Polysiloxaneurethanes: new polymers for potential coating applications

PROGRESS ‘t8w ELSEVIER

Progress in Organic Coatings 27 (I 996) 123- 131

Polysiloxaneurethanes: new polymers for potential coating applications Janusz Kozakiewicz Industrial Chemistry Research Institute, Rydygiera 8, 01-793 Warsaw, Poland

Received 17 October 1994; revised 18 May 1995

Abstract Polysiloxaneurethanes (PSUR) are block copolymers containing polysiloxane and urethane (or polyurethane) segments and showing very interesting mechanical, dielectric and surface related properties. Brief reviews of investigations that have been carried out so far on PSUR are presented with special reference to coating applications of them. The properties of the novel moisture-curable PSUR (MCPSUR), tested before and after moisture curing, are discussed in connection with their chemistry and structure. The properties of aqueous dispersions of PSUR (ADPSUR) synthesised in ICRI are also reviewed. The preliminary results of some coating tests made for MCPSUR and ADPSUR are presented. Keywords: Siloxane-urethane

block copolymers; Moisture-curable polyurethanes; Polyurethane dispersions

1. Introduction

The possibility of combining the advantages of polysiloxanes (PSIL) and polyurethanes (PUR) has attracted the attention of many investigators for a long time. It was expected that such ‘hybrids’ would have better heat resistance and lower temperature flexibility than PUR and better mechanical strength and abrasion characteristics than PSIL. Attempts to reach this goal by simply blending polydimethylsiloxanes (PDMS) with thermoplastic polyurethanes (TPUR) were totally unsatisfactory [l]; distinct deterioration of the TPUR properties was observed. However, the possibility of obtaining coatings from a mixture of solutions of TPUR in DMAc and PSIL in THF was reported [2]. Simultaneous interpenetrating polymer networks (SIN) based on PUR and PSIL were carefully studied [3] and they appeared to be either phase-separated or miscible materials depending mostly on the PSIL structure and PURjPSIL ratio. Using phenylmethyl PSIL (PPMS) instead of PDMS, definitely increased miscibility in such systems. Attempts to increase the poor compatibility of PUR and PSIL by incorporating PUR-b-PDMS block copolymer were made [4,5] but, although its adsorption at the interphase was proved by SEM [4], no improvement in mechanical properties of the blends was achieved. However, again, when PPMS was applied instead of PDMS [6] full compatibility (single T, observed) was noted for certain PUR-PSIL IPNs, especially those 0300-9440/96/%15.00 0 1996 Elsevier Science S.A. All rights reserved SSDI 0300-9440(95)00527-L

rich in PUR. It was explained by the similarity in solubility parameters of PUR, 19.4 x lo3 (Jm-3)1/2, and PPMS 18.6 x lo3 (Jm-3)112. Segmented poly(dimethylsiloxaneurethane) copolymers (PSUR) were also investigated [7] and, again, phase separation occurred due to the extreme segment incompatibility. As the interfacial thickness of a polyurethane block copolymer was expected to increase with the polarity of the soft segment thus leading to improved segment compatibility, PSIL with groups more polar than -CH, were used to synthesise PSUR. While using PSIL with a chloromethyl group did not improve phase miscibility [8] attaching a more polar cyanoethyl group to silicon resulted in a distinctly better segment compability [9], though the copolymers were reported to be still two-phase materials. Best results were obtained when polytetramethylene oxide (PTMO) soft segments were introduced into the copolymer together with PSIL segments. The positive effect of PDMO on segment compatibility in PSUR was fully proved by other authors [lo]. Recently, an interesting study on the orientational behaviour of segmented PSUR was made [l 11. It was found that both hard and soft segments oriented positively when stretched, a different behaviour from that usually observed in other PUR block copolymers. Among many other papers dealing with the properties-structure relationship in PSUR, the work [12] presenting the effect of the PSIL segment molecular weight on the Tg and T,,, of such materials is especially worth mentioning. It was reported that both T, and T,,,

124

J. Kozakiewicz

/Progress

in Organic Coatings 27 (1996) 123-131

OCN- [O-U~U],-O-NC0

(I)

I

better segment compatibility no phase segregation t

worse segment compatibility phase segregation occurs

Fig. 1. Differences in PSUR structures obtained in the reaction of siloxaneurethane prepolymer (I) with dial (‘standard’ system) and with water (moisture-curable system). U = urethane group; ??= diol chain; M = urea group; 0 = diisocyanate chain; = siloxane chain.

distinctly decreased with increasing PSIL chain length, but exchanging some part of PSIL for poly(ethylene adipate) resulted in a distinct increase in T,,, only, while Tg remained almost at the same level. The results of studies on surface properties of PUR [13,14] are also noteworthy since it has been proved that they exhibit antithrombogenic properties and can be used as blood-compatible biomaterials. It is presumably due to the substantial surface enrichment with polysiloxane in such copolymers [15]. Although the possibility of using PSUR in coating applications has been mentioned in several patents, only very few papers dealing directly with this problem are available. Very interesting results of studies on anticorrosive coatings based on silicone-modified epoxy/polyurethane graft copolymers have been reported [16,17]. To make the coating resin, NCO-terminated siloxane-urethane prepolymer was first synthesised and reacted with an especially prepared epoxide group-containing compound. The high molecular weight epoxy resin thus obtained was then emulsified in water and a water-based amine crosslinker was added. Both clear and pigmented formulations were subjected to sea water immersion tests. Other authors [I 81 attempted to develop a solventbased, two-component coating using a solution of the blend of polyetherdiol and siloxane oligomer diol (SOD) as component A and a solution of polyisocyanate as component B. They found that IO-15% SOD in the blend with polyetherdiol was sufficient to get both very good mechanical strength and thermal resistance of the cured film. The UV-curable, acrylate group-terminated PSUR have been studied in detail by Chiang and Shu [19,20]. The results of testing these polymers as coatings proved their very good adhesion, especially to glass, excellent mechanical properties as well as resistance to water and diluted acids and bases. Unexpectedly, flexibility and resistance to organic solvents were not satisfactory. The coating applications of PSUR claimed in the patents are as follows: 0 biocompatible, especially antithrombogenic coatings on biomedical materials [21-271 0 general flexible coatings on paper, metal, glass etc. [28-371

waterproof coatings and finishes for textiles and natural leather [38-431 and wear resistance-imparting binders 0 antifriction for magnetic recording media [44-531 0 heat-resistant layers for thermal recording materials [54-581 ink binders with good adhesion to 0 printing polyamide substrates [59] 0 water- and oil-repellent coatings on glass, ceramics, masonry, wood, paper, metals, leather and textiles (perfluorinated diols were used as chain-extending agents) [59-631 0 antifriction, abrasion-resistant linings for automotive window channels [64,65] coatings for various purposes 0 radiation-curable (PSUR with acrylate functionality were used) [66681 0 peelable coatings (PUR with pendant PDMS chains were used) [69] 0 coatings for hypo-adherent wound dressings [70] 0 antifouling coatings [7 1,721 Other potential applications of PUR-SPIL block copolymers described in numerous patents include: thermoplastic or vulcanisable elastomers, sealants, adhesives, highly selective gas permeable membranes, contact lenses and other biocompatible materials, surface-active agents, internal mould-release agents, optical and air-spinnable fibres, photosensitive compositions, releasability rendering agents for adhesive tapes. It is noteworthy that only very few published patents deal with moisture-curable PSUR (MCPSUR) systems while both moisture-curable systems based on PUR and PSIL alone are well known and widely used [73]. Moreover, there is no published paper available dealing with either synthesis or the properties-structure relationship of MCPSUR. Therefore, it was the objective of this work to investigate the possibility of synthesis of MCPSUR and study their properties both before and after moisture curing. It was believed that such materials would be useful for making novel moisture-curable coatings, sealants and, perhaps, also reactive hot-melt adhesives for special purposes. The important reason for dealing with MCPSUR and not with ‘standard’ diol or diamine extended products was the expected better segment compatibility in the former systems. This is illustrated in Fig. 1 which 0

J. Kozakiewicz

/ Progress

in Organic Coatings 27 (1996) 123-131

shows the simplified structure of diol-extended and water-extended siloxaneurethane prepolymer (I). The other part of this work was aimed at synthesis of PUR-PSIL aqueous dispersions (ADPSUR) useful for coatings. Though such products are presented in quite a few patents, there is still a great deal of interest in PUR-PSIL aqueous systems for environmental reasons. The results presented in this paper are only preliminary and the project is intended to be continued.

2. Experimental NCO-terminated MCPSUR were prepared [74] from diisocyanates, siloxane oligomer diols (SOD) of structure II and, for some part of the study, polypropylene glycol (PPG) using molar excess of diisocyanates (NCO/OH = 2/l). R,

R,

I

I

HO-R, {-Si-O},-Si-R,-OH k3

k

3

II SOD-l (R, = -(CHz),-0-(CH,),-, R, = R, = CH,, x = -20 according to NMR data) was obtained from Shin-Etsu as KF 6001. SOD-2 (R, = -(CH,),-, R2 = R, = CH,, x = - 10 according to NMR data) was obtained from Goldschmidt as Tegomer 2111. PPG of MW = 2000 was obtained from NZPO Rokita (Poland) as Rokopol D 2002. Both aliphatic isophorone diisocyanate (IPDI) obtained from Huls and aromatic-aliphatic tetramethylxylylene diisocyanate (TMXDI) obtained from American Cyanamid were used as obtained. The general structure of the MCPSUR prepared in this study is given in Fig. 1. When in the synthesis of such MCPSUR some part of II was replaced by a polyol, e.g. PPG, the moisture-curable block copolymer with both siloxane and PPG soft segments (III) was obtained (see Fig. 2). All MCPSUR synthesised in this study (viscous liquids or semi-solids) were characterised by FTIR, GPC and NMR (‘H and 13C), and their essential physical properties (e.g. viscosity, NC0 content) were measured using standard laboratory procedures. Unreacted

OCN~[U~U-IU~U~Jl.-UrLIZU-INCO

III Fig. 2. Structure of siloxaneurethane prepolymer segments. 0 = Diisocyanate chain, U = urethane segment; *= PPG segment.

containing PPG group; = SOD

125

diisocyanate content was calculated based on GPC data. The moisture-curing process was conducted at fixed temperature/humidity conditions (25 “C and 50% r.h.). Progress of the cure was monitored by FTIR. Moisture-cured products were studied using FTIR and dielectric spectroscopy (temperature-stimulated discharge current method). Standard procedures were applied for testing mechanical properties (tensile strength, 100% modulus, elongation at break, Shore A hardness, tear strength) and coating properties (adhesion, hardness, low temperature flexibility, water and solvent resistance) of both MCPSUR and ADPSUR. The synthesis of ADPSUR followed the standard procedure for aqueous anionic PUR dispersions described in the literature [75]. Dimethylolpropionic acid (DMPA) was used to introduce COOH groups to the prepolymer chain. Three different ADPSUR were synthesised in this study: ADPSUR- 1: from SOD-l, IPDI and DMPA ADPSUR-2: from SOD-l, IPDI and DMPA, but using different NCOjOH ratios ADPSUR-3: from SOD-2, IPDI, DMPA and a blend of saturated polyesterdiols usuallly recommended for PUR used for coating applications The Si(Me),O content in the dispersion solids was 45, 45 and 4%, respectively.

3. Results and discussion 3.1. Moisture -curable PS UR (MCPSUR) The substantial properties of NCO-terminated siloxaneurethane prepolymers obtained in the reaction of SOD-l and SOD-2 with IPDI and TMXDI (SOD-l only) are presented in Table 1. From thesse results it can be calculated that viscous, clear, optically homogeneous prepolymers can be easily obtained in the reaction between siloxane oligomer diols and diisocyanates. FTIR and NMR evidence showed that no free hydroxyl groups were in the reaction products, and then the reaction was considered complete. The molecular weight of the prepolymers (see Fig. 3 for GPC chromatograms of SOD-l and SOD-l IPDI prepolymer) depended on both the SOD and diisocyanate structure. Changing SOD from less hydrophobic (R, = -(CH,),-0-(CH,),-Oin SOD-l) to more hydrophobic (R, = -(CH,),-Oin SOD-2) resulted in a much higher prepolymer viscosity in the latter without appreciably changing the molecular weight. Whereas replacing IPDI by TMXDI led to a lower prepolymer viscosity and higher molecular

126

J. Kozakiewicz

/Progress

in Organic Coatings 27 (1996) 123-131

Table 1 Properties of MCPSUR of structure I obtained in the reaction of siloxane oligomer diols (SOD) with diisocyanates MCPSUR

Properties

Clarity Viscosity (mPas) NC0 (anal.) (%) NC0 (theor.) (%) Free diisocyanate (from GPC) (%) MW M” k&/M, (from GPC) ‘a’ and % of ‘dimer’ (a= 1) M, (from % NCO) M, (from LS) (without microgels)

SOD-l + IPDI

SOD-l + TMXDI

SOD-2 + IPDI

+ 4600 3.14 3.60 3.25

1+160 3.56 3.68 5.60

+ 42800 3.85 6.10 3.69

5329,3415 1.53 2.59 and 30.0

1511,4444 1.69 3.12 and 18.6

5264,3512 1.50 2.89 and 14.0

4112 5430

5153 6200

3802 n.ta

a n.t. = not tested.

weight. The higher molecular weight obtained for TMXDI-based prepolymer can be explained by the equal reactivity of both NC0 groups in TMXDI while the two NC0 groups in IPDI react with OH at different rates. Fig. 4 presents fragments of the 13CNMR spectra of IPDI and the SOD-l-IPDI prepolymer. The properties of the films obtained from MCPSUR after curing with atmospheric moisture are presented in Table 2 and FTIR spectra of both prepolymers and films (for SOD-l-IPDI reaction product only) in Fig. 5. These results show that the mechanical properties of moisture-cured MCPSUR are excellent, especially for the SOD-l-IPDI reaction product, since they combine high tensile strength (over 10 MPa, with a high value of 17 MPa for the SOD-2-IPDI reaction product) and high Shore A hardness (over 50) with very good elasticity (-700%). Tear strength is less than observed for PUR, but shows an increase when compared to silicones. Decomposition characteristics, especially final

decomposition temperatures, are closer to silicones than to PUR. Water resistance is superb - no swell of the films after 24 h immersion was observed. For coating applications, the excellent transparency of the films is also of great importance. Preliminary results of a few standard tests presented in Table 3 suggest that MCPSUR can be considered for use as coating resins, though obviously much effort has still to be made to develop the commercial coating formulation based on MCPSUR. The great advantages of MCPSUR as coating resins would be superb low temperature flexibility combined with excellent water resistance and film toughness. Superb weatherability can also be expected - ageing tests are in progress. However, the main problem in commercial application of such coatings would be the high cost resulting from the very high price of the SOD reactants. To diminish this disadvantage, MCPSUR of structure III would have to

CARBON-13

NMR_

L

20

25

30 the

, mh

Fig. 3. GPC chromatograms of SOD-l and MCPSUR obtained from SOD-l and IPDI. Columns; 104, 103, 102, 500A, THF solvent, PS standards.

Fig. 4. Fragments of i3C NMR spectra of IPDI and MCPSUR obtained in the reaction of SOD-l with IPDI.

J. Kozakiewicz / Progress in Organic Coatings 27 (1996) 123-131

127

Table 2 Properties of moisture-cured MCPSUR films (film thickness = 0.6 mm) Properties

Clarity Tensile strength (MPa) 100% Modulus (MPa) Elongation at break (%) Shore A hardness Tear strength (N/mm) Decomposition temp. (“C) start end Swell in H,O after 24 h immersion (%)

MCPSUR SOD-l + IPDI

SOD-I + TMXDI

SOD-2 + IPDI

+ 10.9 1.3 690 53 26.4

+ 4.0 1.2 740 63 14.8

+ 17.4 4.0 340 70 nt. d

236 668 0

230 683 0

298 680 0

‘n.t. = not tested.

be used, though compatibility problems which could occur in such systems would have to be overcome. The preliminary results of studies on the morphology of the films made of such MCPSUR (containing both SOD and PPG segments in the main chain) which have been synthesised in this study are presented in Table 4. As can be seen from Table 4, film clarity varied depending on the SOD-l/PPG ratio, suggesting limited segment compatibility in some samples. It is interesting that for SOD-1 /PPG = 3/l, a clear film was obtained, indicating that modification of MCPSUR with some amount of polyol is possible without facing compatibility problems. This opportunity will be further examined in the research on MCPSUR carried out in ICRI. It is noteworthy that the film of the same SOD-l/PPG ratio = 3/l made of the mixture of separately prepared SOD-l -1PDI and PPG-IPDI prepolymers showed distinct phase separation, proving the formation of a copolymer, not a mixture of homopolymers, in the reaction between SOD-l/PPG blend and IPDI. This was further proved by GPC data. As can be clearly seen in Fig. 6 which gives results of recording the temperature-related transitions in MCPSUR using the temperature stimulated discharge current method [76] for SOD-l-IPDI and SOD-l-PPGIPDI reaction products, only one transition temperature in the low temperature region which corresponds to T, of the soft (SOD and PPG) segments was observed for the sample made using SOD-1 /PPG = 3/l molar ratio. This suggests no soft segment segregation in this particular MCPSUR. However, for the other SOD- 1/PPG ratios, two separate low-temperature transitions were noticed, see Fig. 6. The other transitions observed for all samples in the room temperature region can be attributed to urethane-diisocyanate hard segments. While this second transition temperature distinctly increased with increasing SOD-l/PPG ratio, Tg corresponding to PPG soft segments remained almost at the

same level, see Fig. 7. This phenomenon is difficult to explain without further studies, including detailed investigations of MCPSUR morphology using TEM and presumably also SAXS. These investigations are in progress now. 3.2. Aqueous dispersions of PSUR (ADPSUR) The properties of three ADPSUR synthesised in this study are presented in Table 5. The measured values ar typical for standard aqueous anionic PUR dispersions used in coating applications. The properties of the films cast from ADPSUR are presented in Table 6. Tensile strength of all samples was very good (over 10 MPa). However, elongation at break was poor though good elasticity of the films could be expected. Only for the sample containing a very small amount of Si(Me),O segments (ADPSUR3) did the elongation at break exceed 100%. These results are only preliminary and further work is needed to improve the properties of ADPSUR films. The results of simple coating tests made for ADPSUR are presented in Table 7. They show that ADPSUR form transparent coatings with good adhesion to steel and excellent low temperature flexibility. Water and solvent resistance, adhesion and hardness are typical for coatings made of standard PUR dispersions. The essential advantage of ADPSUR over standard PUR dispersions should be better weatherability, but accelerated ageing tests would have to be performed to verify this. Both clear and pigmented coating formulations based on ADPSUR are presently being pursued. 4. Conclusions (1) Clear, homogeneous, NCO-terminated PSUR prepolymers (MCPSUR) can be prepared from various siloxane oligomer diols (SOD) and diisocyanates (IPDI or TMXDI).

J. Kozakiewicz /Progress

128

in Organic Coatings 27 (1996) 123-131

I

4000.9

198.7

--

Fig. 5. FTIR spectra of uncured (1) and moisture-cured (2) MCPSUR obtained from SOD-I and IPDI.

(2) The prepolymers can be moisture-cured to form clear, elastic films of very good mechanical strength, elasticity, adhesion and resistance to water. (3) Modification of MCPSUR chains by incorporating long PPG segments leads to less homogeneous products though for a high SOD/PPG molar ratio (3/l) a clear film has been obtained. (4) Moisture-cured MCPSUR containing PPG segments exhibit one or two transitions in the low temperature region attributed to the Tg of soft (polysiloxane and PPG) segments depending on the SOD/PPG molar ratio and one transition in the room temperature region attributed to the hard (urethane-isocyanate) segments. The latter transition temperature increases with increasing SOD/PPG molar ratio.

Table 4 Morphology of moisture-cured MCPSUR films obtained from blends of SOD-l and PPG SOD-l/PPG

Film clarity Synth.”

O/l

+

l/3 l/l 3/l l/O

++ +

Phase separation Mixt.b

Synth.

Mixt.

-

no distinct distinct no no

total total distinct

a Synth. = MCPSUR prepared from SOD-l and PPG blends. b Mixt. = MCPSUR prepared separately from SOD-l and PPG and mixed before curing.

Table 3 Results of preliminary coating tests made for MCPSUR (film thickness = 10 pm) Test

MCPSUR SOD-l + IPDI

SOD-2 + IPDI

Film appearance (on glass)

clear, transparent, tough, and flexible films; very smooth, silicone rubber-like surface

clear, transparent, tough, and flexible films; very smooth, silicone rubber-like surface

Adhesion test (on steel, 2 mm grid)

lo-20% delamination of the film

no delamination of the film

Low temperature flexibility (on steel and aluminium, 24 h at - 15 “C, 2 mm diameter pin)

no cracks, no delamination of the film; film remains transparent

no cracks, no delamination of the film; film remains transparent

Elevated temperature behavior (on steel and aluminium, 6 h at 70 “C)

no flow, no cracks, no delamination of the film; film remains transparent

no flow, no cracks, no delamination of the film; film remains transparent

Water resistance (on glass, 4 days immersion)

good, no changes in the film observed

good, no changes in the film observed

Solvent resistance (on glass, MEK rubs)

poor, less than 50

poor, less than 50

J. Kozakiewicz / Progress in Organic

Fig. 6. Results of recording the temperature-related method.

Coatings

27 (1996)

129

123-131

transitions in moisture-cured MCPSUR using the temperature-stimulated

20

TPM Y

Table 6 Properties of air-dried films cast from ADPSUR (film thickness = 0.4 mm)

-10

Properties

ADPSUR-I

ADPSUR-2

ADPSUR-3

Clarity Tensile strength (MPa) 100% Modulus (MPa) Elongation at break (%) Swell in Ha0 (24 h immersion) (%) Swell in xylene (24 h immersion) (%)

+ 12.6 48 0

+ 12.2 102 0

+ 10.0 8.5 127 200

130

150

- 30

LO

discharge current

0

40

.-70

-io

Fig. 7. Effect of composition of MCPSUR made of blends of SOD-I and PPG on transition temperatures related to PPG soft segments (Trro), and urethaneediisocyanate hard segments (TH). Table 5 Properties of aqueous dispersions of PSUR (ADPSUR) Properties

ADPSUR-I

ADPSUR-2

ADPSUR-3

PH Solids content, (%) Viscosity (mPas) Stability (min) (centrifuge test)

7.6 29 30 over 120

8.8 34 230 90

7.6 35 60 over 120

(5) Stable aqueous anionic dispersions of PSUR (ADPSUR) can be prepared from SOD and IPDI using DMPA as COOH supplying reactant. ADPSUR can be also prepared either by using SOD as the only diol

reactant or by modification of the diol reactants used in standard PUR dispersions by incorporating a small amount of SOD. The films obtained from ADPSUR are tough, but their elasticity is rather poor (elongation at break below 100%). The coating properties of ADPSUR are similar to standard PUR dispersions.

Acknowledgements

The author thanks Professor Dr M.W. Urban from the Department of Polymers and Coatings of North Dakota State University for helpful discussions. The assistance of M. Cholinska, S. Iwanska, M. Skariynski and P. Myslinski from the Industrial Chemistry Research Institute in the characterization of MCPSUR samples by GPC, FTIR, NMR and dielectric spectroscopy is also gratefully acknowledged.

J. Kozakiewicz /Progress

130

in Organic Coatings 27 (1996) 123-131

Table I Results of preliminary coating tests made for ADPSUR (film thickness = 100 pm) Testa

ADPSUR-1

ADPSUR-2

ADPSUR-3

Film appearance (on glass)

clear, transparent, tough films of silicon rubber-like like surface

clear, transparent, tough films of silicon rubber-like like surface

clear, transparent, tough, hard film

Adhesion test (on steel 2 mm grid) ad adcx, td, tdcx Low temperature flexibility (on steel, 24 h at - 15 “C, 2 mm diameter pin) ad, adcx, td, tdcx

no delamination of the film no delamination of the film

no delamination of the film no delamination of the film

lo-20% delamination no delamination of the film

no cracks

no cracks

no cracks

Water resistance (on glass, 4 days immersion) ad, adcx, td, tdcx

clear film, small bubbles visible

opaque film, small bubbles visible

clear film, no bubbles

Solvent resistance (on glass) ad (50 MEK rubs) adcx (50 MPK rubs) td (80 MEK rubs) tdcx (80 MEK rubs)

poor good good good

good good good good

poor good good good

Hardness on glass (Persoz) td tdcx

0.22 0.19

0.19 0.18

0.4 0.4

aCX-lOO = aziridine crosslinking agent; ad = air-dried, no CX-100; adcx = air-dried, CX-100 added; td = dried at 120 ‘C; tdcx = dried at 120 ‘C, CX-I 00 added.

References PI B. Arkles and C. Carreno, Polym. Mater. Sci. Eng., 50 (1984) 440.

PI W. Lemm and E. Buecherl,

Adu. Eiomater., 3 (1982) 459.

[31 J.R. Ebdon, D.J. Hourston and PG. Klein, Adu. Chem. Ser., 211 (Multicompon. Polym. Mater.) (1986) 179.

[41 P. Knaub, Y. Camberlin and J.F. Gerard, Polymer, 29 (1988) 1365.

[51 J.R. Ebdon and D.J. Hourston, Polymer, 27 (1986) 1807. PI P.G. Klein, J.R. Ebdon and D.J. Hourston, Polymer, 29 (1988) 1079.

[71 X. Yu, M.R. Nagarajan, T.G. Grasel, P. Gibson and S.L. Cooper: J. Polym. Sci., Polym. Phys. Ed., 23 (1985) 2319. PI X. Yu and M.R. Nagarajan, J. Polym. Sci., Polym. Phys. Ed., 24 (1986) 2681.

[91 C. Li, X. Yu, T. Speckhard and S. Cooper, J. Polym. Sci., Polym. Phys. Ed., 26 (1988) 315.

[lOI R.A. Philips, C.J. Stevenson, M.R. Nagarajan and S. Cooper, J. Polym. Sci., Polym. Phys. Ed., 27 (1989) 245.

[ill M. Shibayama, M. Inoue, T. Yamamoto and S. Nomura, Polymer, 31 (1990) 349.

[121 V.Ya Kotonyuk, E.P. Lebedev, V.A. Baburina and O.N. Shulyakova, Kriemniorg. Sojed. Mater. Ikh Osnov., TR Soviesn. Khim. Prakt. Primien, Kriemniorg. Sojed. 5th, 1982, p. 144; Chem. Abstr., 25314 T. [13] S. Pan and V. Zhou, Zhongguo Shengwu Yixne Gongcheng Xuebao, 7(1988) 132; Chem. Abstr., 110 101721 F. [14] A.Z. Okhema and D.J. Fabrizius, Biomaterials, 10 (1989) 23.

P51 R. Benrashid, G.L. Nelson, J.H. Linn, K.H. Hanley and W.R. Wade, J. Appl. Polym. Sci., 49 (1993) 523. [I61 R.M. Stewart, G.E. Heinig and F.L. Keohan, Proc. WaterBorne, Higher Solids and Powder Coatings Symp., New Orleans, 26-28 Feb. 1992, p. 258. P71 R.M. Stewart, G.E. Heinig and F.L. Keohan, Mod. Plast. Coat., 82 (10) (1993) 39 and 45.

WI V.P. Kuznyetsova,

K.V. Zapunnaya

and V.N. Lemyeshko,

Lakokras. Mat. Ikh Primen., (2) (1983) 26. 1191W.Y. Chiang and W.J. Shu, Angew. Makromol. Chem., 160 (1988) 41. WI W.Y. Chiang and W.J. Shu, J. Appl. Polym. Sci., 36(1988) 1889. I211 Paint Resin, 54 (5) (1984) 24. [221 JP 60 34453 (Nippon Zeon); Chem. Abstr., 103 42681~. 1231 US 4 836 646 (Dow Chemical). 1241DE 3 309 657 (Nippon Zeon); Chem. Abstr., 100 12697d. v51 JP 2 041 325 (Toshiba). 1261EP 367 720 (Ciba Geigy). v71 WO 92 09 650 (Bausch and Lomb); Chem. Abstr., 118 105093. WI JP 61 285 270 (Shin-Emu); Chem. Abstr., 107 79651x. 1291HU 891 228; Chem. Abstr., 113 8110~. [301 WO 90 06 968 (Bramite); Chem. Abstr., 114 64410~. [311 SU 827 508; Chem. Abstr., 95 82559n. 1321JP 2 135 210 (Hitachi-Maxell). [331 JP 05 25 239 (Toa Gosei); Chem. Abstr., 119 1059Og. [341 JP 04 266 978 (Toyoda Gosei); Chem. Abstr., 118 171138k. [351 JP 04 266 979 (Toyoda Gosei); Chem. Abstr., 118 171139m. [361 JP 04 292 676 (Toyoda Gosei); Chem. Abstr., 118 105048e. I371 JP 04 236 280 (Toyoda Gosei); Chem. Abstr., 118 105008s. [381 DE 2 908 628 (Bayer); Chem. Abstr., 93 206167~.

J. Kozakiewicz [39] DE 3 730 780 (Chem. Fabrik Stockhausen);

/ Progress

in Organic Coatings 27 (1996) 123-131

Chem. Abstr.,

111

[40] DE 3 507 467 (Bayer); Chem. Abstr., 106 6557r. [41] JP 60 09 973 (Danippon Ink and Chemicals); Chem. Abstr.,

102

222123f. [42] JP 2 112 486 (Dainichiseika). [43] JP O-5163 682 (Danippon Ink and Chemicals); Chem. Abstr.,

120

41318p.

32528r. [44] JP 58 222 436 (Konishiridu Photo Industry); Chem. Abstr., [45]

[46] [47] [48] [49] [50] [51] [52] [53] [54] [55] [56] [57] [58]

[59]

211806p. DE 3 929 168 (BASF). JP 2 165 412 (Daiichi Phann.). JP 2 103 718 (Dainichiseika). JP 2 113 421 (Dainichiseika). JP 2 294 926 (Hitachi-Maxwell). JP 3 237 157 (Sanyo). JP 3 071 454 (Teijin). JP 1 112 517 (Toyobo). JP 1 075 513 (Dainichiseika). JP 2 102 096 (Dainichiseika). JP 2 000 555 (Dainichiseika). JP 1 011 888 (Dainichiseika). JP 05 131 770 (Ricoh); Chem Abstr., JP 04 278 391 (Ricoh); Chem Abstr., JP 1 284 571 (Arakawa).

100

[60] US 5 057 377 (Ciba Geigy). [61] JP 63 282 236. [62] EP 298 364 (Hoechst). [63] EP 325 918 (Chem. Fabr. Pfersee). [64] EP 293 084. [65] JP 04 279 686 (Toyoda Gosei); Chem. Abstr., 118 215029. [66] EP 324 081 (General Electric). [67] JP 60 104 115 (Danippon Printing); Chem. Abstr., 103 1618178. [68] JP 04 209 679 (Nippon Polyurethane Ind.); Chem. Abstr., 118 104989a. [69] JP 1 149 882 (Dainichiseika). [70] GE 2 218 637 (Smith and Nephew). [71] JP 05 17 708 (Toyobo). [72] JP 05 59 306 (Toyo Bosheki). [73] J. Kozakiewicz and A. Lendzion, Proc. 13th Munich Adhesives and Finishing Seminar, Chemical and Radiation Munich, Germany, 1988, p. 50.

119 22821Oe. 118 105081k.

131

Curing Systems,

[74] J. Kozakiewicz, M. Zielecka and P. Rosciszewski, Poster presented at Proc. 10th Int. Symp. Organosilicon Chemistry, Poznan, Aug. 1993. [75] J. W. Rosthauser and K. Nachtkamp, Adv. Urethane Sci. Technol., 10 (1987) 121. [76] P. Myslinski, J. Kozakiewicz and A. Winiarska, Proc. Polish Chemical Society Meet., Torun, Sept. 1993, Papers S-2,

P-9.