Low-temperature curable compositions

Patent metadata

Field	Value
Publication number	US-10563040-B2
Application number	US-201715621323-A
Country	US
Kind code	B2
Filing date	Jun 13, 2017
Priority date	Jun 13, 2017
Publication date	Feb 18, 2020
Grant date	Feb 18, 2020

Abstract

This invention pertains to a curable composition comprising a first component having beta-ketoacetate and/or malonate functionalities and a second component having two or more aldehyde functionalities. The compositions can be cured at room temperature or low temperatures to yield crosslinked networks that are capable of providing desirable properties for coating and adhesive applications. The reactive functionalities of beta-ketoacetate, malonate, and aldehyde can be either on polymers as the main binders or on small molecules as the crosslinkers. The curable compositions desirably are either solventless or organic solvent based.

First claim

We claim:

1. A curable composition comprising:
I. a first component having two or more functional groups selected from the group consisting of β-ketoacetate and malonate functional groups;
II. a second component vinyl polymer having two or more aldehyde functional groups; and
III. a basic catalyst.

2. The composition of claim 1 , wherein the ratio of the ketoacetate and/or malonate-functionalities in the first component and the aldehyde functionality in the second component is from about 1.05 to about 1.0.

3. The composition of claim 1 , wherein the first component is a polyester having two or more beta-ketotoacetate groups, or two or more malonate groups or both beta-ketotoacetate groups and malonate groups.

4. The composition of claim 1 , wherein the first component is a polyester having two or more beta-ketotoacetate groups.

5. The composition of claim 1 , wherein the basic catalyst is one or more selected from the group consisting of 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 1,1,3,3-tetramethylguanidine (TMG), 1,4-diazabicyclo[2.2.2]octane (DABCO), triethylamine, N,N-dimethylethanolamine, ammonium hydroxide, triphenylphosphine, and tributyl phosphine.

6. The composition of claim 1 , wherein the basic catalyst is in an amount ranging from 0.5 to 5 weight % based on the total weight of (I) and (II).

7. The composition of claim 1 further comprising one or more organic solvents selected from the group comprising xylene, methyl amyl ketone, methyl ethyl ketone, 2-butoxyethanol, ethyl-3-ethoxypropionate, toluene, propanol, butanol, cyclopentanone, cyclohexanone, ethyl acetate, and butyl acetate.

8. A curable composition comprising:
I. a first component adduct having two or more β-ketoacetate functional groups;
II. a vinyl polymer having two or more aldehyde functional groups; and
III. a basic catalyst.

9. The composition of claim 8 , wherein the adduct is selected from the group comprising 2,2,4,4-tetramethylcyclobutane-1,3-diol diacetoacetate, glycerol triacetoacetate, trimethylpropane triacetoacetate, pentaerythritol tetraacetoacetate.

10. A curable composition comprising:
I. a first component acetoacetate functional polyester comprising the residues of
a. a hydroxyl component comprising:
i. a diol in an amount ranging from 70 to 100 mole %, based on the total moles of (i) and (ii); and
ii. a polyol in an amount ranging from 0 to 30 mole %, based on the total moles of (i) and (ii);

b. a carboxyl component comprising a polycarboxylic acid compound, a derivative of polycarboxylic acid compound, or a combination thereof; and
c. an alkyl acetoacetate, a diketene, or a combination thereof in an amount ranging from about 5 to about 50 weight %, based on the total weight of (a), (b), and (c);

II. a second component having two or more aldehyde functional groups; and
III. a basic catalyst;

wherein the second component is selected from the group comprising 1,3-cyclohexanedicarboxaldehyde (1,3-CHDAL), 1,4-cyclohexanedicarboxaldehyde (1,4-CHDAL), mixtures of 1,3- and 1,4-CHDAL, 2,6-norbornanedicarboxaldehyde, 2,5-norbornane-dicarboxaldehyde, cyclododecane-1,4,8-tricarbaldehyde, 3,(4-formylcyclohexyl)propanal, and their isomers.

11. The composition of claim 10 , wherein the second component is selected from 1,3-cyclohexanedicarboxaldehyde (1,3-CHDAL), 1,4-cyclohexane-dicarboxaldehyde (1,4-CHDAL), and mixtures of 1,3- and 1,4-CHDAL.

12. The composition of claim 11 , wherein the equivalent ratio of the acetoacetate (AcAc) functionality in the first component and the aldehyde (CHO) functionality in the second component is from about 1.05 to about 1.0.

13. A curable composition comprising:
I. a polyester comprising the residues of:
a. a hydroxyl component comprising:
i. a diol in an amount ranging from 70 to 100 mole %, based on the total moles of (i) and (ii); and
ii. a polyol in an amount ranging from 0 to 30 mole %, based on the total moles of (i) and (ii); and

b. malonic acid, its ester, or a combination thereof; and
c. optionally a carboxyl component, other than malonic acid or its ester, comprising a polycarboxylic acid compound, a derivative of polycarboxylic acid compound, or a combination thereof;

II. an aldehyde component selected from the group consisting of 1,3-cyclohexanedicarboxaldehyde (1,3-CHDAL), 1,4-cyclohexanedicarboxaldehyde (1,4-CHDAL), mixtures of 1,3- and 1,4-CHDAL, 2,6-norbornanedicarboxaldehyde, 2,5-norbornanedicarboxaldehyde, cyclododecane-1,4,8-tricarbaldehyde, 3,(4-formylcyclohexyl)propanal, and their isomers; and
III. a basic catalyst that is one or more selected from the group consisting of 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 1,1,3,3-tetramethylguanidine (TMG), 1,4-diazabicyclo[2.2.2]octane (DABCO), triethylamine, N,N-dimethylethanolamine, ammonium hydroxide, triphenyl phosphine, and tributyl phosphine.

14. A curable composition comprising:
I. an acetoacetate functional polyester comprising the residues of:
a. a hydroxyl component comprising:
i. a diol in an amount ranging from 70 to 100 mole %, based on the total moles of (i) and (ii); and
ii. a polyol in an amount ranging from 0 to 30 mole %, based on the total moles of (i) and (ii);

b. a carboxyl component comprising a polycarboxylic acid compound, a derivative of polycarboxylic acid compound, or a combination thereof; and
c. an alkyl acetoacetate, a diketene, or a combination thereof in an amount ranging from about 5 to about 50 weight %, based on the total weight of (a), (b), and (c);

II. an aldehyde component selected from the group consisting of 1,3-cyclohexanedicarboxaldehyde (1,3-CHDAL), 1,4-cyclohexanedicarboxaldehyde (1,4-CHDAL), mixtures of 1,3- and 1,4-CHDAL, 2,6-norbornanedicarboxaldehyde, 2,5-norbornane-dicarboxaldehyde, cyclododecane-1,4,8-tricarbaldehyde, 3,(4-formylcyclohexyl)propanal, and their isomers; and
III. a basic catalyst that is one or more selected from the group consisting of 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 1,1,3,3-tetramethylguanidine (TMG), 1,4-diazabicyclo[2.2.2]octane (DABCO), triethylamine, N,N-dimethylethanolamine, ammonium hydroxide, triphenyl phosphine, and tributyl phosphine.

Assignees

• Eastman Chem Co

Inventors

• Kuo Thauming
• Bhonde Vasudev R
• Hall Phillip Bryan

Classifications

• C08G16/04

  Chemically modified polycondensates · CPC title

• C08G63/16

  Dicarboxylic acids and dihydroxy compounds · CPC title

• C08G63/914 Primary

  derived from polycarboxylic acids and polyhydroxy compounds · CPC title

• C08G63/20

  Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups · CPC title

• C08K5/053

  Polyhydroxylic alcohols · CPC title