Production and use of polymers comprising hydroxyl groups and acrylate groups

Patent metadata

Field	Value
Publication number	US-9290611-B2
Application number	US-201013382197-A
Country	US
Kind code	B2
Filing date	Jul 15, 2010
Priority date	Jul 17, 2009
Publication date	Mar 22, 2016
Grant date	Mar 22, 2016

Abstract

The present invention relates to polymers which contain hydroxyl groups and acrylate groups, to processes for preparing them, and to their use.

First claim

The invention claimed is:

1. A polymer, comprising:
a hydroxyl group; and
an acrylate group;
wherein:
the polymer is a reaction product of a dicarbonyl compound with a diacrylate compound;
the dicarbonyl compound comprises just two carbonyl groups, each independently selected from the group consisting of an aldehyde group and a keto group, bonded to one another through a substituted or unsubstituted C 1 -C 8 -alkyl, a substituted or unsubstituted C 2 -C 8 -alkenyl, a substituted or unsubstituted carboxy-C 1 -C 8 -alkyl, a substituted or unsubstituted C 6 -C 12 -aryl, a substituted or unsubstituted C 6 -C 12 -arylene, a substituted or unsubstituted C 3 -C 12 -cycloalkylene, or a substituted or unsubstituted C 1 -C 20 -alkylene; and
the dicarbonyl compound and the diacrylate compound are reacted in the presence of at least one tertiary amine or phosphine selected from the group consisting of trimethylamine, triethylamine, tri-n-butylamine, ethyldiisopropylamine, methyldiisopropylamine, N-methylmorpholine, N-methylpiperidine, triethanolamine, N,N-dimethylethanolamine, 2 dimethylaminopyridine, 4-dimethylaminopyridine, diazabicyclooctane, 1,5 diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), pyrrocoline, quinuclidine, quinidine, trimethylphosphine, triethylphosphine, tri-n butylphosphine, dimethylphenylphosphine, and 1,4 diazabicyclo[2.2.2]octane (DABCO).

2. The polymer of claim 1 , wherein the two carbonyl groups are bonded to one another through a unsubstituted C 6 -C 12 -arylene, a substituted or unsubstituted C 3 -C 12 -cycloalkylene, or a substituted or unsubstituted C 1 -C 20 -alkylene.

3. The polymer of claim 1 , wherein the dicarbonyl compound is a dialdehyde.

4. The polymer of claim 3 , wherein the dialdehyde is of formula:
OHC—R 1 —CHO

wherein R 1 is a substituted or unsubstituted C 1 -C 8 -alkyl, a substituted or unsubstituted C 2 -C 8 -alkenyl, a substituted or unsubstituted carboxy-C 1 -C 8 -alkyl, a substituted or unsubstituted C 6 -C 12 -aryl, a substituted or unsubstituted C 6 -C 12 -arylene, a substituted or unsubstituted C 3 -C 12 -cycloalkylene, or a substituted or unsubstituted C 1 -C 20 -alkylene.

5. The polymer of claim 1 , wherein the dicarbonyl compound is selected from the group consisting of succinaldehyde, glutaraldehyde, phthalaldehyde, isophthalaldehyde, and terephthalaldehyde.

6. The polymer of claim 1 , wherein the diacrylate compound comprises at least one selected from the group consisting of a difunctional acrylate of an alkanediol, a difunctional acrylate of a cycloalkane diol, a difunctional acrylate of a lower polyalkylene glycol, and a difunctional acrylate of a diamine.

7. The polymer of claim 1 , wherein the diacrylate compound is at least one diacrylate compound selected from the group consisting of ethylene glycol diacrylate, 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, N,N′-bisacryloyl-2,2-diaminoethane, N,N′-bisacryloyl-1,6-diaminohexane, and N,N′-bisacryloylpiperazine.

8. A process of preparing the polymer of claim 1 , comprising:
reacting the dicarbonyl compound with the diacrylate compound at a temperature of from 0° C. to 100° C. in a stoichiometric ratio of acrylate groups to carbonyl compounds of from 1:0.05 to 1:1.5.

9. A radiation curing process, comprising curing with the polymer of claim 1 .

10. A dual-cure application process, comprising curing with the polymer of claim 1 .

11. A coating material for free-radical curing, radiation curing, dual-cure curing, or a combination thereof, comprising the polymer of claim 1 .

12. The process of claim 8 , comprising reacting the dicarbonyl compound with the diacrylate compound in the presence of a solvent.

13. The process of claim 9 , comprising curing with UV light having a wavelength of from 200 nm to 700 nm.

14. The polymer of claim 4 , wherein R 1 is a C 6 -C 12 -arylene, a C 3 -C 12 -cycloalkylene, or a C 1 -C 20 -alkylene, any of which is optionally substituted with a halogen, a C 1 -C 8 -alkyl group, a C 2 -C 8 -alkenyl group, a carboxyl group, a carboxy-C 1 -C 8 -alkyl group, a C 1 -C 20 -acyl group, a C 1 -C 8 -alkoxy group, or a C 6 -C 12 -aryl group.

15. The polymer of claim 14 , wherein R 1 is an unsubstituted C 6 -C 12 -arylene, an unsubstituted C 3 -C 12 -cycloalkylene, or an unsubstituted C 1 -C 20 -alkylene.

16. The polymer of claim 15 , wherein R 1 is an unsubstituted C 6 -C 12 -arylene or an unsubstituted C 2 -C 20 -alkylene.

17. The process of claim 8 , wherein an amount of the tertiary amine or phosphine is from 1 to 100 mol % with respect to acrylic groups.

18. The polymer of claim 1 , wherein the dicarbonyl compound is selected from the group consisting of isophthalaldehyde and terephthalaldehyde.

19. The polymer of claim 15 , wherein R 1 is an unsubstituted C 6 -C 12 -arylene or an unsubstituted C 2 -C 20 -alkylene.

20. A polymer, comprising:
a hydroxyl group; and
an acrylate group;
wherein:
the polymer is a reaction product of a dialdehyde compound with a diacrylate compound; and
the dialdehyde compound is of formula:
OHC—R 1 —CHO

wherein R 1 is an unsubstituted C 6 -C 12 -arylene or an unsubstituted C 2 -C 20 -alkylene.

21. The polymer of claim 20 , wherein the dialdehyde compound is selected from the group consisting of succinaldehyde, glutaraldehyde, phthalaldehyde, isophthalaldehyde, and terephthalaldehyde.

22. The polymer of claim 20 , wherein the diacrylate compound comprises at least one selected from the group consisting of a difunctional acrylate of an alkanediol, a difunctional acrylate of a cycloalkane diol, a difunctional acrylate of a lower polyalkylene glycol, and a difunctional acrylate of a diamine.

23. The polymer of claim 20 , wherein the diacrylate compound is at least one diacrylate compound selected from the group consisting of ethylene glycol diacrylate, 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, N,N-bisacryloyl-2,2-diaminoethane, N,N′-bisacryloyl-1,6-diaminohexane, and N,N′-bisacryloylpiperazine.

24. A process of preparing the polymer of claim 20 , comprising:
reacting the dialdehyde compound with the diacrylate compound at a temperature of from 0° C. to 100° C., in the presence of a tertiary amine or phosphine, in a stoichiometric ratio of acrylate groups to carbonyl compounds of from 1:0.05 to 1:1.5.

25. A radiation curing process, comprising curing with the polymer of claim 20 .

26. A dual-cure application process, comprising curing with the polymer of claim 20 .

27. A coating material for free-radical curing, radiation curing, dual-cure curing, or a combination thereof, comprising the polymer of claim 20 .

28. The process of claim 24 , wherein reacting the dialdehyde compound with the diacrylate compound is in the presence of a solvent.

29. The process of claim 25 , comprising curing with UV light having a wavelength of from 200 nm to 700 nm.

30. The polymer of claim 20 , wherein R 1 is an unsubstituted C 6 -C 12 -arylene.

31. Th

Assignees

• Klok Harm-Anton
• Ji Sanhao
• Bruchmann Bernd
• Roesch Christine
• Basf Se

Inventors

• Klok Harm-Anton
• Ji Sanhao
• Bruchmann Bernd
• Roesch Christine

Classifications

• C08G2/26

  with compounds containing carbon-to-carbon unsaturation · CPC title

• C08G2261/344

  containing heteroatoms · CPC title

• C08G2/00 Primary

  Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances · CPC title

• C08G61/12 Primary

  Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule · CPC title

• C08F222/1006

  of polyhydric alcohols or polyhydric phenols · CPC title