Claims
- 1. A polymer obtained by curing, using a base catalyst, a first component and a second component, wherein said first component comprises at least one acetoacetylated polymer resin and wherein said second component comprises at least one NCO-free urethane polymer resin having vinylic end groups, wherein said base catalyst is tetramethylguanidine.
- 2. A polymer obtained by curing a first component and a second component in the presence of a base catalyst, wherein:
- (i) said first component comprises at least one acetoacetylated polymer resin; and
- (ii) said second component comprises at least one NCO-free urethane polymer having vinylic end groups and corresponding to one of formula (iv) to (vi); wherein
- formula (iv) is:
- CH.sub.2 .dbd.C(R.sup.1)--CO--O--R.sup.2 --O--(CO--NH--B--NH--CO--O--A--O).sub.n CO--NH--B--NH--CO--O--R.sup.2 --O--CO--C(R.sup.1).dbd.CH.sub.2
- formula (v) is:
- (CH.sub.2 .dbd.C(R.sup.1)COOR.sup.2 OCONH).sub.m X, and
- formula (vi) is:
- (CH.sub.2 .dbd.C(R.sup.1)COOR.sub.2 OCOHNBNHCOO).sub.p A
- wherein:
- each R.sup.1 is independently H or CH.sub.3 ;
- each R.sub.2 is independently a C.sub.2-3 linear or branched saturated alkylene moiety;
- each B is independently a C.sub.2-12 linear or branched saturated alkylene moiety, or a C.sub.4-14 cyclic saturated alkylene moiety, or a C.sub.6-12 arylene moiety;
- each A is independently a C.sub.2-12 linear or branched saturated alkylene moiety, or a C.sub.4-12 cyclic saturated alkylene moiety, or a C.sub.6-12 arylene moiety;
- X is a C.sub.2-12 linear or branched saturated alkylene moiety, or a C.sub.4-12 cyclic saturated alkylene moiety, or a C.sub.6-12 arylene moiety;
- n is an integer of from 1 to 10;
- m is 2, 3 or 4; and
- p is 2, 3 or 4, wherein said base catalyst is tetramethylguandine.
- 3. The polymer of claim 1, wherein said acetoacetylated polymer resin is a (meth)acrylic resin which is a copolymer obtained by copolymerizing 10 to 60 wt. % of a monomer of formula (I)
- CH.dbd.C(R.sup.1)--COO--CH.sub.2 CH.sub.2 --O--CO--CH.sub.2 --CO--CH.sub.3 (I)
- with 90 to 40 wt. % of an alkyl (meth)acrylate of formula (II)
- CH.sub.2 .dbd.C(R)--CO--OR
- wherein R is C.sub.1-12 linear or branched saturated alkyl and R.sup.1 is H or CH.sub.3.
- 4. The polymer of claim 3, wherein said NCO-free urethane polymer is a polymer of formula (IV)
- CH.sub.2 .dbd.C(R.sup.1)--CO--O--R.sup.2 --O--(CO--NH--B--NH--CO--O--A--O).sub.n CO--NH--B--NH--CO--O--R.sup.2 --O--CO--C(R.sup.1).dbd.CH.sub.2 (IV)
- wherein:
- each R.sup.1 is independently H or CH.sub.3 ;
- each R.sup.2 is independently a C.sub.2-3 linear or branched saturated alkylene moiety;
- each B is independently a C.sub.2-12 linear or branched saturated alkylene moiety, or a C.sub.4-12 cyclic saturated alkylene moiety, or a C.sub.6-14 arylene moiety;
- each A is independently a C.sub.2-12 linear or branched saturated alkylene moiety, or a C.sub.4-12 cyclic saturated alkylene mioiety, or a C.sub.6-14 arylene moiety; and
- n is an integer of from 1 to 10.
- 5. The polymer of claim 3, wherein said NCO-free urethane polymer is a polymer of formula (V):
- (CH.sub.2 .dbd.C(R.sup.1)CO--O--R.sup.2 O--CO--NH).sub.m X (V)
- wherein:
- each R.sup.1 is independently H or CH.sub.3 ;
- each R.sup.2 is independently a C.sub.2-3 linear or branched saturated alkylene moiety;
- X is a C.sub.2-12 linear or branched saturated alkylene moiety, or a C.sub.4-12 cyclic saturated alkylene moiety, or a C.sub.6-14 arylene moiety; and
- m is 2, 3 or 4.
- 6. The polymer of claim 3, wherein said NCO-free urethane polymer is a polymer obtained by:
- (1) reacting a reaction mixture of a C.sub.2-12 linear, branched or cyclic alkyl or aryl polyol having an average of 2 to 4 hydroxyl groups per molecule and a C.sub.2-14 linear, branched or cyclic saturated alkyl or aryl diisocyanate, triisocyanate, tetraiisocyanate, or a mixture thereof, at 5.degree. to 20.degree. C., using a molar ratio of OH groups to NCO lowers than 1.0;
- (2) raising the temperature of the mixture of step (1) to 40.degree. to 150.degree. C. and maintaining said temperature at 40.degree. to 150.degree. C. until an NCO content of 4 to 20 wt. % in the reaction mixture is reached;
- (3) adding a hydroxyl substituted alkyl (meth)acrylate of formula (III)
- CH.sub.2 .dbd.C(R.sup.1)--CO--O--R.sup.2 --OH (III)
- wherein: R.sup.1 is H or CH.sub.3 ; and R.sup.2 is a C.sub.2-3 linear or branched saturated alkylene moiety; and maintaining the temperature at 40.degree. to 150.degree. C. until the NCO content of the mixture is below 2 wt. %;
- (4) adding to the reaction mixture a C.sub.1-4 alcohol in an amount appropriate to obtain a molar ratio of OH groups to NCO groups greater than 1.5; and
- (5) obtaining a NCO-free urethane polymer.
- 7. The polymer of claim 3, wherein said acetoacetylated (meth)acrylic resin is obtained by reacting said monomer of formula (I) with said alkyl (meth)acrylate of formula (II) and styrene.
- 8. The polymer of claim 1, wherein said acetoacetylated polymer resin is an acetoacetylated polyester resin obtained by either (1) subjecting hydroxyl group--containing polyester and a C.sub.1-4 alkyl acetoacetate to a transesterification reaction, or (2) subjecting an unsaturated polyester and at least one monomer of formula (I)
- CH.sub.2 .dbd.C(R.sup.1)--COO--CH.sub.2 CH.sub.2 --O--CO--CH.sub.2 --CO--CH.sub.3 (I)
- wherein R.sup.1 is H or CH.sub.3, to a graft polymerization reaction.
- 9. The polymer of claim 8, wherein said NCO-free urethane polymer is a polymer of formula (IV)
- CH.sub.2 .dbd.C(R.sup.1)--CO--O--R.sup.2 --O--(CO--NH--B--NH--CO--O--A--O).sub.n CO--NH--B--NH--CO--O--R.sup.2 --O--CO--C(R.sup.1).dbd.CH.sub.2 (IV)
- wherein:
- each R.sup.1 is independently H or CH.sub.3 ;
- each R.sup.2 is independently a C.sub.2-3 ; linear or branched saturated alkylene moiety;
- each B is independently a C.sub.2-12 linear or branched saturated alkylene moiety, or a C.sub.2-12 cyclic saturated alkylene moiety, or a C.sub.6-14 arylene moiety;
- each A is independently a C.sub.2-12 linear or branched saturated alkylene moiety, or a C.sub.4-12 cyclic saturated alkylene moiety, or a C.sub.6-14 arylene moiety; and
- n is an integer of from 1 to 10.
- 10. The polymer of claim 8, wherein said NCO-free urethane polymer is a polymer of formula (V):
- (CH.sub.2 .dbd.C(R.sup.1)CO--O--R.sup.2 --O--CONH).sub.m X (V)
- wherein:
- each R.sup.1 is independently H or CH.sub.3 ;
- each R.sup.2 is independently a C.sub.2-3 linear or branched saturated alkylene moiety;
- X is a C.sub.2-12 linear or branched saturated alkylene moiety, or a C.sub.4-14 cyclic saturated alkylene moiety, or a C.sub.6-14 arylene moiety; and
- m is 2, 3 or 4.
- 11. The polymer of claim 8, wherein said NCO-free urethane polymer is a polymer obtained by:
- (1) reacting a mixture of C.sub.2-12 linear, branched or cyclic alkyl or aryl polyol having an average of 1 to 4 hydroxyl groups per molecule and a C.sub.2-12 linear, branched or cyclic saturated alkyl or aryl diisocyanate, triisocyanate, tetraiisocyanate, or mixture thereof, at 5.degree. to 20.degree. C.;
- (2) raising the temperature of the mixture of step (1) to 40.degree. to 150.degree. C. and maintaining said temperature at 40.degree. to 150.degree. C. until an NCO content of 4 to 20 wt. % in the reaction mixture is reached;
- (3) adding a hydroxyl substituted alkyl (meth)acrylate of formula (III)
- CH.sub.2 .dbd.C(R.sup.1)--CO--O--R.sup.2 --OH (III)
- wherein: R.sup.1 is H or CH.sub.3 ; and R.sup.2 is a C.sub.2-3 linear or branched saturated alkylene moiety; and maintaining the temperature at 40.degree. to 150.degree. C. until the NCO content of the mixture is below 2 wt. %.
- (4) adding to the reaction mixture a C.sub.1-4 alcohol is an amount appropriate to obtain a molar ratio of OH groups to NCO groups greater than 1.5; and
- (5) obtaining an NCO-free urethane polymer.
- 12. A polymer obtained by curing a first component and a second component in the presence of a base catalyst, wherein:
- (i) said first component comprises at lest one acetoacetylated polymer resin; and
- (ii) said second component comprises at least one NCO-free urethane polymer having vinylic end groups and corresponding to one of formula (iv) to (vi); wherein
- formula (iv) is:
- CH.sub.2 .dbd.C(R.sup.1)--CO--O--R.sup.2 --O--(CO--NH--B--NH--CO--O--A--O).sub.n CO--NH--B--NH--CO--O--R.sup.2 --O--CO--C(R.sup.1).dbd.CH.sub.2
- formula (v) is:
- (CH.sub.2 .dbd.C(R.sup.1) COOR.sup.2 OCONH).sub.m X, and
- formula (VI) is:
- (CH.sub.2 .dbd.C(R.sup.1)COOR.sub.2 OCONHBNHCOO).sub.p A
- wherein:
- each R.sup.1 is independently H or CH.sub.3 ;
- each R.sub.2 is independently a C.sub.2-3 linear or branched saturated alkylene moiety;
- each B is independently a C.sub.2-12 linear or branched saturated alkylene moiety, or a C.sub.4-14 cyclic saturated alkylene moiety, or a C.sub.6-12 arylene moiety;
- each A is independently a C.sub.2-12 linear or branched saturated alkylene moiety, or a C.sub.4-12 cyclic saturated alkylene moiety, or a C.sub.6-12 arylene moiety;
- X is a C.sub.2-12 linear or branched saturated alkylene moiety, or a C.sub.4-12 cyclic saturated alkylene moiety, or a C.sub.6-12 arylene moiety;
- n is an integer of from about 1 to 10;
- m is 2, 3 or 4; and
- p is 2, 3 or 4, wherein said base catalyst is 1,8-diaza-bicycloundecene.
- 13. A polymer obtained by curing, using a base catalyst, a first component and a second component, wherein said first component comprises at least one acetoacetylated polymer resin and wherein said second component comprises at least one NCO-free urethane polymer resin having vinylic end groups, wherein said base catalyst is 1,8-diaza-bicycloundecene.
- 14. The polymer of claim 13, wherein said acetoacetylated polymer resin is a (meth)acrylic resin which is a copolymer obtained by copolymerizing 10 to 60 wt. % of a monomer of formula (I)
- CH.dbd.C(R.sup.1)--COO--CH.sub.2 CH.sub.2 --O--CO--CH.sub.2 --CO--CH.sub.3 (I)
- with 90 to 40 wt. % of an alkyl (meth)acrylate of formula (II)
- CH.sub.2 .dbd.C(R.sup.1)--CO--OR (II)
- wherein R is C.sub.1-12 linear or branched saturated alkyl and R.sup.1 is H or CH.sub.3.
- 15. The polymer of claim 14, wherein said NCO-free urethane polymer is a polymer of formula (IV)
- CH.sub.2 .dbd.C(R.sup.1)--CO--O--R.sup.2 --O--(CO--NH--B--NH--CO--O--A--O).sub.n CO--NH--B--NH--CO--O--R.sup.2 --O--CO--C(R.sup.1).dbd.CH.sub.2 (IV)
- wherein:
- each R.sup.1 is independently H or CH.sub.3 ;
- each R.sup.2 is independently a C.sub.2-3 linear or branched saturated alkylene moiety;
- each B is independently a C.sub.2-12 linear or branched saturated alkylene moiety, or a C.sub.4-12 cyclic saturated alkylene moiety, or a C.sub.6-14 arylene moiety;
- each A is independently a C.sub.2-12 linear or branched saturated alkylene moiety, or a C.sub.4-12 cyclic saturated alkylene mioiety, or a C.sub.6-14 arylene moiety; and
- n is an integer of from 1 to 10.
- 16. The polymer of claim 14, wherein said NCO-free urethane polymer is a polymer of formula (V):
- (CH.sub.2 .dbd.C(R.sup.1)CO--O--R.sup.2 O--CO--NH).sub.m X (V)
- wherein:
- each R.sup.1 is independently H or CH.sub.3 ;
- each R.sup.2 is independently a C.sub.2-3 linear or branched saturated alkylene moiety;
- X is a C.sub.2-12 linear or branched saturated alkylene moiety, or a C.sub.4-12 cyclic saturated alkylene moiety, or a C.sub.6-14 arylene moiety; and
- m is 2, 3 or 4.
- 17. The polymer of claim 14, wherein said NCO-free urethane polymer is a polymer obtained by:
- (1) reacting a reaction mixture of a C.sub.2-12 linear, branched or cyclic alkyl or aryl polyol having an average of 2 to 4 hydroxyl groups per molecule and a C.sub.2-14 linear, branched or cyclic saturated alkyl or aryl diisocyanate, triisocyanate, tetraiisocyanate, or a mixture thereof, at 5.degree. to 20.degree. C., using a molar ratio of OH groups to NCO groups lower than 1.0;
- (2) raising the temperature of the mixture of step (1) to 40.degree. to 150.degree. C. and maintaining said temperature at 40.degree. to 150.degree. C. until an NCO content of 4 to 20 wt. % in the reaction mixture is reached;
- (3) adding a hydroxyl substituted alkyl (meth)acrylate of formula (III)
- CH.sub.2 .dbd.C(R.sup.1)--CO--O--R.sup.2 --OH (III)
- wherein: R.sup.1 is H or CH.sub.3 ; and R.sup.2 is a C.sub.2-3 linear or branched saturated alkylene moiety; and maintaining the temperature at 40.degree. to 150.degree. C. until the NCO content of the mixture is below 2 wt. %;
- (4) adding to the reaction mixture a C.sub.1-4 alcohol is an amount appropriate to obtain a molar ratio of OH groups to NCO groups greater than 1.5; and
- (5) obtaining a NCO-free urethane polymer.
- 18. The polymer of claim 14, wherein said acetoacetylated (meth)acrylic resin is obtained by reacting said monomer of formula (I) with said alkyl (meth)acrylate of formula II) and styrene.
- 19. The polymer of claim 13, wherein said acetoacetylated polymer resin is an acetoacetylated polyester resin obtained by either (1) subjecting hydroxyl group-containing polyester and a C.sub.1-4 alkyl acetoacetate to a transesterification reaction, or (2) subjecting an unsaturated polyester and at least one monomer of formula (I)
- CH.sub.2 .dbd.C(R.sup.1)--COO--CH.sub.2 CH.sub.2 --O--CO--CH.sub.2 --CO--CH.sub.3 (I)
- wherein R.sup.1 is H or CH.sub.3, to a graft polymerization reaction.
- 20. The polymer of claim 19, wherein said NCO-free urethane polymer is a polymer of formula (IV)
- CH.sub.2 .dbd.C(R.sup.1)--CO--O--R.sup.2 --O--(CO--NH--B--NH--CO--O--A--O).sub.n CO--NH--B--NH--CO--O--R.sup.2 --O--CO--C(R.sup.1).dbd.CH.sub.2 (IV)
- wherein:
- each R.sup.1 is independently H or CH.sub.3 ;
- each R.sup.2 is independently a C.sub.2-3 ; linear or branched saturated alkylene moiety;
- each B is independently a C.sub.2-12 linear or branched saturated alkylene moiety, or a C.sub.2-12 cyclic saturated alkylene moiety, or a C.sub.6-14 arylene moiety; p1 each A is independently a C.sub.2-12 linear or branched saturated alkylene moiety, or a C.sub.4-12 cyclic saturated alkylene moiety, or a C.sub.6-14 arylene moiety; and
- n is an integer of from 1 to 10.
- 21. The polymer of claim 19, wherein said NCO-free urethane polymer is a polymer of formula (V):
- (CH.sub.2 .dbd.C(R.sup.1)CO--O--R.sup.2 --O--CONH).sub.m X (V)
- wherein:
- each R.sup.1 is independently H or CH.sub.3 ;
- each R.sup.2 is independently a C.sub.2-3 linear or branched saturated alkylene moiety;
- X is a C.sub.2-12 linear or branched saturated alkylene moiety, or a C.sub.4-14 cyclic saturated alkylene moiety, or a C.sub.6-14 arylene moiety; and
- m is 2, 3 or 4.
- 22. The polymer of claim 19, wherein said NCO-free urethane polymer is a polymer obtained by:
- (1) reacting a mixture of a C.sub.2-12 linear, branched or cyclic alkyl or aryl polyol having an average of 1 to 4 hydroxyl groups per molecule and a C.sub.2-12 linear, branched or cyclic saturated alkyl or aryl diisocyanate, triisocyanate, tetraiisocyanate, or mixture thereof, at 5.degree. to 20.degree. C.;
- (2) raising the temperature of the mixture of step (1) to 40.degree. to 150.degree. C. and maintaining said temperature at 40.degree. to 150.degree. C. until an NCO content of 4 to 20 wt. % in the reaction mixture is reached;
- (3) adding a hydroxyl substituted alkyl (meth)acrylate of formula (III)
- CH.sub.2 .dbd.C(R.sup.1)--CO--O--R.sup.2 --OH (III)
- wherein: R.sup.1 is H or CH.sub.3 ; and R.sup.2 is a C.sub.2-3 linear or branched saturated alkylene moiety; and maintaining the temperature at 40.degree. to 150.degree. C. until the NCO content of the mixture is below 2 wt. %.
- (4) adding to the reaction mixture a C.sub.1-4 alcohol in an amount appropriate to obtain a molar ratio of OH groups to NCO groups greater than 1.5; and
- (5) obtaining an NCO-free urethane polymer.
Parent Case Info
This application is a continuation of application Ser. No. 07/259,033, filed on Oct. 17, 1988, now abandoned.
US Referenced Citations (20)
Foreign Referenced Citations (6)
| Number |
Date |
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Oct 1985 |
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Continuations (1)
|
Number |
Date |
Country |
| Parent |
259033 |
Oct 1988 |
|
Patent Grant
5132367
