Copolymer and molded body

Patent metadata

Field	Value
Publication number	US-9856342-B2
Application number	US-201314768569-A
Country	US
Kind code	B2
Filing date	Dec 27, 2013
Priority date	Feb 18, 2013
Publication date	Jan 2, 2018
Grant date	Jan 2, 2018

Abstract

A copolymer comprising a structural unit (I) derived from a phosphonate monomer (1) such as diethyl methacryloyloxymethyl phosphonate, diethyl 2-methacryloyloxyethyl phosphonate and the like, and a structural unit (II) derived from a radical polymerizable monomer (2) such as methacrylic acid, acrylic acid, 8-tricyclo[5.2.1.0 2,6 ]decanyl methacrylate, t-butyl methacrylate and the like, wherein the content of phosphorus atoms from the phosphonate monomer (1) is 2.0 to 6.0% by mass relative to the mass of the copolymer. A formed article comprising the copolymer.

First claim

The invention claimed is:

1. A copolymer comprising:
a structural unit (I) derived from a phosphonate monomer (1) represented by formula (1); and
a structural unit (II) derived from at least one radical polymerizable monomer (2) selected from the group consisting of methacrylic acid, acrylic acid, a radical polymerizable monomer represented by formula (2a), a radical polymerizable monomer represented by formula (2b) and a radical polymerizable monomer represented by formula (2c);
wherein:
a content of phosphorus derived from the phosphonate monomer (1) is 2.0 to 6.0% by mass relative to the mass of the copolymer;
the copolymer has a glass transition temperature of 90 to 180° C.;

in the formula (1), R 1 represents a hydrogen atom or a methyl group; R 2 represents an alkylene group having 1 to 4 carbon atoms; and R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;

in the formula (2a), R 5 represents a polycyclic aliphatic hydrocarbon group or an alkyl substituted monocyclic aliphatic hydrocarbon group;

in the formula (2b), R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and R 8 represents an alkyl group having 1 to 10 carbon atoms; and

in the formula (2c), R 9 represents —CH 2 CHR 10 R 11 , —CHR 10 —CHR 11 R 12 or —CR 10 R 11 R 13 ; and R 10 , R 11 and R 13 each independently represent an alkyl group having 1 to 3 carbon atoms; and R 12 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

2. The copolymer according to claim 1 , comprising 5 to 60% of the structural unit (II) by mass relative to the mass of the copolymer.

3. The copolymer according to claim 1 , wherein R 5 is selected from the group consisting of a norbornyl group, an isobornyl group, a tricyclodecanyl group, a dicyclopentadienyl group, an adamanthyl group, and a 4-t-butylcyclohexyl group.

4. A formed article comprising the copolymer according to claim 1 .

5. The formed article according to claim 4 , which is a film or a sheet.

6. A layered product comprising the formed article according to claim 4 .

7. The copolymer according to claim 1 , further comprising a structural unit (III) derived from a radical polymerizable monomer (3) that is different from the phosphonate monomer (1) and the radical polymerizable monomer (2).

8. The copolymer according to claim 1 , wherein a weight average molecular weight of the copolymer is fifty thousand to one million.

9. A copolymer selected from the group consisting of a methyl methacrylate/methacrylic acid/diethyl methacryloyloxymethyl phosphonate copolymer, a methyl methacrylate/methacrylic acid/diethyl 2-methacryloyloxyethyl phosphonate copolymer, a methyl methacrylate/acrylic acid/diethyl methacryloyloxymethyl phosphonate copolymer, a methyl methacrylate/acrylic acid/diethyl 2-methacryloyloxyethyl phosphonate copolymer, a methyl methacrylate/8-tricyclo[5.2.1.0 2,6 ]decanyl methacrylate/diethyl methacryloyloxymethyl phosphonate copolymer, a methyl methacrylate/8-tricyclo[5.2.1.0 2,6 ]decanyl methacrylate/diethyl 2-methacryloyloxyethyl phosphonate copolymer, a methyl methacrylate/2-isobornyl methacrylate/diethyl methacryloyloxymethyl phosphonate copolymer, a methyl methacrylate/2-isobornyl methacrylate/diethyl 2-methacryloyloxyethyl phosphonate copolymer, a methyl methacrylate/5-methyl-3-methylidynedihydrofuran-2(3H)-one/diethyl methacryloyloxymethyl phosphonate copolymer, a methyl methacrylate/5-methyl-3-methylidynedihydrofuran-2(3H)-one/diethyl 2-methacryloyloxyethyl phosphonate copolymer, a methyl methacrylate/t-butyl methacrylate/diethyl methacryloyloxymethyl phosphonate copolymer, a methyl methacrylate/t-butyl methacrylate/diethyl 2-methacryloyloxyethyl phosphonate copolymer, a styrene/methacrylic acid/diethyl methacryloyloxymethyl phosphonate copolymer, a styrene/methacrylic acid/diethyl 2-methacryloyloxyethyl phosphonate copolymer, a methyl methacrylate/8-tricyclo[5.2.1.0 2,6 ]decanyl methacrylate/diethyl 2-methacryloyloxyethyl phosphonate/methyl acrylate copolymer, a methyl methacrylate/8-tricyclo[5.2.1.0 2,6 ]decanyl methacrylate/methacrylic acid/diethyl 2-methacryloyloxyethyl phosphonate copolymer, and a methyl methacrylate/8-tricyclo[5.2.1.0 2,6 ]decanyl methacrylate/t-butyl methacrylate/diethyl 2-methacryloyloxyethyl phosphonate copolymer;
wherein a content of phosphorus derived from diethyl methacryloyloxymethyl phosphonate monomers or diethyl 2-methacryloyloxyethyl phosphonate monomers is 2.0 to 6.0% by mass relative to the mass of the copolymer.

10. A formed article comprising the copolymer according to claim 9 .

11. The formed article according to claim 10 , which is a film or a sheet.

12. A layered product comprising the formed article according to claim 10 .

13. A copolymer comprising:
a structural unit (I) derived from a phosphonate monomer (1) represented by formula (1); and
a structural unit (II) derived from at least one radical polymerizable monomer (2) selected from the group consisting of methacrylic acid, acrylic acid, a radical polymerizable monomer represented by formula (2a), a radical polymerizable monomer represented by formula (2b) and a radical polymerizable monomer represented by formula (2c);
wherein:
the structural unit (I) is present in an amount of 15 to 28% of by mole relative to a total number of moles of structural units in the copolymer;
a content of phosphorus derived from the phosphonate monomer (1) is 2.0 to 6.0% by mass relative to the mass of the copolymer;

in the formula (1), R 1 represents a hydrogen atom or a methyl group; R 2 represents an alkylene group having 1 to 4 carbon atoms; and R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;

in the formula (2a), R 5 represents a polycyclic aliphatic hydrocarbon group or an alkyl substituted monocyclic aliphatic hydrocarbon group;

in the formula (2b), R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and R 8 represents an alkyl group having 1 to 10 carbon atoms; and

in the formula (2c), R 9 represents —CH 2 CHR 10 R 11 , —CHR 10 —CHR 11 R 12 or —CR 10 R 11 R 13 ; and R 10 , R 11 and R 13 each independently represent an alkyl group having 1 to 3 carbon atoms; and R 12 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

14. A formed article comprising the copolymer according to claim 13 .

15. The formed article according to claim 14 , which is a film or a sheet.

16. A layered product comprising the formed article according to claim 14 .

17. A copolymer comprising:
a structural unit (I) derived from a phosphonate monome

Assignees

• Kuraray Co

Inventors

• Abe Toru
• Nakahara Atsuhiro
• Konishi Hiroyuki
• Ozawa Hiroshi

Classifications

• C08F220/10

  Esters · CPC title

• C08F230/02 Primary

  containing phosphorus · CPC title

• C08F212/08

  Styrene · CPC title

• C08F220/14

  Methyl esters {, e.g. methyl (meth)acrylate} · CPC title

• C08F220/68 Primary

  Esters · CPC title