Aislamiento

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
specific use of transcarbamoylation reactions to process the nitrogen atom is less available because of interactions with the
materials. In the third part, the blocked isocyanate chemistry is aromatic ring.
reviewed by discussing the addition between isocyanate group Generally speaking, if steric factors are neglected, any
and reactive hydrogen containing compounds and the thermal electron-withdrawing groups attached on the NCO moiety
reversibility of the formed products to finally describe the most increase the positive charge on the carbon atom and so enhance
widespread classes of blocking molecules. Finally, new trends in the reactivity. This leads to the following reactivity
the isocyanate/polyurethane chemistry complete this review classification:11 ClSO2NCO > RSO2NCO (R = alkyl, aryl) >
before comparing, in a conclusive discussion, isocyanate-free or OP(NCO)3 > aryl-NCO (p-NO2C6H4− > p-ClC6H4− > p-
non-isocyanate systems in the prospects of industrial outcomes. CH3C6H4− > p-CH3OC6H4−) > alkyl-NCO.
2.2. Urethanes and Ureas
2. BACKGROUND ON THE ISOCYANATE CHEMISTRY
2.2.1. Preparation of Urethanes, Ureas, and Thiour-
2.1. Structure and Reactivity of Monoisocyanates ethanes. According to the resonance forms presented in
The isocyanate group is a strained linear structure with two Scheme 1, isocyanate easily reacts with active nucleophilic
cumulated double bonds NC and CO. As in the case of reagents XH; the nucleophilic center X attacks the electrophilic
other heterocumulenes, the isocyanate group reactivity is based carbon of isocyanate.
on the polarization induced by the high electronegativities of The most important reactions involving isocyanate are
nitrogen and oxygen atoms, which delocalize the electron additions on alcohol, thiol, or amine: the isocyanate group
density toward the nitrogen and oxygen atoms, as shown in reacts with a hydroxyl group to yield urethane (Scheme 3a),
Scheme 1.
Scheme 3. Common Reactions Used in Polyurethane
Scheme 1. Resonance Structures of the Isocyanate Group Chemistry
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 with a thiol to produce thiourethane (Scheme 3b), and with an
NCO group is perpendicular to the benzene ring plane, amine to give urea bonds (Scheme 3c). The thiol group reacts
whereas Bondarenko et al.10 claimed a completely planar with isocyanates in the same way as its oxygen analog, with
structure for the whole phenylisocyanate molecule. Scheme 2 much less reactivity.3,12 The reaction with water generates
unstable carbamic acid, which decomposes into gaseous carbon
Scheme 2. Geometry and Electron Density of Phenyl dioxide and a primary amine, a common way to produce a wide
Isocyanate According to Sacher 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).
shows the electron density, the distances, and the angles for this −d[RNCO]
molecule according to Sacher. These differences are essential v= = k[RNCO][R′XH]
dt (1)
since they determine the reaction mechanism by specifying (i)
the isomeric cis/trans structure; (ii) which of the double bonds, where [RNCO] and [R′XH] represent the concentration at
NC or CO, is the first affected in the initial stage of reaction time t of isocyanate and nucleophile groups,
reaction, and (iii) whether the lone electron pair on the respectively.
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 solvent: polarity, hydrogen bonding ability, and dielectric
degrees of conversion. As the conversion increases, the constant.
isocyanate group is activated by the formation of a hydrogen Many groups studied the association states of the reactants
bond in which the urethane (or urea) moiety (Scheme 5a) or mainly in the case of alcohol−isocyanate reaction, particularly
even the nucleophile (Scheme 5b) acts as a basic catalyst.14 Baker,22−27 Entelis et al.,28,29 Ephraim, 30 Oberth and
Sato15,16 was the first to develop a kinetic equation taking Bruenner31 and Saunders and Frisch.32 Different parameters
into account the autocatalytic effect of alcohol and urethane (hydrogen bonding, dielectric constant, or basicities of species)
groups. Based on the above mechanism, the formation rate is were proposed to explain such effects with more or less
expressed as: incomplete data explanation.
Chang33 gathered all the kinetic data and proposed a general
d[NCO] k k [RNCO][R′XH][RNHCOXR′]
− = 1 3 ion-pair mechanism based on the electron donation capability
dt k 2 + k 3[RNHCOXR′] of the reactants measured by the electron donor number, DN,
k1′k 3′[RNCO][R′XH]2 as defined by Gutmann.34 First, the monomeric alcohol forms a
+ hydrogen bonding complex with the isocyanate; then a
k 2′ + k 3′[R′XH] (2) molecule S (i.e., any molecule present in the reaction medium,
e.g., solvent, alcohol) solvates the active hydrogen in the
Aromatic isocyanates are highly reactive, and thus, the rate
complex to form an ion pair, which undergoes urethane attack
constant k2 and k2′ are much higher than k3[RNHCOXR′] and
more easily (Scheme 6).
k3′ [RXH], respectively. The rate of reaction (eq 2) becomes
d[NCO] Scheme 6. Uncatalyzed Urethane Formation Mechanism
− = 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 According to Scheme 6, the rate greatly depends upon the
kinetics during the initial stages of the reaction and solvation power (equilibrium b). The electron donor character
subsequently describe autocatalytic third-order kinetics arising of the reactant S controls the reaction rate according to two
from the formation of hydrogen bonds.17,18 Majoros et al.19−21 roles: (i) it can catalyze the reaction by activating the
synthesized aromatic and aliphatic polyurethane prepolymers isocyanate/alcohol complex or (ii) it inhibits the reaction by
by high throughput experiments and checked that the order of forming a hydrogen bonding complex with the oxygen of
reaction in nucleophile is 2. alcohol. The inhibition effect is due to the reduction of the
2.2.2.2. Concentration and Solvent Effects. As explained concentration of the alcohol/isocyanate complex and of
above, the reactivity toward the NCO group is not constant but monomeric alcohol, which entails catalytic activity.
strongly depends on the possible association state of the When the reaction is carried out in alkanes, the low DN value
reactants. The concentration of these complexes, such as (lower than for alcohols) gives no interaction with the
dimeric or trimeric alcohol or alcohol−isocyanate or alcohol− reactants. Here, solvent is considered as a diluent, which first
solvent complexes, not only depends on the concentration of increases the monomeric alcohol concentration and second
the reactants but also is determined by the characteristics of the decreases the alcohol/isocyanate complex concentration. Thus,
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 for a model isocyanate−alcohol reaction catalyzed by tertiary
effects leading to no significant variation of the reaction rate amines. For amine catalysis, the most widespread industrial
compared with bulk reactions (Table 1, line 1). The common catalyst is 2,2′-diazabicyclo[2.2.2]octane or DABCO. It is
aprotic polar solvents that form hydrogen bonds decrease the important to note that their relative reactivity depends on
monomeric alcohol (the active species) and the isocyanate/ catalyst concentration (Table 3).
alcohol complex concentration; the reaction rate is reduced
(Table 1, rows 2−7). On the other hand, some aprotic solvents, Table 3. Relative Rate Constants of Catalysts in an
for example, DMSO and DMF, have higher solvation power Isocyanate−Hydroxyl Reaction49a
than alcohol (higher DN), which increases the solvated ion pair
catalyst concentration (%) relative rate constant
concentration, counteracting the lower complex concentration
to produce a huge catalytic effect (Table 1, rows 8 and 9). uncatalyzed 1
Chlorobenzene, benzene, nitrobenzene, ethyl acetate, acetoni- DABCO 0.1 130
0.2 260
trile, and dioxane have a certain solvation power but lower than
0.3 330
the monomeric alcohol; the overall effect of these solvents is an
DBTDL 0.1 210
inhibition effect.
0.5 670
In the third step (Scheme 6c), the high dielectric constant of
DBTDL + DABCO 0.1 + 0.2 1000
the solvent (ε) helps to dissociate the O−H bond. The a
independence of ε from the reaction rate indicates that OH Reactants not given in the publication.
dissociation is not the controlling step.
2.2.2.3. Catalysis. Tertiary amines and organometallic Generally speaking, metal-based catalysts act as Lewis acids
compounds, such as salts of tin or iron, present catalytic toward alcohol or isocyanate to initiate the reaction. It has been
activity for the reaction between isocyanate and compounds shown that numerous organometallic compounds, such as
bearing a labile hydrogen atom. organo-lead,39 -tin,17 -zirconium,40,41 -magnesium,42 -bismuth,
The catalysis role of tertiary amine is easily explained by the and -iron43,44 are effective catalysts for the isocyanate−hydroxyl
mechanism described in Scheme 6. Amine plays a similar role reaction. The tin compounds, among which those represented
as the solvent molecules, and thus the catalytic activity strongly by the general formula Bu2SnX2 (X is an anion) exhibit
depends on the donor number. With very high donor value in remarkable catalytic activity, for example, the dibutyltin
the range of 30−50, the addition of a small amount of tertiary dilaurate, DBTL. Mercury compounds combine two industrially
amine does not affect the concentration of the isocyanate/ remarkable properties: they initially retard the reaction (good
alcohol complex, but its high DN value leads to strong solvation latency) and thereafter, when the reaction commences, they
effect. Table 2 presents an example of rate constants measured provide a high conversion in short time reaction.45−48 Current
investigations are carried out to replace these highly toxic
Table 2. Relative Rate Constants for the Methanol/Phenyl compounds, so far with mixed results.
Isocyanate (0.24 M/0.24 M) Reaction in Di-n-butyl Ether, in Concerning metal-based catalysis, recent kinetic data40,50−53
Presence of 0.03 M Amine Based Catalysts at 20 °C33,38 tend to prove that the isocyanate activation by tin alkoxide
originally proposed by Bloodworth and Davies54 is more
tertiary amine DN34 relative rate constant relevant than alcohol activation by coordinating with tin as
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 the tin alkoxide previously formed by alcoholysis of the starting
tributyl amine a 54 tin compound as shown in Scheme 7A. Transfer of the alkoxide
triethylamine 50.7 134 anion onto the coordinated isocyanate affords an N-stannylur-
DABCO a 1206 ethane, which then undergoes alcoholysis to give the urethane
and the original tin alkoxide. For a mixture of aliphatic and
a
Not given. aromatic alcohols, catalysis choice orientates the reaction
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 (Scheme 4). The urethane bond formed by addition of
temperature, in presence of DABCO or even in the absence isocyanate on alcohol presents a weak C−NH bond with an
of catalyst, hexamethylene diisocyanate (HDI) reacts first with activation energy of dissociation in the range of 100−130 kJ/
the phenolic OH; whereas with organotin catalyst, the aliphatic mol.64,65 In a temperature range starting from 150 °C and
OH−HDI reaction is faster. For both catalyses, the aliphatic above, four degradation pathways were identified (Scheme 8):
urethane is always thermodynamically favored, so upon first, the urethane linkage can be broken into the initial reagents
refluxing the phenolic-based urethane rearranges to an aliphatic (isocyanate and alcohol). Other pathways, leading to small
urethane.56 molecules such as carbon dioxide and primary and secondary
The catalyst concentration influences the relative reactivity of amines, eventually with olefin formation, are also possible but
reaction (Table 3) and according to Richter et al.,57 the tin occur more slowly and at higher temperature (Scheme 8b,c). In
catalyst has first to dissociate before complexing the isocyanate the presence of a more nucleophilic compound, urethane can
group. This equilibrium is temperature sensitive and thus, the rearrange, via transcarbamoylation, into a new urethane or urea
effective concentration in catalytic active species is difficult to compound (Scheme 8d).
ascertain. Several studies demonstrated that for both amine58 or The main degradation pathway depends on the equilibrium
tin59 catalysis systems, increasing the catalyst concentration between urethane bond and the starting functional groups.
beyond a certain level does not accelerate the reaction further. When temperature increases, the reverse reaction occurs
Synergism between tin and amine catalyst systems has been (Scheme 8a). Generally speaking, the more easily the urethanes
depicted by Tarasov et al.28 for addition of butanol on m- are formed, the less stable they are. Thus, according to the
chlorophenyl isocyanate, by Sojecki and co-worker60,61 for the reactivity classification presented before, the following decom-
TDI-macrodiols reactions or by Frisch and Rumao49 (Table 3). position temperature order is given: alkyl-NCO/alkyl-OH (250
Finally, one should note the recent study on carbene as a °C) > aryl-NCO/alkyl-OH (200 °C) > alkyl-NCO/aryl-OH
catalyst of isocyanate−hydroxyl reaction under mild conditions, (180 °C) > aryl-NCO/aryl-OH (120 °C).67
typically below 70 °C (Scheme 7B).62,63 Electronic effects on the substituents also influence both the
2.2.3. “Transreactions” and Reversibility. The individual kinetics and pathway of the thermal decomposition: aromatic
stages of the reactions between isocyanates and protic groups tend to favor the reverse reaction (Scheme 8a), while
nucleophilic reagents are all reversible and, furthermore, aliphatic ones promote urethane dissociation into primary
characterized by an intrinsic reversibility under heating amine and olefin (Scheme 8b).67 Reverse reaction occurs
exclusively for N-mono substituted polyurethanes while N- (Scheme 9) or by a two-step process: first reverse reaction of
disubstituted ones mainly degrade through dissociation to the urethane linkage (carbamate, -NHCOO-) above the
primary amine, olefin, and CO2.68 melting temperature of HS2 (Tm ≈ 187.6 °C) and then
At a temperature as low as 120 °C, urethane linkage has been reaction of thus-generated -NCO and -OH groups when the
proven to break in the presence of a nucleophilic reagent sample cools to room temperature (Scheme 8a).
(Scheme 8d). O-Alkyl carbamates are quite stable and 2.3. Dimer, Trimer, and Polymer
necessitate high reaction temperature or efficient catalysis.
Jousseaume et al. reported transcarbamoylation reaction of N- 2.3.1. Preparation. In addition to the reaction of addition
hexyl O-methyl carbamate with n-octanol aided by 1% bismuth between an isocyanate group and reactive hydrogen-containing
compounds, isocyanate groups also undergo homocyclization.
trifluoromethanesulfonate or 1,3-dibromodistannoxane, giving
The Scheme 11 presents the different possibilities of isocyanate
yields in the range of 70−90%.69,70 Depending on the
homocyclization depending on the catalyst used.
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 Scheme 11. Isocyanate Self-Reactions
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
If aliphatic isocyanates dimerize with difficulties,72 dimers of
Scheme 10. Structure of Model Compounds Used in aromatic isocyanates are obtained by heating the monomer
Scrambling Reaction Obtained from the Reaction between with a nucleophilic catalyst. Dimerization is an equilibrium
MDI, BDO, and Ethanola 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
a 12).
In Figure 1, molecules are labeled HS1 (for n = 0) to HS4 (for n = 3).
Scheme 12. Dimerization Mechanism of Aryl Isocyanate
chromatography (Figure 1) in tetrahydrofurane (THF) before Catalyzed by Phosphine
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
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
Figure 1. SEC curves of (a) the purified model compound (HS2 = but also promotes reaction of these with diols.77
2MDI + 1BDO + 2ethanol) and (b) the mixture of compounds after Polyisocyanates are synthesized at low temperature (from
heating at 220 °C. Peaks 1, 3, and 4 are equivalent in molar mass to −40° to 100 °C) by anionic chain polymerization. The
HS1, HS3, and HS4. Reprinted with permission from ref 71. homopolymer is not thermally stable because unzipping occurs
Copyright 2003 John Wiley & Sons. and it forms monomers and cyclic trimers around 140 °C or
even at room temperature in presence of basic impurities.78 For Scheme 14. Butyl Phenylcarbamate
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
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
heating at high temperature (180−200 °C).80 Transition
compounds thanks to the hydrogen atom linked to the nitrogen
metals81 and especially organic compounds of main group 5,
atom. Because they are less reactive than hydroxyl or amine
phosphine oxides,82 and nitrogen-containing molecules (such
compounds, the reactions occur especially when isocyanates are
as amide, urea, anilide, or isocyanate derivatives)83,84 catalyze
introduced in excess. By the reaction of isocyanate with
the condensation reaction under mild conditions.
urethane or urea group, an allophanate or biuret, respectively,
2.3.2. Reversibility. If carbodiimide formation is clearly
forms, as summarized in Scheme 15. Due to the electron-
irreversible, homocyclization products can be split off and
withdrawing effect of the carbonyl group, urethane and urea
regenerate isocyanate at high temperature. Querat et al.73
groups have a much lower reactivity than the secondary amine
studied by infrared spectroscopy the dissociation of 2,4-TDI
-N-H groups; in order to promote allophanate or biuret
dimer without catalyst. They reported first-order kinetics up to
formation, a temperature typically greater than 110 °C or a
80% conversion at 160 °C and observed a relatively high
catalyst addition is necessary. To decrease isocyanate toxicity,
activation energy (Ea = 142 kJ/mol). Without catalyst, the free
coating formulations favor high molar mass polyisocyanates
isocyanate regeneration, which depends on the parent
from allophanate, biuret, and isocyanurate chemistry.91
isocyanates, occurs only at high temperature. The uretdiones
When uretdione is heated in the presence of a nucleophile,
of 2,4-TDI, isophorone diisocyanate (IPDI), and HDI (for
such as an alcohol or an amine, two mechanisms were
structures, see Scheme 21) decompose without catalyst at 150,
suggested to occur, one of which generates allophanate or
160, and 200 °C, respectively.7,85 The presence of the
biuret, respectively (see an example, Scheme 16, of allophanate
remaining catalyst lowers the dissociation temperature. In
formation); the reaction proceeds either by free isocyanate
presence of tributylphosphine, Saunders2 reported that TDI
group releasing, generating new ureas, or through direct
dimers are 10% dissociated at 10 °C, 25% dissociated at 25 °C
allophanate formation. The second mechanism competes also
and totally dissociated at 80 °C in benzene solution.
with linear polyurethanes formation, especially when isocyanate
Although the isocyanates can be regenerated from their
is in excess, and so, the gel point is reached at lower conversion
dimers by heating at moderate temperature, a higher temper-
(see section 3 of this review). Singh92 found that the reaction of
ature (>250 °C) leads to isocyanurates via trimerization. While
TDI dimer with alcohols at 90 °C gives principally diurethanes
usually considered thermally stable,86 isocyanurate degradation
with only traces of allophanates. Higher temperatures (in the
has been observed by infrared spectroscopy, thermogravimetric
range of 125−160 °C) and a catalyst such as triethylamine or
analysis,87 and 1H and 13C nuclear magnetic resonance
N-methylmorpholine led to the formation of allophanate and
(NMR).88 Kordomenos et al.89,90 studied by infrared spectros-
triphenyl isocyanates. Di-n-propylamine, di-n-butylamine, and
copy the degradation kinetics of model isocyanurate synthe-
di-n-amylamine ruptured the dimer ring, whereas di-sec-
sized by homocyclization of phenylisocyanate. A temperature
butylamine and dibenzylamine did not affect it.
above 417 °C is required to observe a degradation rate through
2.4.2. Rate of Formation. Formation reactions of
volatilization superior to 0.3 h−1 (Table 4); this temperature
urethane, uretdione, biuret, and allophanates compete between
each other. In a system containing monoalcohol, monoisocya-
Table 4. Kinetic Parameters for the Degradation Reaction of nate, and water in presence of catalyst93 and in a selective
Butyl Phenyl Carbamate and Various Isocyanurates solvent, the following order of rate constants were found:
Ea TD (°C) at urethane ≫ biuret > allophanate. At a given temperature, the
(kJ·mol−1) A (h−1) k = 0.3 h−1 ref equilibrium constant of biuret formation is higher by an order
butyl phenylcarbamate 161.8 7.38 × 1012 277 89 of magnitude than the equilibrium constant of allophanate
isocyanurate of 252.2 3.69 × 1016 417 89 formation.94 The rate of allophanate formation is much smaller
phenylisocyanate than that of urethane formation; therefore allophanates are
poly(aromatic 184.1 8.46 × 1010 441 90 mainly formed when the overall ratio NCO/OH is higher than
isocyanurate)
1. For temperature below 60 °C, biuret and allophanate
poly(aliphatic 246.7 2.12 × 1016 410 90
isocyanurate) 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
must be compared with 277 °C for butyl phenylcarbamate 1 Schwetlich96 studied the alcohol−isocyanate reaction at 50
(Scheme 14). For isocyanurate-based polymer, synthesized °C at NCO/OH ratio smaller than 1 and reported that the
through self-reactions between mono- and diisocyanate, they urethane formation lies almost completely on the product side,
reported a higher stability for aromatic than aliphatic with or without the presence of common urethane formation
isocyanurate, which is explained by the strong char formation catalyst (DBTDL or DABCO). Special catalysts such as amino
during aromatic isocyanurate degradation, which retains volatile alcohols, amidines, or alkoxide anions are needed to enhance
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 Figure 2. Allophanate concentration during the reaction between a
found that the equilibrium constant of the allophanate 4 secondary hydroxyl of poly(propylene glycol) and MDI.98
formation (Keq) equals 0.2 at 128 °C. This constant is
independent of the ratio phenyl isocyanate 2/ethylcarbanilate 3 Scheme 18. Allophanate (X = O) and Biuret (X = N)
(varying from 9 to 12) but decreases when temperature Decompositions
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 aromatic substitution (comparison between 5 and 6 in Figure
increases from a negligible content (less than 1%) to over 10% 3).
of all nitrogen-containing compounds. Both low and high An interesting work of Duff et al.100,101 compared the
molecular species equally participate to the allophanate thermal stability of the different R−NH−CO−X bonds. Such
formation. The presence of such trifunctional groups broadens study was performed on an isocyanurate-rich polymer, obtained
the molar mass distribution. In that case, isocyanurate by homoaddition of 4,4′-methylene diisocyanate (MDI) in the
concentration is much less than the allophanate one. presence of stannous octoate, leading to aromatic N-functions
2.4.3. Reversibility. Allophanate and biuret bonds, as such as urea, amine, uretdione, biuret, and isocyanurate. The
products of addition reactions between isocyanate and thermal stability of this resin was studied by recording the
compounds bearing active hydrogen, are thermally reversible relative content of N-function by 15N cross-polarization/magic
when heated. Their thermal stability is generally considered as angle spinning spectroscopy (CP/MAS NMR) from room
lower than that of the urethane bond. The decomposition rates temperature to 500 °C (Figure 4). Upon increase of the
in halogenated solvent were reported by Kogon (Scheme 18 temperature, degradation of isocyanate, uretdione, and biuret
and Figure 3). The reaction rate increases with temperature for led to an increase of urea linkage concentration up to 230 °C.
allophanate and biuret groups. Allophanate is less stable than Then, between 240 and 260 °C, urea degradation occurred
biuret (comparison between 6 and 7 in Figure 3) and its leading to amine bonds whereas isocyanurate linkage broke
dissociation rate increases with temperature but also with from 280 °C. Since allophanate has been proven to be less
Scheme 17. Allophanate Formation from Phenyl Isocyanate 2 and Ethylcarbanilate 3

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-
Figure 3. First-order rate constant for allophanate and biuret linking density of diepoxy/diisocyanate material can be adjusted
decompositions (structures are given in Scheme 18). 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
Figure 4. Content of N-functions measured by 15N CP/MAS NMR inexpensive aliphatic diamines are not readily available as
for each thermal decomposition temperature. Uretdione functions precursor for diisocyanates, the aromatic diisocyanates, that is,
were identified but not quantifiable.
NCO groups borne by an aromatic moiety, represent more
than 95% of the market. Among them, two products are
stable than biuret, the thermal stability of isocyanate-based
especially widespread, TDI and MDI. Due to its small size and
bonds ensues:73,95 allophanate < biuret < urethane < urea <
symmetry, the para-phenylenediisocyanate molecule (PPDI)
isocyanurate.
provides great reactivity difference between the first NCO to
Very recently, Kozakiewicz and co-workers showed on a
react and the remaining one. Regarding the aliphatic molecules,
model allophanate molecule (obtained from phenyl isocyanate
the main reactants are HDI and to a lesser extent IPDI and
and N-ethylurethane) that not only transurethanization but also
bis(4-isocyanatocyclohexyl)methane (also called hydrogenated
urethane decomposition could regenerate isocyanate functions
MDI, HMDI; see Scheme 21 for the structure of this product).
for further curing. They made use of these findings to introduce
m-Tetramethyl-xylylene (TMXDI) is a special molecule since it
functional blocking agents for efficient gelling reaction during
allows preparation of solvent-free waterborne polyurethane
heat curing.102
dispersions due to its low reactivity toward water (for a recent
2.5. Oxazolidone review, see ref 108).
Heating an epoxy function in the presence of an isocyanate For a symmetric diisocyanate, both isocyanate groups initially
group leads to the formation of an oxazolidone ring, together present the same reactivity (k1 = k2 = k). But, as the NCO
with the trimerization of isocyanate and the homopolymeriza- group itself exhibits an activating effect on the isocyanate
tion of epoxy.103,104 It was found that the main reactions take reactivity, the second (unreacted) isocyanate group undergoes a
place step by step while the temperature increases: (i) substitution effect and its reactivity can be lowered (k′) by the
isocyanurate formation (Scheme 19a), (ii) epoxy−isocyanate electronic and steric effect of created urethane or urea group
reaction leading to oxazolidone rings (Scheme 19b), and (iii) (see Scheme 22a as an example). The first isocyanate group of
isocyanurate decomposition by epoxy groups producing 2,6-TDI reacts 5.8 times faster with poly(propylene) glycol at
oxazolidone rings (Scheme 19c).105 Isocyanurate rings were 60 °C than the second one.109 For longer distance between
found to be stable in the presence of epoxide and isocyanate diisocyanates, the reactivity difference due to substitution is
excesses, that is, reaction b is faster than c.103 A catalyst like smaller. For HMDI, the ratio between k and k′ is reported to
imidazole decreases the reaction temperature and promotes the equal 1.4.110 It should be noted that a temperature increase
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 An efficient catalysis can compensate the reactivity differ-
2.9 at room temperature to 1 at 70 °C for MDI reacting with n- ences; for example, the secondary isocyanate group of IPDI is
butanol.110,111 1.6 times more reactive with n-butanol at 50 °C than the
Asymmetric diisocyanates exhibit two initial different primary NCO group. Using DBTDL, the reactivity of the
reactivities (k1 and k2), which are again altered by the reaction secondary NCO group is 12 times superior to the primary one;
of the first isocyanate group. Thus, a reaction between an while in the presence of DABCO, the primary NCO group is
asymmetric diisocyanate and nucleophilic compound leads to 1.2 times more reactive than the secondary one.72
four reaction rate constants as exemplified in the case of 2,4- 2.7. “Polymeric Isocyanates”
TDI in Scheme 22b. These reactivity differences strongly During the course of dimer and trimer preparations, MDI and
complicate diisocyanate kinetics study. Table 5 shows the HDI, symmetric diisocyanates with close reactivity for both
reactivity ratios between isocyanate groups of 2,4-TDI reacted groups, give both the targeted product and oligomers of low
with different types of alcohol. The discrepancy in the results is molar masses.113 Dimerization of MDI (12) in bulk was studied
attributed to the temperature increase, which decreases the in a wide range of temperature, in both the solid and liquid
selectivity. According to the work of Burel et al.,112 the state (Scheme 21 and Figure 5). In an effort to keep MDI
selectivity between primary and secondary isocyanate groups of under its monomeric state, storage temperature is thus set
IPDI (ksecondary/kprimary) decreases with temperature going from either at very low temperature or just above the melting point,
31 at 25 °C to 15 at 90 °C. where the rate of formation of dimer is the lowest.114
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 Scheme 23. Example of Pentamer Produced from the Self-
Asymmetric Diisocyanate (2,4-TDI) against Hydroxyl Addition of Isophorone Diisocyanate
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 4.2
poly(propylene glycol), 15.8 2.6 2.1
60 °C109
a
NCO group in para position. bNCO group in ortho position.
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
Figure 5. Rate of dimer formation as a function of temperature.
accepted relative reaction rate as a rule of thumb. All these
Reprinted from ref 114 with permission. Copyright 2009 BASF reactions compete among each other and all are reversible.
company. Moreover, for diisocyanate, the situation is even more
complicated by the intrinsic difference of reactivity between
Greater difference of reactivity between the two isocyanate the isocyanate groups. Thus, studying these systems and above
groups facilitates the control of reactions.115 In the case of the all kinetics from a fundamental prospect is extremely complex.
asymmetric IPDI, the primary isocyanate group reacts On the other hand, the flexibility of the isocyanate chemistry is
preferentially, but reaction with the secondary isocyanate a convenient tool to stem from a wide range of compositions in
group likely occurs (r = 2−3).85 Thus, the trimerization an industrial way, as shown in the following section.
reaction of isophorone diisocyanate leads to species from
isocyanate trimer to tridecamer, trimer and pentamer (which 3. IMPLICATIONS OF THE URETHANE/UREA BOND
structure is given in Scheme 23) representing 71 and 19 wt % REVERSIBILITY IN PREPARING POLYURETHANE
of the full mixture, respectively.116 MATERIALS
One should note that polymeric isocyanates strongly increase The synthesis of PU is carried out by one or few of the
the viscosity of solution. Another way of increasing the viscosity reactions described in Scheme 3. If the functionality of the
consists in reacting diisocyanate with monoalcohol to favor the hydroxy-containing compounds or the isocyanate is increased
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

appears for the first time. Before the gel point, the material is a between SSs and HSs occur; the part solidifies and is then
liquid with a finite value of viscosity. As the reaction proceeds, ejected.
the viscosity increases and it tends to infinite at the sol−gel Contrary to RIM, a “two-step” process is often used for cast
critical transition, when a giant macromolecule percolates molding. At the end of the prepolymer synthesis (Scheme 24),
through the sample. Gelation can be roughly estimated as the the diisocyanate excess depends on the initial excess and also
time (extent of reaction) at which the elastic modulus becomes on the reactivity ratio between the two isocyanate groups. As
higher than the loss modulus, or more precisely, at which the sustainable development is the major trend for the future, the
ratio of both moduli (tan δ) becomes independent of the diisocyanate molecules in excess can be a problem to solve.
frequency of the experimental run. The extent of reaction at the There are different routes to decrease the toxicity of volatile low
gel point depends on the functionality (number of reactive molar mass diisocyanates. The first route is to increase the
sites) of precursors: the higher the functionality, the lower the boiling temperature and to decrease the vapor tension by
gel conversion. After gelation, the mass fraction of the insoluble making adducts (as examples trimers of IPDI or adducts of
giant structure increases continuously and so does the elastic HDI + TMP). Other possibilities are to distillate the
modulus of the sample.126 For thermosetting polymers, shaping diisocyanate excess after the synthesis of the prepolymer or
of the part has to be performed before the gel point where the to play with the different reactivities of the diisocyanate (like
material is still in the liquid state. Note finally, that in the case TDI 2,4 or PPDI) to prepare “diisocyanate-free” formulations
of PU, the boundary between thermoplastic and thermosetting (vide inf ra).
is not so clear. Particularly, linear segmented PU can be Finally, in addition to cast and reaction injection molding,
processed as TP granules or as cast PU. In addition when some thermoplastic polyurethanes are sometimes processed in the
urea links are introduced in the linear chains, the polymer melt state where the urethane bond reversibility behavior is
became intractable and has to be processed like a thermosetting exacerbated (see section 3.3).
3.2.2. Reaction in Solution: Coatings, Sealants, and
polymer.
Adhesives. Thanks to their excellent adhesives properties,
3.2. Processing of Polyurethane Materials good weather stability, and versatility of formulation,
3.2.1. Bulk Cross-Linked PUs by Cast Molding (CM) thermosetting PUs are currently the preferred materials for
and Reaction Injection Molding (RIM). Because isocyanate/ coatings, sealants, and adhesives. The majority of conventional
alcohol and isocyanate/amine reactions are very fast, give no formulations are solvent-borne, traditionally containing about
byproduct, and attain high degree of conversion, they are well 25% solids. Organic solvents are used to disperse the different
suited for direct polymerization of two reactive liquids, A and B, constituents of the formulation and to provide the low viscosity
in a mold. Part A is the isocyanate-based component, and part needed for conventional application methods (spray, roller
B is composed of the diols plus a catalyst (or diamines) coating, etc.). Solvent-based PU films are formed by
together with usual additives like antioxidants, pigments, and so simultaneous cross-linking of polymer network precursors and
on. PU formulations for reactive molding follow the same solvent evaporation. This is a complex process in which the
strategy as the one described in Scheme 24. Two cases are cross-linking rate and the development of the network depend
distinguished: (i) all precursors bear the same functionality of 2 on the content, nature, and volatility of the solvent.127 Because
and then an excess of isocyanate is used to generate coating and paint producers as well as end-users wish to reduce
the volatile organic compound (VOC) emissions, progress is
allophanate, resulting in further cross-linking; (ii) some
being made to increase the solid contents of solvent-based
precursors of higher functionality are introduced, for example,
liquid coatings.128
reactive oligomers like polycaprolactone with functionality
3.2.3. Reaction with Water: Preparation of Solid
equal to 3 or 4, isocyanates, such as liquid MDI with f ≥ 2.3 or
Foams. PU foams are an important commercial application
polymeric MDI, or chain extenders like trimethylol propane, of PU chemistry. They are prepared from basically the same
TMP. When increased rigidity and high-temperature perform- raw materials as elastomers by the “one-step” method (Scheme
ance are desired, further cross-linking may be accomplished via 24) and with the use of a RIM machine. Here however, instead
isocyanurate formation, using aromatic isocyanates rather than of the chain extender, water is used to react with isocyanates
aliphatic ones (Scheme 11). In this case, base catalysts, such as and form an amine and CO2, which results in foaming. The
alkoxides, quaternary ammonium, or phosphonium, promote diamine thus created can then react with isocyanate groups
this reaction. giving polyurea short segments. A catalyst can be used; both
The main difference between cast molding and RIM is to be reactions are exothermic and proceed simultaneously to
found in the reactivity. For cast molding, the pot-life is usually generate a cross-linked network, which is blown into a cellular
higher than 5 min, whereas for RIM it has to be less than 1 min, structure by the heat expanded CO2 and entrapped air. A
which means that isocyanate is reacted either with amine or silicone-based surfactant is also introduced as a cell control
with alcohol in presence of catalyst. RIM is similar to agent. Self-assembly of the HSs leads also to the formation of
thermoplastic injection molding except for the curing reaction hard domains.124
in the mold. Two reactive monomeric liquids, A and B, are The main difference between rigid and flexible foams is the
mixed together by impingement and injected into the mold by molar mass of the polyol component, less than 103 g/mol for
the so-called “one-step” method (Scheme 24). It involves the rigid foams and between (2 and 8) × 103 g/mol for the flexible
high-speed mixing of two or more reactive chemicals, just as ones, and also the average functionality of the polyol, much
they are injected into the mold. The low-viscous mixture fills higher than 2 for rigid foams. Industrially, the catalysts not only
the mold at relatively low temperatures and pressures. The bring faster rates for the reaction but also influence the
reactions must be synchronized with the process so that selectivity and thus permit control of the balance between the
gelation does not occur during the filling time. In the mold, following reactions: (i) water + isocyanate producing urea
polymerization and usually reaction induced phase separation linkages and CO2 as blowing molecule; (ii) alcohol +
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) the unpaired electron is in a very active state to promote
alcohol + urethane/urea leading to a cross-linked material urethane formation (Table 7). Isocyanate−hydroxyl reaction is
through allophanate, biuret, and isocyanurate bond formation. also favored over the water−isocyanate one in the presence of
As an example, rate constants for the different reactions zirconium chelates.40
depicted in Scheme 25 are given in Table 7.129 3.2.4. Reaction in Water: Waterborne Coatings. One of
Organotin catalysts preferentially activate alcohols over water the key choices for reducing VOC emissions is the generation
due to the higher nucleophilicity of the oxygen atoms of of waterborne coatings. Ionizable groups (usually carboxyl
alcohols. Thus, DBTDL exhibits very high activity for the chain introduced by the use of dimethylol propionic acid during the
extension through isocyanate/alcohol reaction but generates first step in Scheme 24) are first incorporated into the
weak urea formation and no activity at all on the biuret and polyurethane backbone and neutralized with carboxyl groups
allophanate. Organotin catalysts are also preferred for polyur- with a tertiary amine, before being dispersed in water. Aliphatic
ethane synthesis in aqueous medium (see below).130 Amine and cycloaliphatic isocyanates are preferred because of their low
catalysts provide a higher catalytic activity toward biuret reactivity with water and to prevent yellowing of the final film.
formation compared with allophanate reaction, and depending One difficulty is to control reactions of isocyanates with water,
on their structure, they favor blowing or gelling reaction. For which means a poor control of the stoichiometry and so of the
instance, tertiary amines containing ether bonds with two molar mass of the final PU. Another problem is the coalescence
carbons between amine and ether, such as 2,2′-dimorpholine of the initially stabilized polymer particles which is often
diethyl ether (DMDEE), have a higher affinity to water than incomplete in the final film and may take a long time to reach
alcohol that arises from their capacity to form chelates with equilibrium. For these two reasons and to increase its thermal
water molecules and, thus, to activate urea formation stability, the film is in some cases postcured by a polyisocyanate
preferentially to urethane formation.131 In contrast, DABCO leading to isocyanurate (or uretdione) structures (Scheme 11).
has extremely low steric hindrance on the nitrogen atom and This is accomplished by the use of a two-component, 2K,
system, which is not the preferred solution for end-users. Some TDI dimer was accomplished by interfacial polycondensation at
water-soluble systems are based on bisulfite adducts of room temperature, with ethylene diamine in cyclohexane and in
isocyanate prepared in aqueous solution from sodium bisulfite a polycaprolactone diol. The microcapsule shell is formed by
or sodium pyrosulfite. Bisulfite masked isocyanates are mainly the reaction of the diamine with the isocyanate groups at the
sensitive to pH variation, rather than temperature increase; at surface of the powder. If encapsulation is efficient, reactions
basic pH they hydrolyze and form symmetrical ureas (Scheme between NCO and OH groups take place only after the 2,4-
26). TDI dimer melting.132 The difficulty of this process is the
knowledge of the exact numbers of functional −NCO groups
Scheme 26. (a) Masking Reaction between Isocyanate and inside the capsules.
Sodium Bisulfate and (b) Urea Formation 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
3.2.5. Solvent-Free Reaction: Powder Formulations. established procedures. Their shells are formed of a copolymer
Powder coating technology is another route to apply PU of acrylic acid and an acrylate of a long aliphatic alcohol;
formulations in a solvent-free and hence environmentally diisocyanates (HDI, IPDI, or 4,4′-MDI) are inside. Depending
friendly manner. The two-component powder (plus additives) on type of copolyacrylate, type of surfactant (anionic surfactant
is first produced by an extrusion process. The formulation is sodium dodecylsulfate or nonionic ethoxylated nonylphenol),
applied onto the substrate by electrospray and then the temperature and rate of dispersion the microcapsule sizes were
substrate is heated above Tg (or the melting temperature, Tm) in the range 5−100 μm. To encapsulate the di- or
to produce film flow and cross-linking. The requirements for a polyisocyanates, different polyalkyl acrylates having sharp
one-pack (1K) powder coating formulation are as follows: (i) melting points of 58, 65, and 92 °C were used. About 3−7
Tg/Tm must be at least 20−30 °C above ambient conditions in wt % of different types of microcapsules (with different shell
order to store and handle the powder; (ii) polymers with low temperature melting points) were incorporated in a two-
molar masses are preferred to allow enough flow above Tg/Tm component polyurethane formulation. The most attractive
to obtain a smooth film before the beginning of cure; (iii) the feature of this system is that the factors that cause the most
cure temperature must be placed at 40−50 °C above Tg/Tm to damage to the coating, such as humidity, mechanical
achieve a convenient flow leading to film homogeneity. Typical compromise, and exposure to high temperatures, are the
systems are based on saturated polyesters, α,ω-OH terminated, same factors that initiate self-healing phenomenon.133
cured with an isocyanate-based molecule. In a 1K-powder 3.3. Reversibility of Urethane Bonds and
system, the isocyanate functions have to be blocked up to the Transcarbamoylation during the Processing of
final curing step. To obtain the 1K-powder coating formulation, Polyurethanes
masked isocyanates have to be extruded at about 100 °C with
polyamine or polyalcohol oligomer without reaction. For- 3.3.1. Example 1: Reversibility and Rheological
mation of the polyurethane coating is then accomplished by Behavior. As demonstrated in Figure 1, the thermal
releasing the isocyanates upon heating and then reacting the degradability of polyurethanes in the melt state is inevitable
free isocyanate groups with the hydroxyl component. because melting of the HSs usually occurs around or beyond
1K formulations can be prepared in different ways. One the stability temperature of the urethane linkages.134 The
strategy consists of using a blocking molecule, which releases at thermal degradation of TPUs exerts a significant effect on
high temperature to regenerate an isocyanate. This strategy is rheological behavior, and thus processing conditions. They
extensively described in the next section. Making use of the show a sharp increase in flow, greater than expected due to
difference in reactivity between free isocyanates and uretdione thermal effects only. The viscosity decrease is interpreted in
rings, diisocyanate dimers can also be used as “self-blocked terms of a thermally induced molar mass decrease, and as
isocyanates”. They offer the potential advantage that no volatile expected from the reversal of the urethane formation reaction,
byproducts are formed. As an example, the 2,4-TDI dimer the viscosity equilibrium is associated with a molar mass
contains one uretdione ring, formed by dimerization of two equilibrium. To describe the flow of melt TPU, kinetic models
isocyanate groups, and two free isocyanate groups. The latter have been proposed in which both flow and reversible reaction
react rapidly with the hydroxyl groups of a macrodiol at contribute to the total activation energy for the process.64,135,136
temperatures above its melting temperature (Tm = 80 °C). In Injection molding up to 180 °C gives no change in molar
the presence of additional −OH groups, the regenerated mass but increasing temperature to 220 °C divides the mass-
isocyanate can then react to form urethanes. Experiments have average molar mass (Mw) by two for commercial ester-based
also revealed the formation of allophanate groups as reaction PUs and by three for ether-based ones.137 The same trends
products of a uretdione ring with a hydroxyl group. Application were measured during PU annealing, in which the depolyme-
of branching theory has shown that the system can gel due to rization process is detectable from 180 °C. Moreover, insoluble
allophanate formation in a wide range of initial molar ratios of gels are detected after 60 min at 190 °C.137 Yang et al. observed
NCO to OH groups.73 Formation of allophanates is favored by on model polyurethane oligomers the existence of free
DBTDL. With primary amines, the direct reaction with the isocyanates above 150 °C.138 Free isocyanate groups react
dimer is favored, but biurets are also obtained.7,85 The last either on decomposition products (alcohol or amine) or on the
route for preparing masked isocyanates is by microencapsula- urethane and urea linkages leading to possibly insoluble gels
tion. As an example, the microencapsulation of the solid 2,4- formed by allophanate and biuret cross-links, respectively.
It should be noted that the thermally induced molar mass of cyclic oligomers, etc.) could occur, exerting a significant
decrease is completely reversible. Figure 6 shows the 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
Figure 6. Molar mass decrease as a function of temperature. Labels use reversibility of urethane bonds for in situ reactive
indicate the time necessary to reach equilibrium.64 compatibilization of blends containing at least one TPU, Lu
et al.143 have investigated reactions between urethanes and
equilibrium values reached as a function of temperature. The many functional compounds. A model urethane compound was
higher the initial molar mass, the higher the number of broken synthesized by simply capping 4,4′-MDI with n-octanol. This
bonds.135 Bajsic and Rek139 prepared four PUs by reacting low molar mass diurethane, dioctyl 4,4-methylenebis(phenyl
poly(oxytetramethylene)glycol or poly(caprolactone glycol) carbamate) (OMO) was reacted with several small monofunc-
with HMDI or H12MDI. They recorded the first degradation tional compounds. NMR and FTIR spectroscopies were used
step of PU by TGA between 280 and 300 °C. By rheological for quantitative analyses of formed products. According to the
measurements, Hentschel64 confirmed that at constant temper- conversions of urethane linkages at 200 °C after 5 min, the
ature between 180 and 220 °C, the molar mass of the reactivity of the common functional groups toward urethane
polyurethane melt exponentially drops and asymptotically linkages can be roughly ranked in decreasing order as follows:
approaches a constant value. primary amine > secondary amine ≫ hydroxyl ≈ acid ≈
For the commercial TPU consisting of MDI and hexanediol, anhydride ≫ epoxy. The reactions between OMO and primary
with a molar mass of 30.5 kg·mol−1 (ISOPLAST 2530 from amine were also conducted at different temperatures between
Dow Chemical Company), the so-called ceiling temperature 170 and 200 °C and are best described with a second-order
(Tcl) was determined to be 160 °C using temperature- bimolecular reaction model. In short, the two types of amines
modulated differential scanning calorimetry (TM-DSC). (primary and secondary) are the most well suited function-
Furthermore, the TM-DSC experiments proved that the alities for reactively compatibilizing TPU with other functional
depolymerization reaction of TPU is completely reversible polymers. Anhydride, acid, and hydroxyl groups may also be
and equilibrium is attained almost instantaneously. By another used depending on specific situations. The epoxy functionality
technique, Fourier transform infrared (FT-IR) spectroscopy, is not recommended, given its low reactivity toward urethane
and by measurement of the increase in the isocyanate linkages.
absorption band at 2270 cm−1 with increasing temperature, a 3.3.3. Example 3: Reversibility To Generate “Reproc-
quantitative depolymerization curve was constructed. The essable” Cross-Linked Polymers. The only functional group
complete reversibility of the reaction was checked by both that was not used in the work describe above143 was isocyanate.
the disappearance of the isocyanate absorption band after the In the same way as Lu et al.,143 Lapprand et al.144 have studied
sample cooled to room temperature and the absence of any the reaction of the same low molar mass diurethane, OMO,
absorption band characteristic of products from side irreversible with 4,4′-MDI or trimer of isophorone diisocyanate (tIPDI).
reactions of isocyanate (Scheme 8). By FT-IR spectroscopy, a The products of the reaction were characterized by SEC and
Tcl of 155 °C was derived for the polymer, quite similar to the MALDI-TOF for molar mass determinations, and 1H and 13C
one given by the TM-DSC technique. Furthermore, highly NMR for characterization of functional groups. Thanks to a
elevated temperatures were necessary for complete depolyme- model study, it was possible to clearly identify allophanates as
rization to come back to monomers.140 new functional groups after the reaction of an excess of
To conclude on this first case, and adopting the point of view isocyanates (equimolar NCO/urethane ratio) at high temper-
of the manufacturer who processes TPU, the important result is ature (170 and 200 °C) and after the mixture was cooled to
that both the processing temperature and the residence time of room temperature. Only 10% allophanates were obtained after
the polymer in the molten liquid state strongly affect its flow: 1 h of reaction, but one important and unexpected result was
the viscosity is decreased and thus processing conditions are that no isocyanurate was found as a reaction product.
easier, knowing that the molar mass decrease is in principle Concerning the molar masses and molar mass distribution,
reversible. However, if processing temperatures are too high or the reactive system was composed of residual diurethane,
for too long residence time, other thermal degradation or monourethane, and also numerous compounds of higher molar
nonreversible reactions known for PU (free isocyanate groups masses identified as grafted di- or monourethanes. These latter
forming carbodiimide and carbon dioxide but also dissociation are the result of complex reactions between urethane bonds and
of the urethane group to amine, carbon dioxide, and olefin or isocyanates, which further reacted with dissociated alcohol, for
dissociation to secondary amine and carbon dioxide, formation example, ending in branched molecules. Comparing the two
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 Another proposal is to depolymerize thermoplastic or
experimental conditions, less allophanates and monourethanes thermosetting PU by the use of water, alcohols, or amines.
were formed. Glycolysis technology has been proposed to chemically
These results prove the possibility to create some cross-links depolymerize PU foams.147 The splitting of the polymer chains
through allophanate functions by adding a polyisocyanate to a occurs under continuous stirring and temperature control and
TPU by reactive extrusion. It has been applied to the with the help of a catalyst. Upon completion of the reaction
preparation of self-cross-linkable but still thermoplastic step, the recycled fluid is filtered and discharged. The reclaimed
materials.145 Poly(ethylene adipate) glycol is reacted with an polyol can be added to or mixed with original polyol to be used
excess of isocyanate (NCO/OH = 1.21), generating up to in spray foam applications, flexible foams, elastomers, and other
about 40% of the allophanate groups as cross-linking points, traditional PU applications without any loss of quality. This
while the other part forms only branching.146 Because of the process can be economically acceptable, but it requires further
lateral isocyanate groups, the resulting polymer can be easily development to introduce less contamination in the post-
cross-linked at ambient moisture. A scheme of the strategy used consumer material. Concerning this last remark, it can be said
is given in Scheme 27.145 that PU based on aliphatic diisocyanates are claimed as
This simple modification has already been used to improve nontoxic amine producers during the polyurethane degradation
the mechanical and thermal properties of commercial TPUs. process.
Details of this study are out of the scope of this review, but
basically, it is very important to maintain a nanostructure for 4. MODEL REVERSIBLE UREA/URETHANE BONDS:
the final material, which means the control of the competition THE CASE OF BLOCKED ISOCYANATES
between the chemical reactions and physical microorganization
of soft and hard phases. At the end, the modified and cross- 4.1. Introduction
linked TPU shows better mechanical behavior (creep) at Industrial products take advantage of the reversibility of
moderate temperatures (80−100 °C) and better thermome- isocyanate-based bonds by designing special derivatives of
chanical properties at high temperatures. Additionally the isocyanates that thermally dissociate to regenerate the reactive
chemical cross-links of the modified TPU are reversible, and it isocyanate function at a given temperature. Below this
can be still processed as a conventional thermoplastic temperature, the isocyanate is in a blocked form that decreases
elastomer. the isocyanate reactivity and toxicity. A seminal work reviewing
3.4. Reversibility as a Means of Recycling Polyurethanes blocked isocyanate systems was already done in the last
century.7,148,149 Later on, Wicks et al. published an exhaustive
Knowing that the urethane bond is unstable above 170 °C in review with over 1700 references that covered a broad range of
the solid and molten liquid states, it can be imagined that the industrial applications from 1980 to mid-2000.5,6 Since
chemical recycling of PU materials (thermosets or thermo- discrepancy was systematically found in the deblocking
plastics) can be effective and economical. The properties of temperatures, to the point that the relative order between
recycled granules can be easily readjusted during an extrusion general classes of blocking molecule is still difficult to assess
process. The recycling of PU has been proposed by other nowadays, these reviews attempted to present as many
methods. In the regrind technology, the obtained fines particles examples as possible, taken mainly from patent literature, to
of recycled PU foams (like in automotive seating) were mixed provide a general guidance for applications.
with fresh polyol. Because the solids are so fine, a slurry is Though other possibilities exist, blocked isocyanate is
obtained, and they can be used to replace only up to 12% of the generally described as an adduct containing a weak bond
polyols without affecting the quality of the new PU foam. formed by the reaction of isocyanate with a hydrogen active
During the foaming process, transreactions such as the ones compound. Since it is an equilibrium, this reaction tends to
described previously make the material homogeneous. regenerate the isocyanate group at elevated temperature
(elimination step). Then, the free isocyanate reacts with a order in blocked isocyanate (for instance, between an oxime
substrate containing nucleophile to form thermally more stable blocked isocyanate and an amine, see ref 150).
bonds (addition step). The overall reaction is summarized in On the opposite, supposing that the blocking molecule BH is
Scheme 28. more reactive toward isocyanate than the NuH leads to neglect
K2[NuH] > K−1[BH]. It is important to note that, in that case,
Scheme 28. (a) Blocking and Deblocking Reaction of no curing reaction occurs except if the blocking molecule is
Isocyanate and (b) Curing Reaction 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
Since the adduct is less (or even not) sensitive toward nucleophile molecule addition on the blocked isocyanate
nucleophilic molecules and in particular toward water, blocked followed by the blocking molecule elimination (as shown in
isocyanates make it possible to prepare a one-component Scheme 30) has been proven to apply to some systems where
reactive system with long pot life and lower toxicity and to the kinetics were specifically studied.
drastically reduce or even suppress solvent use.
4.2. Overall Mechanisms for Reactions of Blocked Scheme 30. Addition−Elimination Mechanism
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 Because the initial stage corresponds to the nucleophile
temperature, the adduct splits off to regenerate the free attack on the blocked isocyanate, this mechanism can be
isocyanate group (elimination step), which in turns reacts with thought of as chemical deblocking. The rate of cured material
a nucleophilic substrate (addition step). This elimination− formation is (eq 7)
addition mechanism is shown in Scheme 29.
K3[NuH][BI]
rate =
Scheme 29. Elimination−Addition Mechanism 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
Considering that the rate constant K−2 is negligible, the final elimination−addition mechanism is prominent.151,152 Further-
product formation, under steady-state hypothesis, is written as more, the kinetic models presented above do not consider
in eq 4: many effects such as secondary reactions taking place in the
whole process (allophanate, biuret, isocyanurate, etc.).153 To
K1K 2[NuH][BI]
rate = take into account these limitations, it would be advisable to use
K −1[BH] + K 2[NuH] (4) a more general model such as model-fitting approaches or even
where [NuH], [BI], and [BH] stand for the concentration of a model-free kinetic approach,154 of which details are given in
nucleophile, blocked isocyanate, and blocking group, respec- Supporting Information.
tively. The eq 4 shows two limiting cases given below. 4.3. Recording the Deblocking Reaction
If the curing reaction is much faster than the blocking Because of the discrepancy between the analytical techniques
reaction, K2[NuH] ≫ K−1[BH], then, the rate is independent and for the same technique, between the sample preparations
of the nucleophile content (eq 5): and the analytical methods, comparison between two
rate = K1[BI] deblocking temperatures from distinct publications is tricky, if
(5)
not impossible. For instance, whatever the chosen analytical
This situation occurs for instance in the case of blocked method, the dissociation temperature can be measured during
isocyanate reacting with an amine. The reaction is described by the pure dissociation reaction (without a coreactant) or during
an overall first-order reaction, zero-order in amine and first- a reaction (with coreactant), which by competing with the
blocking equilibrium decreases the apparent dissociation The onset temperature for the different systems is taken as
temperature. This section aims at bringing an overview of the the temperature at which the rate of dissociation is not nil
different aspects to take into account while measuring anymore. Caprolactam 24 blocked isocyanate 21 regenerates a
deblocking temperature. The most traditional techniques are free NCO group more slowly and at higher temperature (T =
described here, e.g. spectroscopic techniques (FTIR, NMR...), 180 °C) than the other systems due to its weak activation
thermal ones (DSC, TGA) or titration methods. parameters (Figure 7). Methyl t-butyl ketoxime 23 blocked
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, Figure 7. Dissociation rate constants of blocked isocyanate complexes
in presence of amine as a function of temperature calculated from
reaction occurs, albeit at various rates. The exponential factor activation parameters measured in toluene (data from ref 150).
(A) is increased by a temperature increase, and for a given
temperature variation, the higher the activation energy (Ea), the cyclohexylisocyanate (T = 200 °C) presents superior activation
more important the change. To get an accentuated threshold energy, and global reaction rate is rapidly multiplied by a
temperature between blocked and free isocyanate, one should temperature increase. Tetramethylcyclobutanone ketoxime 22
increase the activation energy. However a compromise is blocked cyclohexylisocyanate (T = 240 °C), the highest
necessary, because for economical reasons elevated dissociation activation energy system, is extremely sensitive to the
temperature does not comply with industrial requirements. temperature; the high pre-exponential factor offsets the low
Moreover, large activation energy makes the unblocking value of the exponential factor.
reaction too slow unless A is large enough to counteract Ea. 4.3.2. Techniques. FTIR has been successfully employed
Because the pre-exponential factor is a measurement of the to characterize adducts and their minimum deblocking
effects of both the internal degrees of freedom of the reacting temperatures. The NCO group strongly absorbs between
species and the necessary redistribution of that energy so that 2250 and 2270 cm−1, the disappearance of this band indicates
the reaction ensues, the ideal reaction should have a large the completion of the blocking reaction (Table 8). The CO
positive entropy change, such as the cleavage of a ring system to bond frequencies can be shifted to lower vibration frequencies
a ring-opened system, to take advantage of the temperature depending on the hydrogen bonding.155 Typically, the
effect. variations of absorbance are normalized to the C−H stretching
In practical applications, it is however possible to generate a at 2946 cm−1 to compensate the thickness changes during the
“deblocking temperature” according to the onset temperature reaction course. Isocyanate conversion is then calculated as
of dissociation. As an example, different oxime- and follows (eq 9).
caprolactam-blocked isocyanates were heated in toluene in
the presence of amine (1.2−6 equiv relative to blocked (ANCO /A ref )t
α=1−
isocyanate; Scheme 31), and aliquots were analyzed by gas (ANCO /A ref )t = 0 (9)
chromatography to record the rate of appearance of urea.150
Although it is less employed than FTIR, UV spectroscopy
can be used to determine the NCO content. The n−π*
Scheme 31
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
Table 8. IR Band Frequency of Common Groups Involved in the Blocking or Curing Reactions
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).
Figure 8. DSC thermogram of the melting and the dissociation of TDI The isocyanate content can also be quantitatively determined
dimer. Reprinted with permission from ref 73. Copyright 1996 John through titration. Aliquots are withdrawn from the flask and
Wiley & Sons. quenched with di-n-butylamine. The isocyanate content is
determined by back-titration with an acid, such as HCl or
the blocking molecule−isocyanate dissociation at 185 °C. H2SO4 and a color indicator (methyl red11 or bromocresol
Above 200 °C, possible degradations of isocyanate group and green156). Titration method via amine quenching is widespread
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.

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 the temperature range or in a pan with a hole to prevent the
to selective degradation with butylamine.95 Indeed, Furukawa blocking molecule evaporation from blowing up the cell. In the
and co-workers157 showed that aliphatic primary amine open pan, the blocking molecule evaporation will pull the
selectively degrades allophanate and biuret and left urethane reaction toward free isocyanate formation. TGA measurements
and disubstituted urea unmodified. are evidently performed in an open pan. Because this method is
Gas chromatography may also be used either to confirm the based on blocking molecule evaporation, TGA is inappropriate
elimination−addition mechanism by recording the presence of for blocking molecule possessing a boiling point above the
dissociated reactants158 or to check the kinetic data determined deblocking temperature. Concerning infrared analyses, the
with other techniques.150,159 sample can be analyzed in the solid phase as a KBr pellet or in
4.2.3. Operating Conditions. While most of patents claim the liquid phase (the blocked isocyanate solution is placed
a precise “dissociation” or “deblocking” temperature, one between two KBr plates73,161 or on a single KBr plate162). As an
should keep in mind that the “deblocking temperature” does example, the influence of blocking molecule evaporation was
not have any physical meaning; not only can it be measured at perfectly shown by Wicks (Figure 10). Moreover, when the
different stages of the reaction, but it also depends on the measurement cell containing the KBr pellet is evacuated to
recorded physical parameter and the technique sensitivity to remove disturbing air components such as CO2 and water, the
detect a certain extent of the reaction. In other words, since the deblocking reaction is also favored.162
reaction is equilibrated, the measurement conditions or 4.3.4. Presence of Chemical Additives. In addition to
experimental set up greatly influence that temperature. inherent discrepancies due to the numerous techniques and
First, isothermal or nonisothermal conditions give clearly their experimental setups, the presence of solvent or coreactant
diverging results in the extent of reaction. Isocyanate groups are also induces strong disparities in the deblocking temperature
only partly regenerated depending on the temperature. For for a particular system. Contrary to DSC and TGA, NMR
nonisothermal measurement, the extent of reaction increases techniques obviously require working in a solvent. Only IR and
with temperature until potential degradation occurs (Figure UV are flexible enough to tolerate measurements in the
9a). While for isothermal measurements, equilibrium is rapidly presence or in the absence of solvent. The solvent choice affects
reached (Figure 9b) whereas relatively few isocyanate groups the deblocking reaction. As already discussed (vide supra), the
are freed. The reaction extent is far below the one of the mechanism of isocyanate addition on a nucleophile is not
nonisothermal experiment. completely elucidated, but strong evidence supports the idea
Second, the equilibrium reaction can be driven toward free that the solvent greatly influences the kinetics of polyurethane
isocyanate (via the deblocking reaction) through the synthesis. If blocked isocyanate should be synthesized in an
elimination of released blocking molecules. Evaporation turns apolar solvent, the deblocking reaction is favored by strong
out to be a critical point that is influenced by the measurement nucleophilic solvent.163
techniques. In DSC, the sample is analyzed either in a sealed Moreover, the equilibrated deblocking reaction is also
pan if the boiling point of the blocking molecule is higher than assisted by all nucleophiles present. For instance, the NMR
signals of 3,5-dimethylpyrazole 25 (DMP) blocked isocyanate decarboxylates into an amine and carbon dioxide. CO2 is
recorded as a function of temperature demonstrate that first the extracted with a carbon dioxide free, dry nitrogen purge and
isocyanate group is regenerated, and then it reacts with water to made to react with sodium hydroxide165 or barium hydroxide.43
form a urea bond and CO2 (Scheme 32).164 But, as soon as The minimum temperature at which detectable turbidity from
water is totally consumed, the free isocyanate content reaches a carbonate precipitation appears is taken as the minimum
constant value (Figure 11). 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
Figure 11. NMR signal integrations and percentage of free blocking
molecule, expressed as I5.8ppm/(I6.2ppm + I5.8ppm), and various
derivatives.
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

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
4.4.2. Amines. Primary amines react so fast with isocyanate amine-blocked isocyanates.175 Oxime-blocked isocyanates are
that the counter-equilibrium reaction cannot be seen (the easily synthesized at moderate temperature in THF with
temperature of degradation of the complex is below the dibutyltin dilaurate as catalyst.118 Levine et al.156,167 studied the
deblocking temperature). Secondary amines (e.g., piperidine benzophenone oxime blocked TDI 44 derivative deblocking in
derivatives) are very reactive nucleophilic molecules that react presence of dibutylamine in toluene. They reported blocking
easily with isocyanate without external catalysis. Because molecule elimination as the first and rate-determining step
reactivity increases with the blocking molecule nucleophilicity, followed by the NuH molecule addition 45 (Scheme 39).
the blocking reaction rate of isocyanates with amines is always The mechanism, similar to the deblocking reaction of amine-
higher than with alcohol. This high reactivity of isocyanate blocked isocyanate, leads to the following observations: (i) the
toward amines should induce a very high deblocking temper- intramolecular activated complex decreases the deblocking
ature of the adduct. However, in the case of aromatic amines temperature, compared with alcohol-blocked isocyanate; (ii)
(e.g., aniline), an autocatalytic effect is observed; the tertiary the reaction is favored by all the electron-releasing substituents
nitrogen atom of the blocking molecule forms a four-centered X on the blocking molecule, contrary to the alcohol-blocked
complex through an intramolecular hydrogen bond with the isocyanates; these substituents increase the base strength of the
urea hydrogen (Scheme 37). This transition state, proven by nitrogen electron lone pair as presented in Scheme 40 and
Figure 15.
Scheme 37. Formation of a Four-Centered Transition States 4.4.4. Other N-Based Compounds: Amides, Imides
during Deblocking Reaction of Aniline−MDI Adduct 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
NMR,173 weakens the bond between the carbonyl carbon and molecule elimination goes through a five-center complex
the nitrogen atom of the blocking molecule. The N−H similarly to oximes (Scheme 42). Muehlebach measured the
breaking is thus the rate-determining step of the deblocking reactivity of these pyrazole-blocked isocyanates mixed with
reaction. trifunctional amine-terminated prepolymer (Jeffamine T403)
Nasar158 and Gnanarajan174 studied substituted aromatic and reported the following reactivity order: 63 > 62 > 61. The
secondary amine as blocking molecule (37−41) for TDI electron-releasing substituents decrease the deblocking temper-
(Scheme 38). When the deblocking reaction is carried out in ature (Scheme 42).169 Blocked MDI was systematically found
presence of hydroxyl-terminated polybutadiene (42, Scheme to be more reactive than blocked HDI. Other compounds
38), the recording through gel time measurements at 180 °C containing at least two nitrogen atoms, such as 1,2,4-triazole 60
gave the following reactivity order: 37 > 38 > 39.158 Similar and imidazole 57 have been proven to form the same five-
compounds were heated with pyromellitic dianhydride (43, center complex facilitating the deprotonation step during the
Scheme 38) by TGA and in that case, the deblocking deblocking reaction.177
temperature increased as 40 > 37 > 41.174 As predicted by
4.5. Improving Industrial Systems
the proposed mechanism (Scheme 37), the electron-with-
drawing groups (phenyl, naphthyl group attached on the 4.5.1. Conventional Systems. The most used blocking
nitrogen atom, or nitro group on the aromatic ring) drain the molecule in coating and painting industries is ε-caprolactam
electrons from the nitrogen atom hindering the hydrogen (Scheme 43). However, these blocked isocyanate-powder
abstraction. Conversely, the electron-releasing groups such as coatings have to be deblocked at rather high temperature,
methyl and nitro group strengthen the electron density on and they release blocking agents during the hardening process
nitrogen and so enhance the autocatalytic effect. that are undesired both ecologically and economically. A low
4.4.3. Oximes. The third widespread blocking molecule is boiling point compound facilitates the deblocking reaction and
oxime type compounds for which the deblocking reaction acts as a solvent to level off the coating during the cross-linking
follows a similar deblocking mechanism to the one reported for reaction. However, this type of compound brings potential
Scheme 38. Substituted Aromatic Secondary Amines Used To Block TDI (left) and Chemical Additives Used as Coreactant
during the Deblocking Reaction (right)

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:
Scheme 43. ε-Caprolactam-Blocked Trimer of (A) Isophorone Diisocyanate and (B) Hexamethylene Diisocyanate
after unblocking, an intramolecular cyclization reaction from a mixture of isocyanate prepolymer blocked with N-
converts the free oxime 67 into a non-nucleophilic (unreactive) (11′-dimethyl-3-oxobutyl) acrylamide oxime, chain extender,
product 3-methylisoxazol-5-one 68 (Scheme 44). vinyl monomers, and catalysts.186,187 Vinyl isocyanate mono-
mers such as isocyanate ethyl methacrylate or m-isopropenyl-
Scheme 44. Deblocking and Cyclization Reactions of Oxime benzyl isocyanate are also available and were copolymerized
of Ethyl Acetoacetate Blocked Isocyanate 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
The insolubility of the blocked isocyanate and the curing polyurethane acrylates (PUA) are very attractive materials that
molecule at ambient temperature and the slow endothermic combine fairly good mechanical performances (flexibility,
dissolution process at higher temperature enable extension of abrasion resistance, and toughness), high chemical resistance,
the stability, as shown for the mixture of pyrazole-blocked and adhesion properties. For their synthesis, the chain extender
isocyanate and amine-terminated prepolymer.169 To increase of the second step in Scheme 24 is replaced by hydroxyl ethyl
the storage stability, some polyurethane formulations include (meth)acrylate, HE(M)A leading to α−ω (meth)acrylates,
blocked amines as coreactants in addition to blocked which are able to react by free radical polymerization. But up to
isocyanates. Suitable amines are ketimines and enamines, now, due to the presence of inhomogeneities in cross-linking
which react with moisture to regenerate amine functions.182 density, the mechanical properties such as elongation at break
Finally, an interesting study showed that oxime-blocked are less than the ones of the corresponding PU.189 Very
isocyanates induce cross-linking by generating amines and recently, some authors proposed to functionalize the blocking
hydrazines under UV radiation.183,184 agent with self-reacting groups, such as trimethoxysilane or
4.5.3. Dual Networks. Tassel et al.185 synthesized a new (meth)acrylate functions, to promote an anchoring of the
blocking agent, 2-formyloxyethyl methacrylate (69, Scheme blocking molecules during the curing.102
45), bearing two functions: a labile hydrogen and a 4.5.4. Blocking Reaction of Amine Groups. To increase
methacrylate double bond, which can homopolymerize leading the pot-life of cast molding formulations, another strategy used
to polyurethane and polyacrylate interpenetrated networks. In masked amines, such as methylene dianiline (MDA) sodium
the same way, polyurethane−urea/polyvinyl simultaneous chloride complex dispersed in dioctyl phthalate. MDA is
interpenetrating polymer networks were prepared starting commonly used to cure urethane prepolymers based on
diisocyanate, TDI, or MDI and polyether polyols. At room
Scheme 45. Blocking Agent Acting As a Comonomer after temperature, the MDA/NaCl salt is virtually nonreactive,
Deblocking Reaction 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-
tions.193 To lower the reaction temperature, this reaction is lation is commonly used for synthesizing polyurethane from
generally promoted by tertiary amines and imidazoles. A way to polyol and urethane diol.197 Other strategies consist in
improve the latency exploits blocked isocyanates to generate in preparing precursors without facing the hazards of phosgene
situ amines (Scheme 46). Upon heating, substituted ureas 70 handling. Here, we have classified these new systems according
to whether they release isocyanate during the polymerization.
Scheme 46. In situ Generation of Catalyst for Dicyandiamide One should however never forget that, due to the reversibility
Epoxy Reaction 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
dissociate into isocyanate 72 and dimethylamine 71. The latter reaction of the maleic anhydride with (substituted) urea(s) and
reacts with an epoxy group to give a tertiary amine 73, which cyclization with water release (Scheme 51).200
catalyzes the reaction of dicyandiamide with epoxy groups. The Such derivatives were shown to deblock at relatively low
isocyanate moiety reacts with another epoxy unit, forming an temperature (about 100 °C in DMF) and react readily with
1,3-oxazolidin-2-one.193 A similar approach was used to primary alcohols to generate N-carbanylmaleamates. Other
generate a tertiary amine catalyst from blocked isocyanate to authors reported succcinimide or maleimide derivatives of HDI
promote the epoxy isocyanate reaction.106 in the same range of temperature (110 and 130 °C,
4.6.2. Urethane Promoting Ring-Opening Polymer- respectively).176,201
ization of 1,3-Benzoxazine. 1,3-Benzoxazines are cyclic
N,O-acetal-type monomers that polymerize by ring-opening at 5.2. Phosgene-Free Isocyanate-Free Precursors
T > 180 °C without catalyst to give the corresponding phenolic 5.2.1. Carboxamide/Alcohol Polycondensation. From
or phenoxy polymers (Scheme 47).194,195 Lower curing tetramethylene urea and phenyl chloroformate, Ubagh
temperature is highly needed, and attempts to reduce the synthesized N-(hydroxyalkyl)-2-oxo-1,3-diazepan-1-carboxa-
curing temperature have been carried out, with different mide 81 as a polycondensation monomer to lead to
degrees of success, by using various catalysts, such as acidic polyurethane.202,203 Below 100 °C, the equilibrium (Scheme
or basic compounds as well as metal-containing catalysts. 52) is completely shifted to the left; and thus, the O-phenyl
Among them, phenol has proven to be efficient, and urethane urethane is considered as an activated urethane and the 1,3-
reversibility has been used to create in situ the active molecule. diazepan-2-one ring as an intramolecular blocked isocyanate. In
Phenol activates benzoxazine by protonation, the produced the presence of amino alcohol, the urea ring remains intact
species undergoes a ring-opening reaction. Then, the imminium because the nucleophilic amino group reacts selectively with the
moiety reacts readily and irreversibly with phenoxides (Scheme electrophilic carbon of the O-phenyl group. Then, this
48a). Moreover, Sudo196 claimed that the isocyanate moiety monomer is polymerized in the presence of catalyst such as
also induces polymerization by stabilizing the propagating DABCO at 150 °C to form poly(urea-urethane) 82 (Scheme
zwitterionic species and avoiding suppression of the reverse 53).
reaction possibility (Scheme 48b). Another reaction involves carbonylbiscaprolactam 83 (CBC,
Allinco from DSM) with a nucleophile to provide caprolactam-
Scheme 47. Monomer N-Methylbenzoxazine 75 and blocked diisocyanate as an isocyanate- and phosgene-free
Phenolic and Phenoxy Structures of Poly(benzoxazine) 76 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
5. “NEW” TRENDS: TOWARD secondary alcohols and phenols react with CBC by ring-
NON-ISOCYANATE-BASED POLYURETHANES opening and ring elimination depending on the conditions
Recently, several reactions, essentially based on transcarbamoy- (temperature and catalyst) to afford carbonate, urea ester, and
lation, attracted researchers interest due to the possibility to urethanes without isocyanate intermediates. Metal alcoholate
form polyurethanes without isocyanate monomers in the catalysts favor the RO pathway.
formulations, which complies with the new environment and 5.2.2. Dicarbonate/Amine Condensation. A promising
safety requirements. Nowadays industrially, the transcarbamoy- approach toward phosgene-free polyurethane is the carbonate−
Scheme 48. Mechanism for the Promoting Effect of Urethanes on the Polymerization of Benzoxazine
Scheme 49. Curtius Rearrangement Scheme 51. Formation of Maleimide-Blocked Isocyanate by

a Phosgene-Free Reaction and Further Deblocking
Reaction199
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 5.2.3. The Specific Case of Cyclocarbonate/Amine
as the organic superbase guanidine 1,5,7-triazabicyclododecene Addition. As early as 1957, Groszos et al.212 patented PU
(TBD, see Figure 17), increase the rate and the selectivity of preparation using a non-isocyanate route based on the reaction
aliphatic amine−carbonate reaction.209 Urethane bonds are between cyclocarbonate and polyamine urea. Recently, this
formed by dicarbonate−aliphatic or aromatic amine reaction synthesis strategy has attracted more and more interest since no
catalyzed by bases such as sodium methoxide at 90 °C. The volatile compounds are released during the reaction. Cyclic bio-
best results for the carboxymethylation of aniline with based alkylenes are reactive intermediates known for more than
dimethylcarbonate in terms of selectivity (urethane/N-methyl 50 years,213 but since the 1990s, seminal work has been done to
derivative) are achieved with zinc or tin catalysts.210 explore the high reactivity of five-membered alkylene carbonate.
Uncatalyzed urethane formation can also be performed under Primary or secondary amine has long been shown to open the
high pressure (8 kbar).211 Very recently, Tang et al. showed cyclocarbonate at room temperature without catalyst.213−215
that a superbase catalyst conventionally used in ring-opening Using diamine and bicyclocarbonate allows synthesis of original
polymerization (ROP) of various cyclic monomers (including polymers that could not be obtained by common isocyanate−
cyclocarbonates), namely, TBD, promotes transurethanization alcohol addition, for instance, amorphous polyhydroxyur-
reaction between dicarbamates and diamine functionalized ethane.216 A very recent review proposes practical aspects of
molecules to generate bio-based, isocyanate-free polyurethane NIPU preparation and applications.217
of similar structuration and mechanical properties as conven- 5.2.3.1. Synthesis of Pentacyclocarbonate. Several meth-
tional TPUs.209 ods were used to synthesize five-membered cyclic carbonates as
Scheme 50. Formation of Isocyanate from Amine and Carbodiimidazole199

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
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
Figure 17. Synthesis of isocyanate-free polyurethane via the
transurethanization between dicarbamates and diamino-terminated remains the addition of carbon dioxide on cyclic ethers,227−229
polymers catalyzed by organic superbase guanidine 1,5,7-triazabicy- for which the catalysts and synthetic methods were nicely
clododecene. described by Daresbourg.230
Scheme 56. Synthetic Routes to Five-Membered Cyclocarbonates
Various techniques are likely available to synthesize with carbon dioxide.239 Note that a tristar poly(ethylene glycol)
dicyclocarbonates: (i) reaction of diglycidyl ether of bisphenol terminated by cyclocarbonate 92 is commercialized by the
A (BADGE) and CO2 in presence of sodium iodide and company Macromer Ltd., Russia, under the trade name
triphenylphosphane at 100 °C;231 (ii) transesterification of Laprolate L.803 (Scheme 58).240
polyols such as 3,4-O-isopropylidene-D-mannitol with ethylene
carbonate with yields around 65%;232 (iii) highly selective Scheme 58. Chemical Structure of Laprolate L.803
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
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-
lead to different cyclocarbonates, symmetric or asymmet- opening reaction were found. The secondary hydroxyl
ric.216,236 The same product was also obtained by Steblyanko containing compound (96 in Scheme 59) predominates in
from CO2 and diglycidyl terephthalate, previously synthesized the medium (96/95 = 4.4:1); theoretical calculations confirmed
from 2-oxiranylmethanol and terephthaloyl dichloride.237 Very the stability of 96 (ΔHf = −9.77 kcal/mol) over 97 (ΔHf =
recently, this method, in combination with ROP of the same −8.10 kcal/mol).
cyclocarbonate, was applied to prepare cyclocarbonate-termi- The ratio between secondary and primary hydroxyl
nated polycarbonates.238 compound is determined by substituents introduced at the α-
Carbon dioxide was also added to other glycidyl ethers to methylene of the bicyclocarbonate 98: a more electron-
synthesize polyfunctional cyclocarbonates.227 Koen-Raadt withdrawing group draws the reaction toward secondary
reported the preparation of tris(2-oxo-1,3-dioxolanyl-4- hydroxyl containing product 99 (Scheme 60).242 Chemical
methyl)isocyanurate by reaction of triglycidyl isocyanurate structure and molar mass govern the amine reactivity:
Scheme 59. Ring-Opening Model Reaction of Cyclocarbonate by Amine237
aromaticity, α- and β-electron-withdrawing substituents, and mass of the molecules increases; catalyst or higher temperature
high molar mass lower the reactivity.240 are then required. Typically with diethylene triamine (DETA),
8 days at room temperature is required for a quantitative
Scheme 60. Polyhydroxyurethane Synthesis 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
5.2.3.2.2. Reactivity. Kotzev240 studied in 2004 the reaction °C and 10 times more at 70 °C, than C5 while reacting them
between the Laprolate and various amines, which structures are with 4,9-dioxadodecane-1,12-diamine. Guillaume et al. have
given in Scheme 61. The reactivity decrease for bulk reaction is prepared various cyclocarbonates in C7 starting from levunilic
explained by the amine concentration dropping off as the molar and itaconic acids but engaged these molecules exclusively in
Scheme 61. Scale of Reactivity of Various Amines toward a Model Pentacyclocarbonate

ring-opening metathesis polymerization (ROMP) to prepare 5.3. Conclusion

polycarbonates.243 The carbonate/amine reaction produces polyurethane materials
5.2.3.3. Polymer Synthesis and Properties. Kihara and Endo overcoming the use of toxic isocyanates. However, catalyst
synthesized linear polyhydroxyurethanes from reaction between addition is required to enhance the reaction rate and the
diamines and dicyclocarbonates obtained from epoxy mole- selectivity. Cyclocarbonates, especially five-membered cyclo-
cules.231 Burgel and Fedtke also prepared linear polyhydroxyur- carbonates, drew additional interest compared with carbonates
ethanes from dicyclocarbonates and diamines.244 Finally, Lee et since no volatile compounds are released during the polymer
al.245 designed new linear polyhydroxyurethanes by poly- formation. The obtained products from these cyclic carbonates
addition between dicyclocarbonates and various amines. bear a hydroxyl group at the β-carbon atom of the urethane
Dicyclocarbonates were obtained from bisphenol S of diglycidyl moiety, which brings improved properties such as pore-free PU.
ether monomer and carbon dioxide.245 The work was also The thermal stability of nonisocyanate PU is also claimed to be
extended to polymers functionalized with bicyclocarbonate, improved compared with conventional PU. However, this
which react with polyamines to yield cross-linked polyhydrox- parameter has only been checked through thermogravimetric
yurethanes.246 Various types of catalysts such as acid (glacial analyses; the molar mass stability when heating should also be
acid acetic, methanesulfonic acid), base (triethylamine, verified. Indeed, the reversibility of the β-hydroxyurethane
piperazine, tetrabutyl ammonium bromide), or metal (metatin bond would produce isocyanate and an excess of OH groups,
type catalyst) increase the reaction rate.240 which upon recondensation could induce a strong molar mass
Because the molar mass obtained by this process is usually decrease. An opposite possibility would be exclusive exchange
below 10,000 g/mol and ultimately less than 20,000 g/mol, this reactions without depolymerization; if that occurs, it would be
reaction is essentially used to synthesize prepolymer247 or to possible to prepare malleable materials from permanent organic
cross-link cyclocarbonate bearing polymer248 or for chain networks, as proposed recently for conventional epoxy−acide
extension of preformed polymers. The Tg of this material chemistry.256
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 6. FINAL CONCLUSION: ISOCYANATE-FREE VERSUS
and amines resulting in pore-free polyurethanes. The influence NONISOCYANATE SOLUTIONS IN VIEW OF AN
of hydroxyl functions on thermal properties of poly- INDUSTRIAL CONTEXT
(hydroxyurethane) (PHU) is remarkable. Indeed, the intra- As stated in the Introduction, urethane/urea bonds have proven
molecular hydrogen bonding between the alcohol and urethane their versatility. One clear advantage of the NCO chemistry is
functions (Scheme 62) seems to be responsible for lowering the high reactivity of this function, even at room temperature.
This allows fast curing of cast-molded materials or coatings, as
Scheme 62. Hydrogen Bonding in a Hydroxyurethane well as a facility to prepare solid foam (chemical reaction rate
Function249 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
the susceptibility of the backbone to hydrolysis resulting in then curing requires high temperature to deblock the chains.
substantial increase of the chemical resistance.249 The chemical Another disadvantage of blocked isocyanates is the loss of
resistance of materials containing intramolecular hydrogen (high) reactivity of the −NCO groups, as we have seen in this
bonds is 1.5−2 times superior to materials with a similar review. This approach is then particularly preferred when one is
chemical structure without such bonds.250 Tomita has shown seeking a one-pot, slow polymerization process, as in coatings
that the water absorption percentages and thermal decom- for instance. One solution to enhance the reactivity consists in
position temperatures of the film cast from synthesized PHU preparing prepolymers, which react by transcarbamoylation
were reduced by 30% and from 32 to 88 °C higher, with polyols to cross-link the materials; such a trick is regularly
respectively, than those from commercial PU.223−225 used in industry.
5.2.3.4. Bio-Based Materials from this Chemistry. As a A major problem of concern in isocyanate chemistry is the
current trend, researchers tend to go further by producing high toxicity of the precursors, that is, diisocyanates. Upon the
nonisocyanate PU from renewable resources. In that frame, most conventional formulation available nowadays, the industry
vegetable oils as feedstocks for polymeric materials attract proposes formulations where telechelic isocyanate prepolymers
are prepared beforehand by reaction of a diol oligomer with an
increasing attention, because they tend to be very inexpensive
excess of diisocyanate and distillation of the remaining small
and available in large quantities. They are used either as a
reactant. The polyurethane materials are then prepared by
source of polyol251 or as polycyclocarbonate obtained from adding a short diol or upon action of water in a one-pot
epoxidized oils.252,253 As an example, Boyer et al.254 synthesized formulation. This process, called “diisocyanate-free polyur-
internal carbonated fatty acid diester and terminal carbonated ethane” technology, allows the same reactivity as in the
fatty acid diester from sunflower oil. Interestingly, carbonate conventional diisocyanate chemistry to be retained, while the
and dialkyl carbonates can be prepared from bio-based recent regulation rules, such as REACh, which requires
products, such as dianhydrohexitol,255 leading to green, discarding MDI or TDI hazardous molecules, are respected.
biosourced polyurethane. Still, the presence of isocyanate functions at the end of
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

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
Etienne Delebecq was born in Lille, France, in 1984. He received his co-workers now synthesize bio-based materials such as epoxy resins
B.S. degree in Chemistry in 2005 from Ecole Nationale Supérieure de obtained from natural polyphenols (flavonoids, gallic acid and
Chimie de Montpellier (ENSCM, France). In 2008, he received a M.S. derivatives, and cardanol) and isocyanate-free polyurethanes through
degree from Université Montpellier and a Ingénieur Chimiste degree the carbonate−amine reaction. He has supervised more than 100
from ENSCM. In 2011, he earned his Ph.D. in Material Science at Ph.D. students, published 2 books, more than 500 peer-reviewed
ENSCM, working under the direction of Dr. François Ganachaud. His articles, and 25 reviews or chapters of books. He is the coinventor of
research activities are focused on the improvement of thermal and more than 120 patents.

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
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Review

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

3.2.1. Bulk Cross-Linked PUs by Cast Molding

Surprisingly, the electron density distribution, as well as the

Scheme 4. General Mechanism of Isocyanate/Nucleophile Reaction

Scheme 8. Possible Degradation Reactions of Urethane Bond

Scheme 9. Transurethanization Reaction

Exchange reactions have been evidenced by heating up a

Trimerization of alkyl and aryl isocyanates is promoted by

Scheme 13. Carbodiimide Formation Starting from

Scheme 16. Transreactions between Uretdione and Alcohol

allophanate and isocyanurate formation; nevertheless alcohol is

Scheme 17. Allophanate Formation from Phenyl Isocyanate 2 and Ethylcarbanilate 3

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

Scheme 19. Epoxy Isocyanate Reactions

trimerization, but not the oxazolidone formation, while tertiary

Adapted from ref 107.

formation of low molar mass allophanate species.117 High

Scheme 24. Schematic Synthesis of Linear Segmented Polyurethane

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

Scheme 25. Model Reactions Involving Isocyanate Group in Polyurethane Foams

k = A e−Ea /(RT ) (8)

TDI evaporation occur. A weight loss of 95% was recorded

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

Most of the works measured the deblocking reaction in the

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

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

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

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

Scheme 40. Substituted Benzophenone Oxime

Figure 16. Deblocking temperature of amide− and imidazole−

Scheme 42. Deblocking Reaction of Pyrazole Blocked

Scheme 49. Curtius Rearrangement Scheme 51. Formation of Maleimide-Blocked Isocyanate by

amine reaction that leads to β-hydroxyurethane. Depending on

Scheme 50. Formation of Isocyanate from Amine and Carbodiimidazole199

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

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

summarized in Scheme 56. These include the reaction between

Scheme 56. Synthetic Routes to Five-Membered Cyclocarbonates

Scheme 57. Synthesis of Dicyclocarbonate Using Glycerin

5.2.3.2. Cyclocarbonate/Amine Reaction. 5.2.3.2.1. Iso-

Scheme 59. Ring-Opening Model Reaction of Cyclocarbonate by Amine237

Scheme 61. Scale of Reactivity of Various Amines toward a Model Pentacyclocarbonate

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

ring-opening metathesis polymerization (ROMP) to prepare 5.3. Conclusion

Bernard Boutevin earned his Chemical Engineering degree from the

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

MDA methylene dianiline

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

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

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

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

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

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