Production and use of polymers comprising hydroxyl groups and acrylate groups

• US 9,290,611 B2
• Filed: 07/15/2010
• Issued: 03/22/2016
• Est. Priority Date: 07/17/2009
• Status: Active Grant

• Current Assignee: Construction Research & Technology GmbH (BASF SE)
• Original Assignee: BASF SE
• Inventors: Klok, Harm-Anton, Ji, Sanhao, Bruchmann, Bernd, Roesch, Christine
• Primary Examiner(s): JONES JR., ROBERT STOCKTON
• Application Number:
  US13/382,197
• Publication Number:
  US 20120129971A1
• Time in Patent Office: 2,077 Days
• Field of Search: 525/154, 525/400, 525/401, 528/245, 528/246, 528/392
• US Class Current: 1/1
• CPC Class Codes: C08F 222/102 of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• CPC Class Codes: C08G 2/00 Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
• CPC Class Codes: C08G 2/26 with compounds containing carbon-to-carbon unsaturation
• CPC Class Codes: C08G 2261/344 containing heteroatoms
• CPC Class Codes: C08G 61/12 Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule

Abstract

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

Claims

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 C₁-C₈-alkyl, a substituted or unsubstituted C₂-C₈-alkenyl, a substituted or unsubstituted carboxy-C₁-C₈-alkyl, a substituted or unsubstituted C₆-C₁₂-aryl, a substituted or unsubstituted C₆-C₁₂-arylene, a substituted or unsubstituted C₃-C₁₂-cycloalkylene, or a substituted or unsubstituted C₁-C₂₀-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 C₆-C₁₂-arylene, a substituted or unsubstituted C₃-C₁₂-cycloalkylene, or a substituted or unsubstituted C₁-C₂₀-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—

R¹—

CHO

wherein R¹ is a substituted or unsubstituted C₁-C₈-alkyl, a substituted or unsubstituted C₂-C₈-alkenyl, a substituted or unsubstituted carboxy-C₁-C₈-alkyl, a substituted or unsubstituted C₆-C₁₂-aryl, a substituted or unsubstituted C₆-C₁₂-arylene, a substituted or unsubstituted C₃-C₁₂-cycloalkylene, or a substituted or unsubstituted C₁-C₂₀-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 R¹ is a C₆-C₁₂-arylene, a C₃-C₁₂-cycloalkylene, or a C₁-C₂₀-alkylene, any of which is optionally substituted with a halogen, a C₁-C₈-alkyl group, a C₂-C₈-alkenyl group, a carboxyl group, a carboxy-C₁-C₈-alkyl group, a C₁-C₂₀-acyl group, a C₁-C₈-alkoxy group, or a C₆-C₁₂-aryl group.

15. The polymer of claim 14, wherein R¹ is an unsubstituted C₆-C₁₂-arylene, an unsubstituted C₃-C₁₂-cycloalkylene, or an unsubstituted C₁-C₂₀-alkylene.

16. The polymer of claim 15, wherein R¹ is an unsubstituted C₆-C₁₂-arylene or an unsubstituted C₂-C₂₀-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 R¹ is an unsubstituted C₆-C₁₂-arylene or an unsubstituted C₂-C₂₀-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—

R¹—

CHO

wherein R¹ is an unsubstituted C₆-C₁₂-arylene or an unsubstituted C₂-C₂₀-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 R¹ is an unsubstituted C₆-C₁₂-arylene.

31. The polymer of claim 20, wherein R¹ is an unsubstituted C₂-C₂₀-alkylene.

32. The process of claim 24, wherein reacting the dialdehyde compound and the diacrylate compound is 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).

33. The process of claim 24, wherein an amount of the tertiary amine or phosphine is from 1 to 100 mol % with respect to acrylic groups.

34. The polymer of claim 20, wherein the dialdehyde compound is selected from the group consisting of isophthalaldehyde and terephthalaldehyde.