Nanostructured Hybrid Nonisocyanate

Polyurethane Coatings
Processes and materials that contribute to negative environmental effects are under serious
revision. Now alternative, ecologically safer solutions are demanded. Cyclocarbonates are a
relatively new class of compounds attracting research interest due to their potential use in the
preparations of "green," porous-free and moisture-insensitive polyurethanes. Cyclocarbonates
can be synthesized from corresponding epoxy precursors. Network or linear non-isocyanatebased polyurethanes can be formed from the reaction of cyclocarbonate resins and amines.12,14-17,22

No volatile or non-volatile by-products are produced via this reaction, resulting in porous-free
polyurethanes and an intermolecular hydrogen bond (Figure 1) that seems to be responsible for
lowering the susceptibility of the backbone to hydrolysis. This results in a substantial increase of
the chemical resistance.
Polyurethanes have an inherent weakness because of their molecular composition. Within their
polymer structure are hydrolytically unstable bonds, making the material vulnerable to
environmental degradation. By modifying the structure of the polymer, a new and promising
method of raising hydrolytic stability is introduced and readily displayed in nonisocyanate
polyurethane - a modified polyurethane material with lower permeability, increased resistance
properties and safe fabrication processes.
Network nonisocyanate polyurethanes are formed from the reaction between cyclocarbonate
oligomers and primary aliphatic amine oligomers.3 By using this reaction, an intermolecular
hydrogen bond is formed through the hydroxyl group at the b-carbon atom of the polyurethane
chain, as illustrated in Figure 1.

The Main Problem of Polyurethanes

The application of polyurethane materials (plastics, synthetic rubbers, foams, paint, varnishes
and adhesives) is increasing more than other kinds of thermosetting polymeric materials. While
their mechanical properties are sufficiently utilized, conventional monolithic polyurethanes are
porous and have poor hydrolytic stability and insufficient permeability. The involvement of toxic
components, such as isocyanates, in their fabrication process may render production extremely
toxic and dangerous.3
People exposed to isocyanates can develop a range of short-term health problems. More
seriously, isocyanate exposure can lead to long-term asthma and dermatitis if individuals
become sensitized. Sensitization is a condition in which breathing or skin conditions can return
with increasing severity upon any further exposure to the original sensitizing agent or similar
substances, even at very low exposures.18
The lethal concentration of MXDA (the most toxic amine used for manufacturing nonisocyanate
polyurethanes) is 700 ppm/hour; MDI (the most used polyisocyanate) is 178 mm/m3. This means
that the LC50 for MXDA is less than the LC50 for MDI by 20-40 times. The lowest published toxic
concentration of MDI that can lead to an increased immune response is 130 ppb/30 min for
humans.

Cyclocarbonate Oligomer Synthesis

Basic cyclocarbonate oligomers are formed by bubbling carbon dioxide through epoxy liquid
oligomers in the presence of a catalyst, and by interacting oligomeric chlorohydrin ethers with
carbonates of alkaline metals or oligomeric polyols with an ester (chloride) of carbonic
acid.3,20,22
The authors have studied the reaction of aromatic diamines with cyclocarbonate and epoxy
groups. It was found that up to 150 C, aromatic amines do not react with cyclocarbonates.21 In
a prior publication, the authors described a new synthesis method for advanced

cyclocarbonates.8 And one of the best constructions of a reactor for the gas-liquid interaction is
also described in a prior publication.7 Due to the holes in the stirrer, CO2 is involved intensively
in the liquid-gas reaction.
The main syntheses of cyclocarbonates are given by Clements.23 Multi-alkylene carbonates are
prepared from epoxy resins via CO2 insertion.23 An example is the insertion of the 3 mol of CO2
into Heloxy Modifier 84 (Shell), a trifunctional epoxy-terminated polyoxypropylene based on
glycerin. The result is the trifunctional alkylene carbonate shown in Figure 2.
As with other cyclic carbonates, these and similar materials can be further reacted with amines to
yield novel polyurethanes. Researches at Fiber-Cote have reacted this material with
isophoronediamine (IPDA) to prepare an amine-functional adduct. This adduct is more reaction
able with interacting with terminated epoxy group than IFDA. The result is an adduct that can be
reacted with epoxy resins to form useful urethane coatings without the need for isocyanates.20
Some patents describe methods of synthesis of network polymers based on cyclocarbonate
oligomers.12-14

Applications of Unsaturated Cyclic Carbonates

The copolymerization behavior of vinyl ethylene carbonate (VEC) was studied. VEC is readily
prepared by the catalyzed addition of carbon dioxide to epoxy-butene (Figure 3). VEC is a
sluggish monomer toward free radical polymerization. Due to the electronic structure of the
double bond, VEC copolymerizes with vinyl ester monomers over a wide compositional range.
However, VEC cannot be completely incorporated into an acrylic copolymer. When
copolymerization with styrene is attempted, VEC is barely incorporated.22
Copolymers with good solubility in common organic solvents and good compatibility with amine
crosslinkers can be prepared with VEC levels of up to 40%. Studies of the reaction rates of
various amines with propylene carbonate in solution were used to identify amines that are
suitable as crosslinkers. Hard and glossy clear coatings with good solvent resistance could be
readily prepared, providing that the level of VEC in the copolymer was at an adequate level.
The monomers that have been explored the most extensively are propylene carbonate
methacrylate (PCMA) and propylene carbonate acrylate (PCA). These monomers are readily
copolymerized with other commonly used unsaturated monomers to yield polymers with cyclic
carbonate functionality. There are a few patents discussing the formation of coatings by the

amine crosslinking of these cyclocarbonate functional polymers. However, it does not appear
commercially available. Thus, their use in the preparation of cyclic carbonate functional polymers
has been limited.
The authors have recommended cyclocarbonization of acrylic epoxy resins and preparation of
nonisocyanate polyurethanes by curing acrylic cyclocarbonates with primary amines.20

Reactivity of Cyclocarbonate Groups With Amines

The kinetic features of the interaction of the cyclocarbonate modifying groups of epoxy
compositions with amino groups were studied by Garipov et al.24 The first stage of the process
is the nucleophilic attack of the amine at the carboxylic group of the alkylene carbonate, resulting
in the formation of a tetrahedral intermediate (Figure 4).
The next stage also involves the second molecule of the amine. This molecule deprotonates the
tetrahedral intermediate that has the character of a bipolar ion (Figure 5)
Then, the carbon-oxygen bond is broken, which is favored by the high electron density at the
nitrogen atom, and the nascent alkoxide ion transforms relatively rapidly into the reaction product
illustrated in Figure 6.
Regarding the site of the cyclo carbonate opening, the ratio of the resulting isomeric products
depends on the inductive effect of the substituent R, as well as on the volumes of R' or R".
When the reaction occurs in protogenic solvents, the limiting stage determining the reaction order
is obviously the deprotonation stage that stipulates the overall third order of the reaction and
second order with respect to the amine. In this case, the first stage occurs relatively rapidly due
to the increase in the positive charge on the carbonyl carbon atom resulting from the formation of
hydrogen bonds between solvent molecules and oxygen atoms of the ring (Figure 7).
In aprotic solvents, the rate-controlling stage of the reaction is obviously the nucleophilic attack of
the amine at the carbonyl carbon of the ring. In this case, the solvent molecules are not capable
of forming hydrogen bonds that favor the first stage. This stage is limiting and determines the
overall second order of the reaction in aprotic solvents.

The presence of electron-releasing substituents in the alkylene carbonates results in a decrease

in the partial positive charge on the carbonyl carbon (Figure 8). This results in a decrease in the
reactivity of the cyclocarbonate. Electron-withdrawing substituents, which increase the
electrophilicity of the carbonyl carbon, favor aminolysis at a higher rate. This is clearly confirmed
by the data obtained.
Thus, the constants of the reaction of epoxy and cyclocarbonate groups with primary amino
groups are comparable with one another and have values of the order of 10-4 and 50 C. Which
reaction will occur upon the cure of epoxy-amine systems containing cyclocarbonate modifiers
strongly depends on the reaction mechanism and the structure and mobility of the modifier
molecule. Information about the kinetics was also published by Diakoumakos.11
Laprolate-803 (L-803, aliphatic tricyclocarbonate) was used as the model cyclocarbonate resin
for reactivity and kinetic studies of non-isocyanate-based solventless polyurethanes derived from
the reaction of amines with 1,3-dioxolan-2-one (dioxolanone) rings of L-803. The L-803 resin
shows a very characteristic absorption at 1795 cm-1 (C=O, stretching), whereas the urethane
carbonyl absorbs (stretching vibration) at 1701 cm-1. The increase of the absorption intensity at
1701 cm-1 was recorded as a function of time for reaction temperatures (25, 60, 80 C) in the
presence and absence of triethylamine (catalyst).
In the case where no catalyst was used, the activation energy of the reaction was equal to 6.33
KJ/mol. The Ea of the reaction is rather low, permitting the initiation of the addition-type
polymerization to proceed very fast. This probably results in an abrupt increase of the viscosity of
the mixture inhibiting the completion the reaction of all the dioxolanone rings with amino groups
at relatively low conversion. The reaction was completed after 8 days (no absorption at 1795 cm1) at ambient temperature, whilst 4 days were necessary for the reaction's completion at 60 C.
When triethylamine (1% w/w on total reactants' weight) was used as a potential catalyst, the
activation energy of reaction was found equal to 5.23KJ/mol. Although the activation energy of
the uncatalyzed reaction was low, the introduction of triethylamine was beneficiary, as it
contributed to a further decrease of the activation energy by approximately 17.5% and halved the
reaction times necessary for 100% conversion at both 25 and 60 C.
The reaction can undergo various types of catalysis, acid or base or metal catalysis. From all the
substances tested as potential catalysts, triethylamine, piperazine, tetrabutylammonium bromide,
glacial acetic acid, methanesulfonic acid and metatin type substances emerge as the most
efficient catalysts, providing polyurethanes with 100% conversion of the dioxolanone ring to
urethane groups after 3-4 days at ambient temperature and 1-2 days at 60 C. This information
confirms the author's results.

Thermostability and Polymer Properties Using Nanostructuring

It was found that b-hydroxyurethanes have low thermostability. It may be explained by
weakening of the bond between the carbonyl carbon and oxygen in the urethane group due to
the influence of the OH-group.20
The most interesting way of increasing thermostability of non-isocyanate polyurethane is by
using urethane glycols as "blocked" isocyanates and curing at 180 C in the presence of a
catalyst (Figure 9). The resultant coatings have high mechanical, dielectric properties and
chemical resistance. All properties are equal to properties of conventional polyurethanes created
by using isocyanates.4
It is possible to use aminosilanes and cyclocarbonates for preparing thermostable compounds.
After curing, "weak" bonds will be near hard segments, and the compound will be stable to
increased temperature. Using organosilane pentacyclocarbonate as a base, a compound was
prepared with high adhesion to steel and glass (up to 47mPa), and high impact resistance.5
These compounds have to be investigated in detail. We have studied (1) peculiarities of
organization or self-organization of nano-scale systems based on IPN and (2) the properties of
nano-scale systems (composites) based on an IPN network.
Synthesis of the curing agent was accomplished by hydrolyses of aminopropyltriethoxy silane
(AMEO, Degussa) 29.1 g, diphenylmethoxysilane (Huls) 64.2g and water 6.7 g. After adding
water, the mixture became turbid, but after 20 min became clear. Mixtures of silanols were used
for curing the epoxy resin: Epon 828 (Shell) 190 g and curing agent 249 g. After curing at 24 hrs
@ RT (or 2 hrs @110 C) a network polymer was obtained. The coating is glossy, hardness H,
impact test 50 kg cm, weight loss after 120 hrs in water 0%. The polymer has weight loss at 200
C during 10 hours 0%, gel fraction 94% (curing 24 hrs @RT). By using polyaminosiloxane
hardener "ASOT" and epoxy resin, coatings were prepared with externally high water and solvent
resistance and high adhesion to different substrates.6 Due to alkoxy radicals, formations of
highly dispersed phase by self-condensation of the silanols is possible. This inorganic phase is
highly dispersed.10
Proposed aminosilane oligomers have high functionality. Reactive groups, -Si(OR)n, can react
with -OH groups forming inorganic nano-layers. It is known that a 2% addition of nano-layered
silicate in nylon-6 significantly improves the heat distortion temperature without a significant loss
of impact strength. Proposed composites may be used as coatings, floorings, adhesives and
sealants. Nanocomposites based on IPM have good adhesive and other high mechanical
properties. Preparation of the modified organic coatings with high-wear resistance and superior
photostability is possible.

The dendroaminosilane hardeners allow the possibility of introducing the siloxane fragments into
the aromatic structure of the diphenylolpropane-based epoxy-amine or cyclocarbonate-amine
network polymers. Additional hydrolysis of aminosilane oligomer creates the secondary nanostructured network polymer that improves the service properties of the compound.9
The acrylic non-isocyanate polyurethane has high weathering stability, but only if cured at 110
C. By using dendroaminosilanes we have prepared coatings at RT. We prepared
cyclocarbonate on the base of acrylic resin Setalux 17-1433 (Akzo Nobel) by using the reaction
of epoxy groups with CO2 in the presence of a catalyst. Synthesis of the curing agent was
provided by hydrolysis of 764 g aminopropylmethyldiethoxy silane (Dynasylane 1505, Huls), 208
g TEOS (Aldrich Chemical Company) and 216 g water. After adding water, the mixture became
turbid, and after 5-10 sec became clear. Gel fraction after curing 24 hrs at RT is 84%. Formation
of nano-particles is occurring by the reaction of alkoxy groups with water.
The newly built silanol-hydroxyl reacts with the surface hydroxyl groups and forms strong bonds.
Organic groups on the other hand react with the organic components of the paint.
It is possible to hydrolyze aminosilane with water and by doing so to prepare a polyfunctional
aminosilane (Figure 10).
The scheme of the reaction of the curing agent with a surface substrate is shown in Figure 11.
The hydrolytic behavior depends on the structure of the organo-functional silanes.
According to the data in Table 1, hydrolysis occurs easily at RT. Stability depends on the
structure of the components and conditions of hydrolysis. If one provides hydrolysis by adding
H2O to the mixture of aminosilanes, the mixture converted into gel during 15 sec. But if TEOS is
added to the hydrolysis mixture of aminosilanes after reaction, the reaction product is stable.
Structural formulas of new nano-forming agents are given in Figure 12. Structures of hydrolyzed
aminosilanes may be very different. Formation of nanoparticles occurs under moisture.
Nanoparticles are formed by the addition of silica via a sol-gel process (Figure 13).

A Novel Industrial Cyclocarbonate-Based Technology

Based on our work, the German company EFM GmbH produces novel non-isocyanate nanostructured polyurethane binders for monolithic flooring and industrial paint compositions.25 The
two-component binders have unique properties that combine the best mechanical properties of
polyurethane with the chemical resistance of epoxy binders. Polyurethane EFM-binders do not
present health hazards since they do not consist of isocyanate components at any stage of
preparation. The environmentally friendly binders are insensitive to the moisture in the air or the
coated surface and provide for making monolithic nonporous materials with decreased
permeability.

Conclusions
Cyclocarbonate resins offer a reliable alternative for the preparation of non-isocyanate-based
porous-free polyurethanes, the moisture-insensitive process of which poses minimal, if any,
environmental threat. Industrial manufacture of non-isocyanate polyurethane binders is available.
It is possible to use HNIPU as coatings, floorings, chemical-resistant materials, adhesives and
foams.
References
1 Blank, N; Figovsky, O. "Nonisocyanate polyurethane glues for jointing reinforced plastics",
Proceedings of International Adhesion Symposium, 87-8, Tokyo, Japan, 1994.
2 Shapovalov, L; Blank, N; Tartakovsky, A. "Nonisocyanate polyurethane for protective coatings",
Abstracts of the 2nd Conference of the Corrosion Forum (NACE), No 1.1.3., Tel-Aviv, Israel,
1996.
3 Figovsky, O. Interface Phenomena in Polymer Coating. Encyclopedia of Surface and Colloid
Science, N.Y. Marcell Dekker, Inc. 2002, pp 2653-2660.
4 Micheev, V. "Using of urethaneglycoles as blocked diisocyanates", LKM & ich primemnenie,
1983, No. 6, pp.5-6 (in Russian).
5 Figovsky, O. et al. "Nonisocyanate polyurethane adhesives and coatings", Express information,
no. 15, v.6, 1990 (in Russian).
6 Figovsky, O.; Shapovalov, N. Blank. Monolithic Chemical Resistant Floor Covering Based on
Non-Isocyanate Polyurethanes. Corrosion and its Control. Proceedings of International
Conference on Corrosion CORCON-97, Mumbai, India, Dec. 3-6, 1997, pp. 757-763.
7 WO 03028644, EP 1432488.
8 WO 0042033.
9 Buslov, F.; Shapovalov, L.; Figovsky, O. Advanced Synthesis of Organic-Inorganic Nanohybrid
Materials for Coatings. Proceedings of Third World Congress "Nanocomposites 2003", Nov. 1012, 2003, San Francisco, Calif., pp. 32/1-7.
10 Polymer Nanocomposites, Washington, DC, ACS Symposium series, 805, p. IX, 2001.
11 Diakoumakos, K; Kotzev, D. Nonisocyanate-based polyurethanes derived upon the reactions
of amines with cyclocarbonate resin. Macromolecular Symposia, 2004, pp. 37-46.
12 Rappoport, L; Brown, R.D. 1992, US Pat. 5,175,231.
13 Crawford, W.C.; Marquis, E.T.; Klein, H.P. 1994, US Pat. 5,340,889.
14 Figovsky, L. Hybrid Nonisocyanate Polyurethane Network Polymers and Composites Formed
there form. 1999, US 6,120,905 (2000). WO 9,965,969, CA 2,335,000 AU 4,441,099 and EP
1,088,021.
15 Shapovalov, L.; Blank, N.; Figovsky, O. EP 1020457, 2000.

16 Figovsky, O.; Shapovalov, L. Nonisocyanate Polyurethanes for Adhesives and Coatings. First
International IEEE Conference on Polymers and Adhesives in Electronics, Potsdam, Germany,
Oct. 21-24, 2001, pp. 257-264.
17 Figovsky, O.; Shapovalov, L.; Ioelovich, M.; Axenov, O. Advanced Coatings for Industrial
Application. 75th JSCM Anniversary Conference "New Technology on Colour Materials for 21st
Century," Tokyo, Japan, April 2-4, 2002, pp. 90-93.
18 Electronic version http://www.safetyline.wa.gov.au/ page bin/
19 NIOSH, electronic version.
20 Figovsky, O.; Buslov, F.; Shapovalov, L. UV and Thermostable nonisocyanate polyurethane
coatings, XXVII FATIPEC Congress, Paris, France, 2004.
21 Figovsky, O.; Shapovalov, L.; et al. Double liaison, No. 318, pp.61-64, 2002, European
Coatings, 3, pp.18-25, 2003 and Surface Coatings International, Part B: Coatings Transactions,
vol. 82, B2, pp.83-90.
22 Webster, D.C.; et al. Synthesis and applications of cyclic carbonate functional polymers in
thermosetting coats, Progress in Organic Coatings 40, 2000, 75-282.
23 Clements, J. Reactive applications of cyclic alkylene carbonates, ACS web-publication. 2002.
24 Doklady Physical Chemistry, vol. 393, Nos-1-3, 2003, pp. 289-292 Translated from Doklady
Akademii Nauk, vol. 393, No.1, 2003, pp. 61-64.
25 A novel Cyclocarbonate-based technology, The Polyurethane Newsletter, Issue 68, 2004,
electronic version, 2004. PU2PU.
26 Figorsky, O.; Shapovalov, L. Hybrid Nonisocyanate Polyurethane Adhesives. Proceeding of
International Conference "Polymer Bonding 2004", April 27-28, 2004, Munich, Germany; pp.99103.
This paper was presented at the Nano and Hybrid Coatings conference sponsored by The Paint
Research Association, January 2005, Manchester, UK. Conference proceedings can be obtained
by contacting Janet Saraty, conference administrator, at [email protected].