with gas release speed, thus facilitating trapping of it
in the network). Additionally, the reversibility of covalent links
based on isocyanate chemistry is an open door to combining
processability, reparability, and high elastomeric or rigid
performance in a variety of applications.
Reversibility of urethane bonds is the key to blocked
isocyanate technology. Blocking the isocyanate function is a
way of getting rid of isocyanate groups in a formulation, but
then curing requires high temperature to deblock the chains.
Another disadvantage of blocked isocyanates is the loss of
(high) reactivity of the −NCO groups, as we have seen in this
review. This approach is then particularly preferred when one is
seeking a one-pot, slow polymerization process, as in coatings
for instance. One solution to enhance the reactivity consists in
preparing prepolymers, which react by transcarbamoylation
with polyols to cross-link the materials; such a trick is regularly
used in industry.
A major problem of concern in isocyanate chemistry is the
high toxicity of the precursors, that is, diisocyanates. Upon the
most conventional formulation available nowadays, the industry
proposes formulations where telechelic isocyanate prepolymers
are prepared beforehand by reaction of a diol oligomer with an
excess of diisocyanate and distillation of the remaining small
reactant. The polyurethane materials are then prepared by
adding a short diol or upon action of water in a one-pot
formulation. This process, called “diisocyanate-free polyur-
ethane” technology, allows the same reactivity as in the
conventional diisocyanate chemistry to be retained, while the
recent regulation rules, such as REACh, which requires
discarding MDI or TDI hazardous molecules, are respected.
Still, the presence of isocyanate functions at the end of
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Chemical Reviews Review

oligomers can bring toxicity to the end-user, necessitating mechanical properties of silicone materials, as well as the synthesis of
special security requirements during implementation. functional polydimethylsiloxane.
The carbonate−amine reaction seems to be the best way to
solve these toxicity problems, because it avoids the use of
isocyanate functions. The range of materials issued from this
technology are called “non-isocyanate polyurethanes” (NIPUs).
Up to now, the rate of this reaction has been shown to be quite
slow compared with the direct −NCO + −OH reaction; still,
methods are available nowadays to circumvent this lack of
reactivity. For instance, working with less stranded cyclo-
carbonate or tailoring the nature of the catalyst may enhance
the reactivity of the system. Linear NIPU have found various
applications given the pending regulations.257,258 However
important issues that remain concern especially the mechanical
properties and chemical resistance of these materials to alkali
and acid solutions. Also, the elasticity of NIPU does not permit
elastomer applications. A way to circumvent all these drawbacks
makes use of hybrid NIPU, based on the epoxy−amine−
Professor Jean-Pierre Pascault is Emeritus from 2005 at National
cyclocarbonate oligomers to build a network structure.217
Institute of Applied Science (INSA), Lyon, France. He was Professor
Though quite old, urethane/urea chemistry definitively
proposes many future new challenges in chemistry and material in the same Institute from 1983 to October 2005, Director of the
sciences. Laboratory of Macromolecular Materials (Associated with CNRS)
from 1982 to 1998, Director of a CNRS Polymer Network Group (FR
ASSOCIATED CONTENT CNRS) from 2000 to 2006, and President of the French Polymer
*
S Supporting Information
Group, GFP, and of the Polymer Division of the French Chemical
Society, SFC, from 2001 to 2004. He has authored over 320 scientific
Comparison of deblocking temperatures using different publications including several book chapters and two books
techniques, comparison within blocker families, model-free
(Thermosetting Polymers and Epoxy Polymers: New Materials and
kinetics equations for describing complex reactions, and the
Innovations) and 32 patents. His main research themes concern
case of β-dicarbonyl compounds as blocking agents. This
material is available free of charge via the Internet at http:// polyaddition/polycondensation reactions and new green polyur-
pubs.acs.org. ethane/epoxy materials.

AUTHOR INFORMATION
Corresponding Author
*E-mail: francois.ganachaud@insa-lyon.fr. Fax: +33 4 72 43 85
27.
Notes
The authors declare no competing financial interest.
Biographies

Bernard Boutevin earned his Chemical Engineering degree from the

Etienne Delebecq was born in Lille, France, in 1984. He received his
B.S. degree in Chemistry in 2005 from Ecole Nationale Supérieure de
Chimie de Montpellier (ENSCM, France). In 2008, he received a M.S.
degree from Université Montpellier and a Ingénieur Chimiste degree
from ENSCM. In 2011, he earned his Ph.D. in Material Science at
ENSCM, working under the direction of Dr. François Ganachaud. His
research activities are focused on the improvement of thermal and
School of Chemistry in Montpellier (France) and then received his
Ph.D. degree in 1975 from Montpellier University, where he became a
CNRS researcher. The topics of his research first concerned
telomerization, and later he investigated all of the methods of living
radical polymerization (NMP, ATRP, ITP, RITP, and RAFT) in order
to prepare original architectured polymers such as block, grafted,
gradient, or alternated. Since 2005, he shifted his main theme of
research towards green and sustainable polymer chemistry. He and his
co-workers now synthesize bio-based materials such as epoxy resins
obtained from natural polyphenols (flavonoids, gallic acid and
derivatives, and cardanol) and isocyanate-free polyurethanes through
the carbonate−amine reaction. He has supervised more than 100
Ph.D. students, published 2 books, more than 500 peer-reviewed
articles, and 25 reviews or chapters of books. He is the coinventor of
more than 120 patents.

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Chemical Reviews Review

MDA methylene dianiline

MDI methylene diphenyl isocyanate
NIPU non-isocyanate polyurethanes
OMO dioctyl 4,4-methylenebis(phenyl carba-
mate)
PHU poly(hydroxyurethane)
PPDI paraphenylene diisocyanate molecule
PU polyurethane
PUA polyurethane acrylates
REACh Registration, Evaluation, Authorisation and
Restriction of Chemical substances
RO/RE ring-opening/ring elimination (mecha-
nisms)
RO(M)P ring-opening (metathesis) polymerization
François Ganachaud studied chemistry at CPE Lyon before graduating SN2 nucleophilic substitution type 2
with a Ph.D. in 1997 from University Claude Bernard in Lyon. After 1 RIM reaction injection molding
year postdoctoral work in Sydney at the KCPC, he took a CNRS TBD 1,5,7-triazabicyclododecene
research position first in Paris (1999−2003) and then in Montpellier TDI toluene diisocyanate
(2003−2011, habilitation in 2004). Back to Lyon from September TEA triethylamine
2011 as a senior CNRS scientist, his current research interests are (i) TGA thermal gravimetry analysis
ionic polymerization in aqueous media, (ii) functional silicones and THF tetrahydrofurane
related materials, and (iii) emulsification by the Ouzo effect. tIPDI trimer of isophorone diisocyanate
TM-DSC temperature-modulated differential scan-
ning calorimetry
ACKNOWLEDGMENTS TMP trimethyl-ol propane
E.D. thanks FCI automotive for sponsoring his Ph.D. grant. J.- TMXDI m-tetramethyl-xylylene
P.P. and F.G. thank Françoise Méchin for several remarks and TP(U) thermoplastic (polyurethane)
references brought to the paper. TS thermosetting (material)
VOC volatile organic compound
SYMBOLS AND ABBREVIATIONS
ε dielectric constant REFERENCES
γ hydrogen bonding index (1) Verheugen, G. J. Eur. Union 2009, L164/7.
χ interaction parameter (2) Saunders, J. H.; Slocombe, R. J. Chem. Rev. 1948, 43, 203.
δ solubility parameters (3) Arnold, R. G.; Nelson, J. A.; Verbanc, J. J. Chem. Rev. 1957, 57,
Mw mass-average molar mass 47.
N degree of polymerization (4) Krol, P. Prog. Mater. Sci. 2007, 52, 915.
Tcl ceiling temperature (5) Wicks, D. A.; Wicks, Z. W. Prog. Org. Coat. 1999, 36, 148.
(6) Wicks, D. A.; Wicks, Z. W. Prog. Org. Coat. 2000, 41, 1.
Tg glass transition (7) Wicks, D. A.; Wicks, Z. W. Prog. Org. Coat. 2001, 43, 131.
Tm melting temperature (8) Caraculacu, A. A.; Coseri, S. Prog. Polym. Sci. 2001, 26, 799.
1K/2K one-pack/two-pack (reaction) (9) Sacher, E. J. Macromol. Sci., Part B: Phys. 1979, B16, 525.
acac acetylacetonate (10) Borisov, E. V.; Vasyanina, L. K.; Bondarenko, S. P.; Zabrodin, V.
BDO butanediol B. Zh. Fiz. Khim. 1977, 51, 1930.
CBC carbonylbiscaprolactam (11) Ozaki, S. Yuki Gosei Kagaku Kyokai Shi 1970, 28, 17.
(CP/MAS) NMR (cross-polarization/magic angle spinning) (12) Dyer, E.; Glenn, J. F.; Lendrat, E. G. J. Org. Chem. 1961, 26,
nuclear magnetic resonance 2919.
DABCO 2,2′-diazabicyclo[2.2.2]octane (13) Wegener, G.; Brandt, M.; Duda, L.; Hofmann, J. R.;
DBTDL dibutyltin dilaurate Klesczewski, B.; Koch, D.; Kumpf, R.-J.; Orzesek, H.; Pirkl, H.-G.;
Six, C.; Steinlein, C.; Weisbeck, M. Appl. Catal., A 2001, 221, 303.
DBU 1,8-diazabicyclo[5.4.0]-7-undecene (14) Bertoldo, M.; Cappelli, C.; Catanorchi, S.; Liuzzo, V.; Bronco, S.
DETA diethylene triamine Macromolecules 2005, 38, 1385.
DMC dimethylcarbonate (15) Sato, M. J. Org. Chem. 1961, 26, 770.
DMDEE 2,2′-dimorpholine diethyl ether (16) Sato, M. J. Org. Chem. 1962, 27, 819.
DMF dimethylformamide (17) Han, Q.; Urban, M. W. J. Appl. Polym. Sci. 2002, 86, 2322.
DMP 3,5-dimethylpyrazole (18) Han, J. L.; Yu, C. H.; Lin, Y. H.; Hsieh, K. H. J. Appl. Polym. Sci.
DMSO dimethylsulfoxide 2008, 107, 3891.
DN electron donor number (19) Majoros, L. I.; Dekeyser, B.; Hoogenboom, R.; Fijten, M. W. M.;
FT-IR Fourier transform infrared (spectroscopy) Haucourt, N.; Schubert, U. S. J. Polym. Sci., Part A: Polym. Chem. 2009,
HDI hexamethylene diisocyanate 47, 3729.
(20) Majoros, L. I.; Dekeyser, B.; Hoogenboom, R.; Fijten, M. W. M.;
HE(M)A hydroxyl ethyl (meth)acrylate Geeraert, J.; Haucourt, N.; Schubert, U. S. J. Polym. Sci., Part A: Polym.
HMDI bis(4-isocyanatocyclohexyl)methane or hy- Chem. 2009, 48, 570.
drogenated MDI (21) Majoros, L. I.; Dekeyser, B.; Haucourt, N.; Castelein, P.; Paul, J.;
HPLC high-performance liquid chromatography Kranenburg, J. M.; Rettler, E.; Hoogenboom, R.; Schubert, U. S. J.
HS/SS hard segment/soft segment Polym. Sci., Part A: Polym. Chem. 2009, 49, 301.
IPDI isophorone diisocyanate (22) Baker, J. W.; Bailey, D. N. J. Chem. Soc. 1957, 4652.

114 dx.doi.org/10.1021/cr300195n | Chem. Rev. 2013, 113, 80−118

Chemical Reviews
(23) Baker, J. W.; Bailey, D. N. J. Chem. Soc. 1957, 4649.
(24) Baker, J. W.; Gaunt, J. J. Chem. Soc. 1949, 27.
(25) Baker, J. W.; Davies, M. M.; Gaunt, J. J. Chem. Soc. 1949, 24.
(26) Baker, J. W.; Gaunt, J. J. Chem. Soc. 1949, 19.
(27) Baker, J. W.; Gaunt, J. J. Chem. Soc. 1949, 9.
(28) Tarasov, D. N.; Tiger, R. P.; Chirkov, Y. N.; Entelis, S. G.;
Tondeur, J. J. Kinet. Catal. 2000, 41, 355.
(29) Tiger, R. P.; Levina, M. A.; Entelis, S. G.; Andreev, M. A. Kinet.
Catal. 2002, 43, 662.
(30) Ephraim, S.; Woodward, A. E.; Mesrobian, R. B. J. Am. Chem.
Soc. 1958, 80, 1326.
(31) Oberth, A. E.; Bruenner, R. S. J. Phys. Chem. 1968, 72, 845.
(32) Saunders, J. H.; Frisch, K. C. Polyurethanes: Chemistry and
Technology; Interscience Publishers: New York, 1962.
(33) Chang, M. C.; Chen, S. A. J. Polym. Sci., Part A: Polym. Chem.
1987, 25, 2543.
(34) Gutmann, V. Electrochim. Acta 1976, 21, 661.
(35) Marcus, Y. J. Solution Chem. 1984, 13, 599.
(36) Crowley, J. D.; Teague, G. S., Jr.; Lowe, J. W. J. Paint Technol.
1967, 39, 19.
(37) Crowley, J. D.; Teague, G. S., Jr.; Lowe, J. W., Jr. J. Paint
Technol. 1966, 38, 269.
(38) Baker, J. W.; Holdsworth, J. B. J. Chem. Soc. 1947, 713.
(39) Rand, L.; Thir, B.; Reegen, S. L.; Frisch, K. C. J. Appl. Polym. Sci.
1965, 9, 1787.
(40) Blank, W. J.; He, Z. A.; Hessell, E. T. Prog. Org. Coat. 1999, 35,
19.
(41) Petrak, S.; Shadurka, V.; Binder, W. H. Prog. Org. Coat. 2009, 66,
296.
(42) Gertzmann, R.; Guertler, C. Tetrahedron Lett. 2005, 46, 6659.
(43) Ahmad, I.; Zaidi, J. H.; Hussain, R.; Munir, A. Polym. Int. 2007,
56, 1521.
(44) Korah Bina, C.; Kannan, K. G.; Ninan, K. N. J. Therm. Anal.
Calorim. 2004, 78, 753.
(45) Willett, J. T. (Wyandotte Chemicals Corp.) Mercury
compounds as catalysts for the polyurethane reaction, U.S. Patent
3,419,509, 1968.
(46) Fertig, J. E.; Lederer, S. J. (Merck and Co., Inc.) Polyurethanes,
German Patent DE2021757, 1970.
(47) Robins, J. (Minnesota Mining and Manufacturing Co.)
Organomercury catalysts for producing urethane polymers, U.S.
Patent 3,583,945, 1971.
(48) Gallagher, J. A.; Brizgys, B. (BASF Wyandotte Corp., USA)
Monomercury organo catalyst, U.S. Patent 3,927,053, 1975.
(49) Frisch, K. C.; Rumao, L. P. J. Macromol. Sci., Rev. Macromol.
Chem. 1970, 5, 103.
(50) Majumdar, K. K.; Kundu, A.; Das, I.; Roy, S. Appl. Organomet.
Chem. 2000, 14, 79.
(51) Houghton, R. P.; Mulvaney, A. W. J. Organomet. Chem. 1996,
518, 21.
(52) Draye, A.-C.; Tondeur, J.-J. J. Mol. Catal. A: Chem. 1999, 138,
135.
(53) Draye, A.-C.; Tondeur, J.-J. J. Mol. Catal. A: Chem. 1999, 140,
31.
(54) Bloodworth, A. J.; Davies, A. G. Proc. Chem. Soc., London 1963,
264.
(55) Entelis, S. G.; Nesterov, O. V.; Tiger, R. P. J. Cell. Plast. 1967, 3,
360.
(56) Subrayan, R. P.; Zhang, S.; Jones, F. N.; Swarup, V.; Yezrielev, A.
I. J. Appl. Polym. Sci. 2000, 77, 2212.
(57) Richter, E. B.; Macosko, C. W. Polym. Eng. Sci. 1978, 18, 1012.
(58) Chen, L. W.; Ho, K. S. J. Polym. Sci., Part A: Polym. Chem. 1997,
35, 1711.
(59) Higginbottom, H. P.; Bowers, G. R.; Hill, L. W.; Courtier, J. F.
Prog. Org. Coat. 1998, 34, 27.
(60) Sojecki, R.; Trzcinski, S. Eur. Polym. J. 1998, 34, 1793.
(61) Sojecki, R.; Trzcinski, S. Eur. Polym. J. 2000, 36, 1511.
(62) Mignani, G.; Destarac, M.; Taton, D.; Gnanou, Y.; Baceiredo,
A.; Kato, T.; Bonnette, F.; Sivasankarapillai, G. (Rhodia Operations,
115
Review
Fr.; Centre National de la Recherche Scientifique (C.N.R.S))
Synthesis of urethanes and of polyurethanes catalyzed by carbenes,
International Patent WO2009016322, 2009.
(63) Coutelier, O.; El Ezzi, M.; Destarac, M.; Bonnett, F.; Kato, T.;
Baceiredo, A.; Sivasankarapillar, G.; Granou, Y.; Taton, D. Polym.
Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 2011, 52, 290.
(64) Hentschel, T.; Munstedt, H. Polymer 2001, 42, 3195.
(65) Chattopadhyay, D. K.; Webster, D. C. Prog. Polym. Sci. 2009, 34,
1068.
(66) Pielichowski, K.; Kulesza, K.; Pearce, E. M. J. Appl. Polym. Sci.
2003, 88, 2319.
(67) Simon, J.; Barla, F.; Kelemen-Haller, A.; Farkas, F.; Kraxner, M.
Chromatographia 1988, 25, 99.
(68) Montaudo, G.; Puglisi, C.; Scamporrino, E.; Vitalini, D.
Macromolecules 1984, 17, 1605.
(69) Jousseaume, B.; Laporte, C.; Toupance, T.; Bernard, J. M.
Tetrahedron Lett. 2002, 43, 6305.
(70) Jousseaume, B.; Laporte, C.; Toupance, T.; Bernard, J. M.
Tetrahedron Lett. 2003, 44, 5983.
(71) Camberlin, Y.; Pascault, J. P.; Letoffe, J. M.; Claudy, P. J. Polym.
Sci., Polym. Chem. Ed. 1982, 20, 383.
(72) Ulrich, H., Ed. Chemistry and Technology of Isocyanates; John
Wiley & Sons: Chichester, U.K., 1996.
(73) Querat, E.; Tighzert, L.; Pascault, J. P.; Dusek, K. Angew.
Makromol. Chem. 1996, 242, 1.
(74) Wakeshima, I.; Kijima, I. Bull. Chem. Soc. Jpn. 1975, 48, 953.
(75) Wakeshima, I.; Suzuki, H.; Kijima, I. Bull. Chem. Soc. Jpn. 1975,
48, 1069.
(76) Kresta, J. E.; Hsieh, K. H. Polym. Prepr. (Am. Chem. Soc., Div.
Polym. Chem.) 1979, 20, 488.
(77) Bantu, B.; Pawar, G. M.; Decker, U.; Wurst, K.; Schmidt, A. M.;
Buchmeiser, M. R. Chem.Eur. J. 2009, 15, 3103.
(78) Sandler, S. R.; Karo, W. Polymerization Reactions of Mono- and
Diisocyanates. In Polymer Synthesis, 2nd ed.; Academic Press: San
Diego, CA, 1996.
(79) Bur, A. J.; Fetters, L. J. Chem. Rev. 1976, 76, 727.
(80) Farrissey, W. J., Jr.; Ricciardi, R. J.; Sayigh, A. A. R. J. Org. Chem.
1968, 33, 1913.
(81) Braunstein, P.; Nobel, D. Chem. Rev. 1989, 89, 1927.
(82) Ostrogovich, G.; Kerek, F.; Buzas, A.; Doca, N. Tetrahedron
1969, 25, 1875.
(83) Meisert, E.; Fischer, P. (Farbenfabriken Bayer A.-G.)
Carbodiimides and carbodiimide-isocyanate adducts, German Patent
19660318, GB1115260, 1968.
(84) Hennig, H. J.; Fischer, P. (Farbenfabriken Bayer A.-G.)
Polyisocyanates containing a carbodiimide-isocyanate adduct, French
Patent FR2000741, 1969.
(85) Spyrou, E.; Metternich, H. J.; Franke, R. Prog. Org. Coat. 2003,
48, 201.
(86) Singh, H.; Jain, A. K. J. Appl. Polym. Sci. 2009, 111, 1115.
(87) Semsarzadeh, M. A.; Navarchian, A. H. J. Appl. Polym. Sci. 2003,
90, 963.
(88) Dick, C.; Dominguez-Rosado, E.; Eling, B.; Liggat, J. J.; Lindsay,
C. I.; Martin, S. C.; Mohammed, M. H.; Seeley, G.; Snape, C. E.
Polymer 2000, 42, 913.
(89) Kordomenos, P. I.; Kresta, J. E. Macromolecules 1981, 14, 1434.
(90) Kordomenos, P. I.; Kresta, J. E.; Frisch, K. C. Macromolecules
1987, 20, 2077.
(91) Dearth, R. S.; Mertes, H.; Jacobs, P. J. Prog. Org. Coat. 1996, 29,
73.
(92) Singh, P.; Boivin, J. L. Can. J. Chem. 1962, 40, 935.
(93) Dusek, K.; Spirkova, M.; Havlicek, I. Macromolecules 2002, 23,
1774.
(94) Spirkova, M.; Kubin, M.; Dusek, K. J. Macromol. Sci., Chem.
1990, A27, 509.
(95) Spirkova, M.; Dusek, K. Polym. Bull. (Berlin) 1989, 22, 191.
(96) Schwetlick, K.; Noack, R. J. Chem. Soc., Perkin Trans. 2 1995,
395.
(97) Kogon, I. C. J. Org. Chem. 1959, 24, 83.
dx.doi.org/10.1021/cr300195n | Chem. Rev. 2013, 113, 80−118
Chemical Reviews
(98) Heintz, A. M.; Duffy, D. J.; Hsu, S. L.; Suen, W.; Chu, W.; Paul,
C. W. Macromolecules 2003, 36, 2695.
(99) Kogon, I. C. J. Org. Chem. 1958, 23, 1594.
(100) Duff, D. W.; Maciel, G. E. Macromolecules 1990, 23, 3069.
(101) Duff, D. W.; Maciel, G. E. Macromolecules 1991, 24, 651.
(102) Kozakiewicz, J.; Przybylski, J.; Sylwestrzak, K.; Ofat, I. Prog.
Org. Coat. 2011, 72, 120.
(103) Galante, M. J.; Williams, R. J. J. J. Appl. Polym. Sci. 1995, 55, 89.
(104) Kadurina, T. I.; Prokopenko, V. A.; Omel’chenko, S. I. Polymer
1992, 33, 3858.
(105) Caille, D.; Pascault, J. P.; Tighzert, L. Polym. Bull. (Berlin)
1990, 24, 23.
(106) Caille, D.; Pascault, J. P.; Tighzert, L. Polym. Bull. (Berlin)
1990, 24, 31.
(107) Okumoto, S.; Yamabe, S. J. Comput. Chem. 2001, 22, 316.
(108) Howarth, G. A.; Manock, H. L. Rivestimenti Mater. Compos.
1998, 6, 25.
(109) Grepinet, B.; Pla, F.; Hobbes, P.; Monge, T.; Swaels, P. J. Appl.
Polym. Sci. 2001, 81, 3149.
(110) Ionescu, M. Chemistry and Technology of Polyols for
Polyurethanes; Rapra Technology, Ltd.: Shawbury, Shrewsbury,
Shropshire, U.K., 2005.
(111) Huang, X. Y.; Yu, W.; Sung, C. S. P. Macromolecules 1990, 23,
390.
(112) Burel, F.; Feldman, A.; Bunel, C. Polymer 2005, 46, 15.
(113) Ni, H.; Aaserud, D. J.; Simonsick, W. J., Jr.; Soucek, M. D.
Polymer 2000, 41, 57.
(114) BASF_Corporation MDI Handbook, 2009.
(115) Schmitt, F.; Wenning, A.; Weiss, J.-V. Prog. Org. Coat. 1998,
34, 227.
(116) Burel, F.; Feldman, A.; Loutelier-Bourhis, C.; Bunel, C. e-
Polymers 2004, No. 011.
(117) Bernard, J. M.; Schwarz, J.; Olier, P. (Perstorp Tolonates
France) Manufacture of low-viscosity allophanates for low-viscosity
crosslinkers for coatings, French Patent FR2939433 2008.
(118) Fravel, H. G., Jr.; Regulski, T. W.; Thomas, M. R. Ind. Eng.
Chem. Prod. Res. Dev. 1984, 23, 586.
(119) Zhang, C.-L.; Feng, L.-F.; Gu, X.-P.; Hoppe, S.; Hu, G.-H.
Polym. Eng. Sci. 2012, 52, 300.
(120) Wu, H.-S.; Chuang, M.-H.; Hwang, J.-W. J. Appl. Polym. Sci.
1999, 73, 2763.
(121) Mohammed, S.; Daniels, E. S.; Klein, A.; El-Aasser, M. S. J.
Appl. Polym. Sci. 1998, 67, 559.
(122) Ryan, A. J.; Macosko, C. W.; Bras, W. Macromolecules 1992, 25,
6277.
(123) Ryan, A. J.; Willkomm, W. R.; Bergstrom, T. B.; Macosko, C.
W.; Koberstein, J. T.; Yu, C. C.; Russell, T. P. Macromolecules 1991,
24, 2883.
(124) Elwell, M. J.; Ryan, A. J.; Gruenbauer, H. J. M.; Van Lieshout,
H. C. Macromolecules 1996, 29, 2960.
(125) Wilkinson, A. N.; Naylor, S.; Elwell, M. J.; Draper, P.;
Komanschek, B. U.; Stanford, J. L.; Ryan, A. J. Polymer 1996, 37, 2021.
(126) Pascault, J.-P.; Sautereau, H.; Verdu, J.; Williams, R. J. J.
Thermosetting Polymers; Marcel Dekker Inc: New York, 2002.
(127) Dusek, K.; Duskova-Smrckova, M. Prog. Polym. Sci. 2000, 25,
1215.
(128) Potter, T. A.; Schmelzer, H. G.; Baker, R. D. Prog. Org. Coat.
1984, 12, 321.
(129) TOSOH_CORPORATION, Catalytic Activities of Various
Tertiary Amines For Urethane Formation Reactions, 2002, http://
www.tosohusa.com/NR/rdonlyres/AC621B08-8CBF-425F-91AD-
AAA2CC6BD464/0/
TEDAandToyocatReviewCatalyticActivitiesStudy.pdf.
(130) Barrere, M.; Landfester, K. Macromolecules 2003, 36, 5119.
(131) Daniel-da-Silva, A. L.; Bordado, J. C. M.; Martin-Martinez, J.
M. J. Appl. Polym. Sci. 2008, 107, 700.
(132) Querat, E.; Tighzert, L.; Pascault, J.-P. J. Coat. Technol. 1996,
68, 83.
116
Review
(133) Baghdachi, J.; Perez, H.; Shah, A. Design and Development of
Self-Healing Polymers and Coatings. In Smart Coatings III; Baghdachi,
J., Provder, T., Eds.; ACS Symposium Series 1050; American Chemical
Society: Washington, DC, 2010.
(134) Bayer, O. In Das Diisocyanat-Polyadditionsverahren (The
Diisocyanate Polyaddition Process); Hanser, C., Ed., Carl Hanser
Verlag: Munich; 1963.
(135) Endres, W.; Lechner, M. D.; Steinberger, R. Macromol. Mater.
Eng. 2003, 288, 525.
(136) Lu, Q.-W.; Hernandez-Hernandez, M. E.; Macosko, C. W.
Polymer 2003, 44, 3309.
(137) Yoon, P. J.; Han, C. D. Macromolecules 2000, 33, 2171.
(138) Yang, W. P.; Macosko, C. W.; Wellinghoff, S. T. Polymer 1986,
27, 1235.
(139) Bajsic, E. G.; Rek, V. J. Appl. Polym. Sci. 2000, 79, 864.
(140) van Pelt, W. W. G. J.; Goossens, J. G. P. Anal. Chim. Acta 2007,
604, 69.
(141) Welker, T.; Boes, U.; Menzel, F.; Kuhn, D.; Schachtely, U.;
Lagneaux, D.; Sautel, H. (Evonik Degussa GmbH, Germany)
Processing aid for thermoplastic polyurethanes, preparation and use
of processing aid, U.S. Patent US20100092710, 2010.
(142) Majumdar, B.; Paul, D. Reactive Compatibilization. In Polymer
Blends: Formulation and Performance; Paul, D. R., Bucknall, C. B., Eds.;
John Wiley & Sons, Inc.: 2000; Vol. 1.
(143) Lu, Q.-W.; Hoye, T. R.; Macosko, C. W. J. Polym. Sci., Part A:
Polym. Chem. 2002, 40, 2310.
(144) Lapprand, A.; Boisson, F.; Delolme, F.; Mechin, F.; Pascault, J.
P. Polym. Degrad. Stab. 2005, 90, 363.
(145) Lapprand, A.; Mechin, F.; Pascault, J. P. J. Appl. Polym. Sci.
2007, 105, 99.
(146) Nierzwicki, W. J. Appl. Polym. Sci. 1985, 30, 761.
(147) Molero, C.; de Lucas, A.; Rodriguez, J. F. Polym. Degrad. Stab.
2006, 91, 894.
(148) Wicks, Z. W., Jr. Prog. Org. Coat 1975, 3, 73.
(149) Wicks, Z. W., Jr. Prog. Org. Coat. 1981, 9, 3.
(150) Witzeman, J. S. Prog. Org. Coat. 1996, 27, 269.
(151) Wicks, Z. W., Jr.; Jones, F. N.; Pappas, S. P. Organic Coatings:
Science and Technology, Vol. 2: Applications, Properties, and Performance;
Wiley: New York, 1994.
(152) Wicks, Z. W., Jr.; Jones, F. N.; Pappas, S. P. Organic Coatings:
Science and Technology, Vol. 1: Applications, Properties, and Performance;
Wiley: New York, 1992.
(153) Fernandez d’Arlas, B.; Rueda, L.; Stefani, P. M.; de la Caba, K.;
Mondragon, I.; Eceiza, A. Thermochim. Acta 2007, 459, 94.
(154) Vyazovkin, S.; Sbirrazzuoli, N. Macromol. Rapid Commun.
2006, 27, 1515.
(155) Mishra, A. K.; Chattopadhyay, D. K.; Sreedhar, B.; Raju, K. V.
S. N. Prog. Org. Coat. 2006, 55, 231.
(156) Levine, A. W.; Fech, J., Jr. J. Org. Chem. 1972, 37, 1500.
(157) Furukawa, M.; Yokoyama, T. J. Polym. Sci., Polym. Lett. Ed.
1979, 17, 175.
(158) Nasar, A. S.; Subramani, S.; Radhakrishnan, G. J. Polym. Sci.,
Part A: Polym. Chem. 1999, 37, 1815.
(159) Ni, H.; Nash, H. A.; Worden, J. G.; Soucek, M. D. J. Polym. Sci.,
Part A: Polym. Chem. 2002, 40, 1677.
(160) Delebecq, E. Ph.D. Thesis, École Nationale Supérieure de
Montpellier, 2011.
(161) Sankar, G.; Nasar, A. S. J. Appl. Polym. Sci. 2008, 109, 1168.
(162) Gedan-Smolka, M.; Haussler, L.; Fischer, D. Thermochim. Acta
2000, 351, 95.
(163) Griffin, G. R.; Willwerth, L. J. Ind. Eng. Chem. Prod. Res. Dev.
1962, 1, 265.
(164) Delebecq, E.; Ganachaud, F. Unpublished results.
(165) Ho, K. S.; Chen, L. W. J. Polym. Sci., Part A: Polym. Chem.
1997, 35, 1703.
(166) Seshadri, S. R.; Gitlitz, M.; Bossert, E. C. Proc. Int. Waterborne,
High-Solids, Powder Coat. Symp. 1996, 23rd, 492.
(167) Levine, A. W.; Fech, J., Jr. J. Org. Chem. 1972, 37, 2455.
dx.doi.org/10.1021/cr300195n | Chem. Rev. 2013, 113, 80−118
Chemical Reviews
(168) Vandenabeele-Trambouze, O.; Mion, L.; Garrelly, L.;
Commeyras, A. Adv. Environ. Res. 2001, 6, 45.
(169) Muehlebach, A. J. Polym. Sci., Part A: Polym. Chem. 1994, 32,
753.
(170) Kothandaraman, H.; Nasar, A. S. Polymer 1993, 34, 610.
(171) Rand, L.; Lateef, A. B.; Reeder, J. A. J. Org. Chem. 1971, 36,
2295.
(172) Mohanty, S.; Krishnamurti, N. Eur. Polym. J. 1998, 34, 77.
(173) Sankar, G.; Nasar, A. S. J. Polym. Sci., Part A: Polym. Chem.
2007, 45, 1557.
(174) Gnanarajan, T. P.; Iyer, N. P.; Nasar, A. S.; Radhakrishnan, G.
Polym. Int. 2002, 51, 195.
(175) Kothandaraman, H.; Thangavel, R. J. Polym. Sci., Part A: Polym.
Chem. 1993, 31, 2653.
(176) Muramatsu, I.; Tanimoto, Y.; Kase, M.; Okoshi, N. Prog. Org.
Coat. 1993, 22, 279.
(177) Nasar, A. S.; Subramani, S.; Radhakrishnan, G. Polym. Int.
1999, 48, 614.
(178) Subramani, S.; Nasar, A. S.; Gnanarajan, T. P.; Iyer, N. P.;
Radhakrishnan, G. Polym. Int. 2000, 49, 546.
(179) Huang, Y.; Jones, F. N. Polym. Mater. Sci. Eng. 1993, 70, 120.
(180) Huang, Y.; Chu, G.; Nieh, M.; Jones, F. N. J. Coat. Technol.
1995, 67, 33.
(181) Carter, J. W.; Pappas, S. P. J. Coat. Technol. 1992, 64, 29.
(182) Subramani, S. Paintindia 2002, 52, 33, 36, 40, 44.
(183) Suyama, K.; Iriyama, H.; Tsunooka, M.; Shirai, M. J. Polym. Sci.,
Part A: Polym. Chem. 2004, 42, 2612.
(184) Tinnemans, A.; Roescher, A. Prog. Org. Coat. 2000, 40, 191.
(185) Tassel, X.; Barbry, D.; Tighzert, L. Eur. Polym. J. 2000, 36,
1745.
(186) Michaud, P.; Camberlin, Y. J. Polym. Sci., Part A: Polym. Chem.
1987, 25, 1717.
(187) Michaud, P.; Camberlin, Y.; Mai, C. Polym. Eng. Sci. 1988, 28,
775.
(188) Lucas Howard, R.; Wu, K. J. J. Coat. Technol. 1993, 65, 59.
(189) Barbeau, P. H.; Gerard, J. F.; Magny, B.; Pascault, J. P.; Vigier,
G. J. Polym. Sci., Part B: Polym. Phys. 1999, 37, 919.
(190) Nybakken, G. H.; Palinkas, R. L.; Laskowitz, I.; Peter, T. H.
(Chemtura Corporation, USA) Polyurethane elastomer articles from
low free diphenylmethane diisocyanate prepolymers, International
Patent WO2009108510, 2009.
(191) Caruso, P. P.; Verbanc, J. J. (du Pont de Nemours, E. I., and
Co.) Storage stable, one-package amine-cured polyurethane, German
Patent DE2430744, 1975.
(192) Burckhardt, U. (Sika Technology A.-G., Switzerland)
Aldimines and polyurethane compositions containing aldimines,
International Patent WO2010063741, 2010.
(193) Poisson, N.; Maazouz, A.; Sautereau, H.; Taha, M.; Gambert,
X. J. Appl. Polym. Sci. 1998, 69, 2487.
(194) Andreu, R.; Reina, J. A.; Ronda, J. C. J. Polym. Sci., Part A:
Polym. Chem. 2008, 46, 3353.
(195) Liu, C.; Shen, D.; Sebastian, R. M.; Marquet, J.; Schönfeld, R.
Macromolecules 2011, 44, 4616.
(196) Sudo, A.; Mori, A.; Endo, T. J. Polym. Sci., Part A: Polym. Chem.
2011, 49, 2183.
(197) Tramontano, V. J.; Thomas, M. E.; Coughlin, R. D. Polym.
Mater. Sci. Eng. 1995, 73, 99.
(198) Klinger, D.; Chang, J. Y.; Theato, P. Macromol. Rapid Commun.
2007, 28, 718.
(199) Köster, R. Angew. Chem. 1961, 73, 66.
(200) Tawney, P. O.; Snyder, R. H.; Bryan, C. E.; Conger, R. P.;
Dovell, F. S.; Kelly, R. J.; Stiteler, C. H. J. Org. Chem. 1960, 25, 56.
(201) Muramatsu, I.; Tanimoto, Y.; Kase, M.; Okoshi, N. Prog. Org.
Coat. 1999, 37, 205.
(202) Ubaghs, L.; Novi, C.; Keul, H.; Hoecker, H. Macromol. Chem.
Phys. 2004, 205, 888.
(203) Ubaghs, L.; Keul, H.; Hoecker, H. Polymer 2005, 46, 1459.
(204) Maier, S.; Loontjens, T.; Scholtens, B.; Mtilhaupt, R.
Macromolecules 2003, 36, 4727.
117
Review
(205) Kidd, T. J.; Loontjens, T. J. A.; Leigh, D. A.; Wong, J. K. Y.
Angew. Chem., Int. Ed. 2003, 42, 3379.
(206) Loontjes, J. A.; Plum, B. J. (DSM) Process for the preparation
of an N-alkyl or N-aryl carbamoyl derivative, U.S. Patent 6,448,394,
2000.
(207) Maier, S.; Loontjens, T.; Scholtens, B.; Muelhaupt, R. Angew.
Chem., Int. Ed. 2003, 42, 5094.
(208) Tundo, P.; Aricò, F.; Rosamilia, A. E.; Grego, S.; Rossi, L.;
Tundo, P.; Esposito, V. Dimethyl Carbonate: Green Solvent and
Ambident Reagent. Green Chemical Reactions; Springer: Netherlands,
2008.
(209) Tang, D.; Mulder, D.-J.; Noordover, B. A. J.; Koning, C. E.
Macromol. Rapid Commun. 2011, 32, 1379.
(210) Bosetti, A.; Cesti, P.; Calderazzo, F. (Ministero Dell’
Universita’ E Della Ricerca Scientifica E Tecnologica, Italy) Process
and catalysts for the production of aromatic carbamates from aromatic
amines and alkyl carbonates, European Patent EP0752413, 1997.
(211) Margetic, D.; Antonac, I. Z.; Glasovac, Z.; Eckert-Maksic, M.;
Maksimovic, L. Synth. Commun. 2011, 41, 2283.
(212) Grozos, S. J.; Drechsel, E. K. (American Cyanamid Co.)
Polyurethans, U.S. Patent 2,802,022, 1957.
(213) Whelan, J. M.; Hill, M.; Cotter, R. J. (Union Carbide
Corporation) Multiple Cyclic Carbonate Polymers, U.S. Patent
US3072613, 1963.
(214) Ried, W.; Merkel, W. Angew. Chem., Int. Ed. Engl. 1969, 8, 379.
(215) Mikheev, V. V.; Svetlakov, N. V.; Sysoev, V. A.; Gumerova, R.
K. Zh. Org. Khim. 1983, 19, 498.
(216) Ubaghs, L.; Fricke, N.; Keul, H.; Hoecker, H. Macromol. Rapid
Commun. 2004, 25, 517.
(217) Guan, J.; Song, Y.; Lin, Y.; Yin, X.; Zuo, M.; Zhao, Y.; Tao, X.;
Zheng, Q. Ind. Eng. Chem. Res. 2011, 50, 6517.
(218) Nishikubo, T.; Iizawa, T.; Iida, M.; Isobe, N. Tetrahedron Lett.
1986, 27, 3741.
(219) Zhao, F. A process for preparing propylene carbonate via
heterocyclization of CO2 with 1,2-propanediol, Chinese Patent
CN101376632, 2009.
(220) Aresta, M.; Dibenedetto, A.; Dileo, C.; Tommasi, I.; Amodio,
E. J. Supercrit. Fluids 2003, 25, 177.
(221) Claude, S.; Mouloungui, Z.; Yoo, J.-W.; Gaset, A.
(Organisation Nationale Interprofessionnelle Des Oleagineux- ONI-
DOL, France) Process for the preparation of glycerol carbonate,
European Patent EP955298, 1999.
(222) Mouloungui, Z.; Yoo, J.-W.; Gachen, C.-A.; Gaset, A.;
Vermeersch, G. (Organisation Nationale Interprofessionnelle Des
Oleagineux- Onidol, France) Process for the preparation of glycerol
carbonate from glycerol and ethylene or propylene carbonates,
European Patent EP739888, 1996.
(223) Tomita, H.; Sanda, F.; Endo, T. J. Polym. Sci., Part A: Polym.
Chem. 2001, 39, 4091.
(224) Tomita, H.; Sanda, F.; Endo, T. J. Polym. Sci., Part A: Polym.
Chem. 2001, 39, 860.
(225) Tomita, H.; Sanda, F.; Endo, T. J. Polym. Sci., Part A: Polym.
Chem. 2000, 39, 162.
(226) Yeo, I.-S.; Woo, B.-W.; Yoon, S.-W.; Lee, J.-H.; Park, S.-H.;
Jang, N.-J. (Foosung Co., Ltd., South Korea) Method of
manufacturing vinylethylene carbonate, U.S. Patent US20100048918,
2009.
(227) Komura, H.; Yoshino, T.; Ishido, Y. Bull. Chem. Soc. Jpn. 1973,
46, 550.
(228) Kim, H. S.; Kim, J. J.; Lee, B. G.; Kim, H. G. (Korea Institute of
Science and Technology, South Korea) Synthesis of alkylene
carbonates using a catalyst system comprising metal halide and
pyridine or pyridine derivatives, U.S. Pat. Appl. US2001-780235
20020013477, 2002.
(229) Kawanami, H.; Sasaki, A.; Matsui, K.; Ikushima, Y. Chem.
Commun. 2003, 896.
(230) Darensbourg, D. J.; Holtcamp, M. W. Coord. Chem. Rev. 1996,
153, 155.
dx.doi.org/10.1021/cr300195n | Chem. Rev. 2013, 113, 80−118
Chemical Reviews Review

(231) Kihara, N.; Endo, T. J. Polym. Sci., Part A: Polym. Chem. 1993,
31, 2765.
(232) Proempers, G.; Keul, H.; Hoecker, H. Des. Monomers Polym.
2005, 8, 547.
(233) Rannard, S. P.; Davis, N. J. Org. Lett. 1999, 1, 933.
(234) Sprott, K. T.; Corey, E. J. Org. Lett. 2003, 5, 2465.
(235) Benyahya, S.; Boutevin, B.; Caillol, S.; Lapinte, V.; Habas, J.-P.
Polym. Int. 2011, 61, 918.
(236) Lachowicz, A.; Grahe, G. F. (DAINIPPON INK &
CHEMICALS) Cyclo-carbonate-contg. ester(s) - by reaction of
corresp. cyclo-carbonate-alcohol(s) with mono- or di-carboxylic acids
in the presence of acid catalyst and solvent, German Patent
DE3937116, 2008.
(237) Steblyanko, A.; Choi, W.; Sanda, F.; Endo, T. J. Polym. Sci., Part
A: Polym. Chem. 2000, 38, 2375.
(238) Helou, M.; Carpentier, J.-F.; Guillaume, S. M. Green Chem.
2011, 13, 266.
(239) Koenraadt, M. A. A. M.; Noomen, A.; Van Den Berg, K. J.;
Klinkenberg, H.; Hobel, K. (Akzo Nobel N.V., Netherlands)
Thermosetting powder coating composition, International Patent
WO9724408, 1997.
(240) Diakoumakos, C. D.; Kotzev, D. L. Macromol. Symp. 2004, 216,
37.
(241) Tomita, H.; Sanda, F.; Endo, T. J. Polym. Sci., Part A: Polym.
Chem. 2001, 39, 851.
(242) Tomita, H.; Sanda, F.; Endo, T. J. Polym. Sci., Part A: Polym.
Chem. 2001, 39, 3678.
(243) Brignou, P.; Priebe Gil, M.; Casagrande, O.; Carpentier, J.-F.;
Guillaume, S. M. Macromolecules 2010, 43, 8007.
(244) Buergel, T.; Fedtke, M.; Franzke, M. Polym. Bull. (Berlin) 1993,
30, 155.
(245) Kim, M.-R.; Kim, H.-S.; Ha, C.-S.; Park, D.-W.; Lee, J.-K. J.
Appl. Polym. Sci. 2001, 81, 2735.
(246) Webster, D. C. Prog. Org. Coat. 2003, 47, 77.
(247) Figovsky, O. L.; Shapovalov, L. D. Macromol. Symp. 2002, 187,
325.
(248) Webster, D. C.; Crain, A. L. Prog. Org. Coat. 2000, 40, 275.
(249) Tomita, H.; Sanda, F.; Endo, T. Macromolecules 2001, 34,
7601.
(250) Figovsky, O. L.; Shapovalov, L.; Beilin, D. Presented at the 9th
International Conference:Modern Building Materials, Structures and
Techniques, Vilnius, Lithuania, 2007.
(251) Pfister, D. P.; Xia, Y.; Larock, R. C. ChemSusChem 2011, 4,
703.
(252) Leykin, A.; Beilin, D.; Birukova, O.; Figovsky, O.; Shapovalov,
L. Sci. Isr.–Technol. Advantages 2009, 11, 160.
(253) Cramail, H.; Boyer, A.; Cloutet, E.; Gadenne, B.; Alfos, C.
(Centre National de la Recherche Scientifique (C.N.R.S), France)
Bicarbonate precursors, method for preparing same and uses thereof,
International Patent WO2011061452, 2011.
(254) Boyer, A.; Cloutet, E.; Tassaing, T.; Gadenne, B.; Alfos, C.;
Cramail, H. Green Chem. 2011, 12, 2205.
(255) Fuertes, P.; Ibert, M.; Josien, E.; Tundo, P.; Arico, F.
(Roquette Freres, France) Method for preparing a dialkyl carbonate of
1,4:3,6-dianhydrohexitol, International Patent WO2011039483, 2011.
(256) Montarnal, D.; Capelot, M.; Tournilhac, F.; Leibler, L. Science
2011, 334, 965.
(257) Clements, J. H. Ind. Eng. Chem. Res. 2003, 42, 663.
(258) Figovsky, O.; Shapovalov, L.; Buslov, F. Surf. Coat. Int., Part B
2005, 88, 67.

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