ELSEVIER

Progress in Organic Coatings 30 (I 997) 265-270

Amine chemistries for isocyanate-based coatings

Douglas A. Wicks*, Philip E. Yeske
Bayer Corporation, ICD Coatings, 100 Bayaer Road, Pittsburgh. PA 15205, USA

Received 15 July 1996; accepted 30 October 1996

Abstract
The inherent high reactivity and color instability of primary amines has limited their applicability in polyisocyanate-based coatings. However, recent developments in the use of modified amine functional coreactants in such formulations shows significant progress towards having two-component systems with excellent application and durability properties. The systems reviewed here use amine functional groups which are either blocked by addition of carbonyl compounds, or are of reduced reactivity through steric hindrance and intramolecular hydrogen bonding. The relative benefits and drawbacks of the various systems are detailed along with their applicability to high solids coatings. 0 1997 Elsevier Science S.A.
Keywords:

Amines; Isocyanate-based coatings; Two-component

systems

1. Background
Two-component polyurethanes have become a dominant

technology in many application areas[ 11.They have shown significant market penetration in automotive, heavy duty maintenanceand light industrial coatings where high performance is required. In particular the following performance characteristics stand out as representative of polyurethane coatings: durability; abrasionresistance;weatherability; environmental etch resistance. Two-component polyurethanes are formulated with the polyol and polyisocyanate componentsbeing kept separate until just before use. After mixing at the proper stoichiometric ratio, the coating is applied. Years of research and field application experience have afforded a clear understanding of the factors affecting pot-life, dry-time and ultimate film properties.Formulators have a clear picture of the affects of solvents, catalysts and resin systems on these important properties. High molecular weight polyester and acrylic polyols can be readily formulated with polyisocyanate componentsto have long pot-lives and fast dry-times. As the industry moves towards higher solids,it is running into several limitations in its raw material base.Examination of the two-component formulations readily demon* Corresponding author.

stratesthat the solvent demand of the polyol component is much higher than that of the polyisocyanate. Great strides have been made in reducing this solvent demand by lowering the molecular weight and changing the molecular architecture of acrylic and polyester polyols but additional gainswill be difficult without sacrificing application properties. Acrylic polyols, which are the standard for high performance in conventional systems, face significant difficulties in maintaining a low level of non-functional and monofunctional components as their molecular weight is reduced [2]. They also lose their ability to lacquer dry, necessitating attainment of physical dry through chemical crosslinking. Polyurethanes are also being challenged by the reaction kinetics limitations associatedwith the high solids systems. As the solids content of two-component polyurethane systems increases,there is a significant increasein the relative concentration of reactive groups, not only through the removal of solvent but through the reduction of polyol equivalent weight. The combination of thesetwo effects results in a significant reduction in pot-life becauseof the increased rate of reaction. Rate = K[NCO][OH] These systems also suffer from prolonged dry-times. As mentioned earlier, the lower molecular weight polyols no

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longer afford a partial lacquer dry to the coating, so molecular weight must be built up by having reactions take place. This dilemma is complicated even further by the reduction of catalyst level that is required to extend useful pot-life. As the industry pushes to reduce the final solvent content to near zero, the fundamentals of existing two-component polyurethane coatings must be rethought. Clearly new chemistries for and approaches to low viscosity coreactants for polyisocyanates are needed. Amine functional coreactants are one such approach. Amine functional products provide a viable route to very high solids coatings. In the past, the inherent high reactivity and color instability of primary amines has limited their applicability, but recent developments in the use of modified amine functional coreactants in such formulations shows significant progress towards having two-component systems with excellent application and durability properties. Increasingly, these are low viscosity materials that are significantly less reactive than the parent amine. To make full use of these products in the development of very high solids systems, a full understanding of the chemistry and control of the chemistry is required.

R-NC0

H,O

--)

R-NH*

COz 4

R-NC0

R-NH,

HbN,C.NOH R R

Fig. 2. Urea formation

from water and isocyanates.

2. Polyurea

coatings

The reaction of polyisocyanates and primary or secondary polyamines to form polyureas is too fast to be widely useful for most applications (Fig. 1). Gel times of these types of systems are measured in seconds, thus precluding a useful pot-life. Some systems have been formulated for application with plural component equipment with impingement mixing. As one would assume, these products exhibit very rapid dry-times and additionally show very poor flow and leveling. These systems typically are formed from aromatic polyisocyanates reacting with amine functional polyethers or aromatic diamine/polyether blends. 2.1. Moisture cure polyurethanes Another application that involves the formation of polyureas is in one component moisture cure urethanes. The moisture cure systems are finding widespread use and interest within the heavy duty maintenance and military CARC markets. These systems make use of both aromatic and aliphatic systems with the former being favored for primers and interior applications and the latter finding significant use in topcoat. In both cases, the use of a moisture cure system is preferred because it is a completely formulated

coating in one package, thus there is no need to be concerned with the accuracy of mixing in a field setting. As shown in Fig. 2, this application makes use of environmental moisture as a reactant to initiate the formation of urea. The moisture reacts with the isocyanate group to generate free amine and carbon dioxide. The generated amine then immediately reacts with another isocyanate functional groups affording the urea linkage. Typical isocyanates used in these applications range from urethane prepolymers derived from aliphatic and aromatic diisocyanates to adducts of isophorone diisocyanate and hexamethylene diisocyanate. These products have been demonstrated as useful in making high solids coatings for use as primers, sealers and topcoats in the heavy duty maintenance area [3]. In these applications, the resulting polyurea films showed long term performance equal or superior to the corresponding two-component polyurethane coatings. As should be expected these systems show a large dependence on the amount of environmental moisture available when the coating is applied. Too low a humidity level results in prolonged dry times, high humidity leads to surface skinning and potential solvent entrapment. Also, film thickness is restricted to relatively thin coats by the formation of bubbles resulting from CO:! evolution in the reaction.

3. Modified

amine chemistries

3.1. Aspartic acid esters Recently there have been advances in hindered amine chemistry which allow amines to be used in high solids coatings without the use of specialized equipment. These hindered amines are obtained by the Michael addition of primary amines to dialkyl maleates (Fig. 3). The resulting secondary amine, an aspartic acid ester, has reduced reactivity due to steric effects and hydrogen bonding. Like the parent amines, aspartic acid esters react, as shown in Fig. 4, with isocyanates to form ureas. The reactivity of these amines towards polyisocyanates was found to be dependent on the structure of the parent
CO,R CO,R + CO,R Fig. 3. Formation R-N /JI CO,R H of aspartic esters.

R-NC0

H-N

3
R

N,c.NI

R R

R-NH,

Fig. 1. Urea formation.

D.A. Wicks, P.E. Yeske /Progress CO,R R-NC0 + R-7 H---O Fig. 4. Reaction C-OR II + R-T-C-N. H 8 JI R CO,R CO,R

in Organic

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30 (I 997) 265-270

261

of an aspartic acid ester with an isocyanate.

amine [4,5]. Two representative bis-aspartic acid esters which highlight the differences in reactivity are shown in Fig. 5. Acyclic structures, such as the bis-aspartic acid ester derived from hexamethylene diamine (HDA), show gel times with polyisocyanates of 15 min. This is much slower than typical primary or secondary diamines but still too fast for use in conventional spray equipment. Cycloaliphatic bisaspartic acid esters, such as the one based on methane dicyclohexane diamine (Hi*MDA), yield gel times of several hours, bringing them into a useful reactivity for the formation of two-component coatings. Adding a methyl group on the ring CY the amine, extends the gel time to greater than a to day due to steric hindrance. With an ethyl group in that position, the reaction with an isocyanate is nearly precluded. Significant differences in catalysis of these products compared to that of hydroxyl/isocyanate chemistries has also been reported. In direct contrast to urethane reactions, the rate of aspartic acid ester reaction with isocyanates was inhibited by the presence of the common urethane catalyst, dibutyltin dilaurate [6]. In general, any tin(IV) compound was successful at inhibiting the aspartate-isocyanate reaction and maintaining relatively short dry-times. Interestingly, further testing on other urethane catalysts showed that tin(IV) compounds appear to be the only ones that inhibit the reaction. Dibutyltin dilaurate displayed the best cure profile and was chosen as the standard additive for evaluating other parameters. Although a good understanding of the reaction of aspartic acid esters with isocyanates has been developed and these systems are now moving into commercial use, they still do not represent a perfect partner for isocyanates in two-component systems. Specifically, they still react too fast with polyisocyanates in the can after mixing, thus limiting their utility in a fast dry system. 3.2. Oxazolidines Oxazolidines bring a new twist to having water as a reactant in the system. These heterocycles have been demonstrated to be more reactive towards water than the isocyanate and the reaction yields a difunctional isocyanate reactive species along with a carbonyl compound (Fig. 6) [7]. The reactive species contains both hydroxyl and amine

functionality resulting in both urethane and urea bond formation. These products have the advantage of multifunctionality and the reaction by-product is an organic compound which is less likely to cause bubbling. On the negative side is the generation of VOC by release of the volatile carbonyl compound. A variety of different structures have been commercially made available. Viscosities at 1007~ active resin range from 20 mPa s up to 8000 mPa s. Monooxazolidines with R being alkyl give the lowest viscosity and the use of isobutyraldehyde as the parent carbonyl compound appears to be universal among these products. Bis-oxazolidines derived from diethanol amine (Fig. 7), offer tetrafunctionality at a reasonable viscosity. The viscosity of the bisoxazolidine is strongly dependent on the linking group X, with a carbonate group being lower than an adipic ester which is much lower than a diurethane. Recent presentations about the these products show them to be versatile diluents for two-component polyurethanes [8,9]. They demonstrate good chemical and weathering properties, but do not bring any significant drying speed advantages over the low molecular polyols they are replacing. 3.3. Use of imines as isocyanate coreactants Another route to blocked amines is through imine formation. These would appear to be excellent choices for high solids coatings applications because of their viscosities which range between 5 and 100 mPa s at 100% active resin, thus allowing for significant displacement of organic solvent. As is shown in Fig. 8, amines readily react with carbonyl-containing compounds in an equilibrium process to produce imines and water. There are two basic types of imines used in the coatings chemistry. The first, a ketimine, is the result of a ketone and a primary amine combining. When an aldehyde is the source of carbonyl. the result is an aldimine. Because imine formation is an equilibrium process, parameters such as reaction temperature, solution pH and reactant concentration play an important role in the effectiveness of amine to imine conversion. The following sections will compare and contrast the preparation and stability of ketimines and aldimines and discuss the unique manner in which these materials react with aliphatic polyisocyanates. 3.4. Preparation of ketimines versus aldimines

The most common method of preparing imines is the reaction of amines with ketones or aldehydes, as shown in

Fig. 5. Bis-aspartic

acid esters of HDA

and H,?MDA

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265-270 R R +w R RKetimine Aldimine R + Hz0

R-NT + I-W R,)cR 1

--)

R-N-OH H
of oxazolidine

+ 04~ R
with water. Fig. 8. Imine formation R--NH, + o

Fig. 6. Reaction

R, R = Alkyl R = H, R = Alkyl compounds.

Fig. 9. For the current study, we compared the bis-ketimine formed from isophorone diamine (IPDA) and methylisobutyl ketone (A) with the corresponding bis-aldimine derived from isobutyraldehyde (B). In the preparation of A, water must be removed from the reaction mixture to drive it to completion. Amines react with aldehydes at room temperature to produce the desired aldimines quantitatively. Even better, the reaction to form B goes to completion without the need to remove the evolved water. Because the reaction with ketones requires higher temperatures and longer reaction times, the ketimine products develop a yellow color during production. For example, B has an APHA color of about 20, whereas the ketimine product (A) has an APHA color of about 1.50. The ketimines also contain more impurities, because side reactions occur under these conditions. Some of these impurities are higher molecular weight and lead to higher viscosity products. The viscosity of B at 25C is 15 mPa s, whereas the ketimine (A) has a viscosity of about 80 mPa s. 3.5. Hydrolytic stability

from a primary

amine and carbonyl

The relative hydrolytic stabilities of the ketimine and aldimine of IPDA were compared by first dissolving 1 g of each compound in 5 g of tetrahydrofuran, to which was added 2 equivalents of water for each equivalent of imine. Infrared spectra of the solutions were taken at 0 h, 3 h, 1 and 3 days. Evidence for hydrolysis of the imine was taken as the appearance of a peak at about 1720 cm-, which would be due to a carbonyl group absorption. In the spectra shown in Fig. 10, it was found that within 3 h the ketimine (A) began to produce a peak at 1717 cm-. This indicated that the ketimine was hydrolyzing to yield the starting ketone and amine. Within 3 days, the carbonyl and imine absorption peaks were almost of the same intensity. In sharp contrast the aldimine did not produce a noticeable carbonyl peak even after 3 days. This is strong evidence that the aldimine (B) is not hydrolyzing to any appreciable amount under ambient conditions. 3.6. Ketimines as isocyanate coreactants Work by Bock and Halpaap [lo] showed that there was potential for a different reaction mechanism when ketimines

were employed with isocyanates. As with epoxy coatings, ketimines in isocyanate systems were found to give inhibition of reaction before application with acceleration taking place after application of the coating. In isocyanate-based systems, it appears that the ketimine no longer has to hydrolyze to react. This reaction has been shown by Bock and Halpaap to go to very high conversion in thermally cured coatings even in the absence of moisture. With isocyanate-based systems, the ketimine no longer has to hydrolyze to react, but instead can react in a direct manner. This reaction is extremely slow in the absence of weak acid catalysis but proceeds very quickly to a high yield when exposed to ambient moisture. Analysis of a model reaction between butylisocyanate and the MIBK ketimine of cyclohexylamine showed the presence of several reaction products (Fig. 11) (111. These products indicated that several reaction pathways in addition to hydrolysis and the direct reaction are possible. For coatings cured under ambient conditions, the direct reaction between isocyanate and ketimine is competing with the hydrolysis of the ketimine. The kinetics of this competition are primarily dependent on the structure of the ketimine and the presence of catalytic groups, such as carboxylic acids. Taking retained solids as a measure of the direct reaction, it was found that between 50 and 75% of the ketimine groups react directly with isocyanates and the remainder hydrolyze before reacting. 3.7. Aldimines as isocyanate coreactants The initial promising results with ketimines led to further investigations of the direct reaction between isocyanates and imine groups with emphasis on finding structures with a reduced tendency towards hydrolysis. All attempts at varying the ketone structure resulted in either an increased number of unwanted side reactions or an increased hydrolysis rate. Surprisingly, the use of an aldehyde to form an aldimine showed promise for control of the reaction product profile.

Oq-CH H t Fig. 7. Bis-oxazolidine hyde.

2CH 2 -0-X-0-CH,CH2-N

b H t B Fig. 9. Formation of ketimine and aldimine of IPDA.

derived

from

&ethanol

amine and isobutryalde-

D.A.

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269

Ketimine

(A)

Aldimine

(B)

I1800 1700 1600 Wavenumber (cm-) Fig. 10. Infrared spectra of hydrolysis

1 3 hrs24 hrs72 hrs Fig. 12. Postulated mechanism for the formation of an enurea

1800 1700 1600 Wavenumber (cm-) experiments.

3.8. Structure determination The direct reaction between an aldimine and an isocyanate was investigated in model studies using a difunctional aldimine (similar in structure to B) and a monofunctional isocyanate (octadecylisocyanate) [ 121. After heating the mixture at 70-80C for 72 h the reaction products were analyzed by H and C NMR. It was found that the reaction yielded one predominate product that could be described as an enurea (Fig. 12). The general structure and postulated reaction pathway are shown below. Further model studieswere carried out and have shown that hydrolysis can take place under ambient application conditions. For example in the reaction between butyl isocyanate and the isobutyraldehyde aldimine of cyclohexyl amine, it is possible to form the urea product resulting from hydrolysis when the reaction was carried out at high humidity. The hydrolysis product is evidenced by the presence of the Amide II band at 1580 cm- in the infrared spectrum shown in Fig. 13. However, the same reaction carried out at elevated temperature afforded the previously described enurea structure without any evidence of the Amide II band in the IR. The actual retention of solids of the aldimine group in reaction with an isocyanateIS dependenton many variables, including: structure of the parent amine; catalysis, i.e. carboxylic acidsand alcohols; solventsusedin the formulation; additives; and curing conditions. 3.9. Imines in coatings systems The advantagesof imines in coatings can be seenin the

reactivity of aldimines towards isocyanatesas measured by solution viscosity build and dry-time measurements a of simplified high solids model system. In this system, the imines were combined with a polyisocyanurate of hexamethylene diisocyanate at an NCOiN ratio of 1: 1 and reduced with butyl acetate to 75% resin solids. The ketimine (A) system had an initial viscosity of 15 mPa s which increased over a 2-h period to 35 mPa s. After 48 h, the reaction mixture had solidified. When the aldimine (B) was used, the initial viscosity was 10 mPa s and remainedunchanged over a 2-h period. After 48 h, a viscosity of 15 mPa s was observed and gel times of more than 6 weeks after mixing can be obtained. Films cast from both formulations dried to the touch within 1 h. Both systemsshowedexcellent solvent resistancewithin 24 h of application, indicating that complete chemical cure was obtained.

4. Summary Amine functional coreactants for use with polyisocyanates in two-component applications represents a rapid growth area for new product development. These coreactants allow for the formulation of high performancecoatings characterized by: low organic solvent content; long pot-life; dry-times approaching that of a lacquer; excellent durability. These amine chemistries, although very useful in high solids applications will require that coatings chemistsredevelop a lot of the basic understandingsof two-component applications. The catalysis requirements of amine-isocyanate systems are almost completely opposite that of the well-known hydroxyl-isocyanate chemistry. As detailed here, theseproducts react with isocyanatesthrough a variety of different mechanisms,often involving both direct and indirect pathways at the sametime.

Wavenumber Fig. I 1, Reaction products of isocyanate + ketimine. Fig. 13. Infrared

(cm-)

Wavenumber

(cm-) products

spectra of cured aldimine/isocyanate

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Acknowledgements The authors wish to acknowledge Dr. Lanny Venham, Dr. S. Ming Lee, Dr. A. Donald Meltzer, Sharon Hicks, Mike Butcher, Mike Jeffries and Jack Hunter for their part in evaluating Bayer Corporation products in high solids twocomponent systems.

References
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[S] Ch. Zwiener, L. Schmalstieg and M. Sonntag, Eur. Coat. J., 10 (1992) 588. [6] D.A. Wicks and P.E. Yeske, Proc. 20th Waterborne and Higher Solids and Powder Coatings Symposium, 1993, p. 49. [7] W.D. Emmons, A. Mercurio and S.N. Lewis, J. Coat. Technol., 4 (1977) 631. [E] G.A. Howarth, Proc. 23rd Waterborne and Higher Solids and Powder Coatings Symp., 1996, 92. [9] M.D. Hoffman, M.J. Hourani and T.L. Johnson, Proc. 23rd Waterborne and Higher Solids and Powder Coatings Symp., 1996, p. 5 16. [lo] M. Bock and R. Halpaap, J. Coat. Technol., 59 (1987) 259. [ 111 E.P. Squiller and D.A. Wicks. Proc. 20th Waterborne and Higher Solids and Powder Coatings Symp., 1993, p. 15. [12] S.M. Lee, A.D. Meltzer, L.D. Venham, D.A. Wicks and P.E. Yeske. Proc. 22nd Waterborne and Higher Solids and Powder Coatings Symp., 1995.