(Meth) acrylic block copolymer and process for producing the same

Patent metadata

Field	Value
Publication number	US-9988477-B2
Application number	US-201414767676-A
Country	US
Kind code	B2
Filing date	Mar 5, 2014
Priority date	Mar 18, 2013
Publication date	Jun 5, 2018
Grant date	Jun 5, 2018

Abstract

A (meth)acrylic block copolymer includes a methacrylic polymer block including at least one structural unit derived from a dimethacrylate according to formula (2):

where R 1 is a methyl group, R 2 and R 3 are each independently a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 5, and a (meth)acrylic polymer block having no active energy ray curable groups. A method of preparing the (meth)acrylic block copolymer and an active energy ray curable composition are provided.

First claim

The invention claimed is:

1. A (meth)acrylic block copolymer, comprising:
a methacrylic polymer block (A) having at least one active energy ray curable group represented by formula (1) and comprising structural units derived from a dimethacrylate according to formula (2) and a monomethacrylate:

where R 1 is a methyl group, R 2 and R 3 are each independently a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 5; and
a (meth)acrylic polymer block (B) having no active energy ray curable groups;
wherein:
the methacrylic polymer block (A) has a number average molecular weight of at least 1,000; and
the (meth)acrylic polymer block (B) has a number average molecular weight of at least 3,000.

2. A process for producing the meth(acrylic) block copolymer according to claim 1 , the process comprising:
anionically polymerizing a methacrylate ester in the presence of an organolithium compound, a tertiary organoaluminum compound and at least one Lewis base selected from the group consisting of ethers and tertiary polyamines, then
adding and anionically polymerizing a mono(meth)acrylate;
wherein:
the methacrylate ester comprises 5 to 80 mol % of a dimethacrylate represented by Formula (2) and 95 to 20 mol % of a monomethacrylate:

where R 1 is a methyl group, R 2 and R 3 are each independently a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 5, and
the tertiary organoaluminum compound is represented by Formula (3-1) or (3-2):
AlR 4 (R 5 )(R 6 )  (3-1)

where R 4 is a monovalent saturated hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group, an aryloxy group, or an N,N-disubstituted amino group, and R 5 and R 6 are each independently an aryloxy group or are bonded to each other to form an arylenedioxy group;
AlR 7 (R 8 )(R 9 )  (3-2)

where R 7 is an aryloxy group, and R 8 and R 9 are each independently a monovalent saturated hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group or an N,N-disubstituted amino group.

3. The process according to claim 2 , wherein anionically polymerizing the mono(meth)acrylate comprises adding and anionically polymerizing a monoacrylate after the adding and the anionically polymerizing of the monomethacrylate.

4. The process according to claim 2 , further comprising:
repeating the adding and the anionically polymerizing of the methacrylate esters after the adding and the anionically polymerizing of the mono(meth)acrylate.

5. An active energy ray curable composition comprising the (meth)acrylic block copolymer according to claim 1 .

6. The process according to claim 3 , further comprising:
repeating the adding and the anionically polymerizing of the methacrylate after the adding and the anionically polymerizing of the monoacrylate.

7. The (meth)acrylic block copolymer according to claim 1 , wherein:
the methacrylic polymer block (A) has a number average molecular weight of 1,000 to 1,000,000; and
the (meth)acrylic polymer block (B) has a number average molecular weight of 3,000 to 5,000,000.

8. The (meth)acrylic block copolymer according to claim 7 , wherein a mass ratio of the methacrylic polymer block (A) to the (meth)acrylic polymer block (B) in the copolymer is 90:10 to 5:95.

9. The (meth)acrylic block copolymer according to claim 8 , wherein the dimethacrylate according to formula (2) is 1,1-dimethylpropane-1,3-diol dimethacrylate.

10. The (meth)acrylic block copolymer according to claim 1 , wherein:
the methacrylic polymer block (A) has a number average molecular weight of 1,000 to 300,000; and
the (meth)acrylic polymer block (B) has a number average molecular weight of 5,000 to 1,000,000.

11. The (meth)acrylic block copolymer according to claim 10 , wherein a mass ratio of the methacrylic polymer block (A) to the (meth)acrylic polymer block (B) in the copolymer is 90:10 to 5:95.

12. The (meth)acrylic block copolymer according to claim 11 , wherein the dimethacrylate according to formula (2) is 1,1-dimethylpropane-1,3-diol dimethacrylate.

Assignees

• Kuraray Co

Inventors

• Shimizu Seiya
• Ida Hirotsugu

Classifications

• C08F222/102

  of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate · CPC title

• C09J153/00

  Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers · CPC title

• C08F220/20

  of polyhydric alcohols or phenols {, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate} · CPC title

• C08F297/026

  polymerising acrylic acid, methacrylic acid or derivatives thereof · CPC title

• C08F220/10 Primary

  Esters · CPC title