Benzoxazine polymerization

Patent metadata

Field	Value
Publication number	US-10040905-B2
Application number	US-201415023753-A
Country	US
Kind code	B2
Filing date	Oct 6, 2014
Priority date	Oct 16, 2013
Publication date	Aug 7, 2018
Grant date	Aug 7, 2018

Abstract

Poly(benzoxazine) polymer are prepared by heating a benzoxazine compound in the presence of a (meth)acrylate copolymer having pendent tosylate groups, resulting in an interpenetrating polymer network of a poly(benzoxazine) and a crosslinked (meth)acrylate copolymer.

First claim

What is claimed is:

1. A polymerizable composition comprising:
a) a benzoxazine, and
b) a (meth)acrylate copolymer having pendent tosylate groups;
where the benzoxazine is of the formula:

wherein
each R 1 is H or an alkyl group, and is the residue of an aliphatic aldehyde,
R 2 is H, a covalent bond, a phenol or a polyvalent (hetero)hydrocarbyl group;
R 5 is aryl residue of a primary amino compound, R 5 (NH 2 ) m , where R 5 is an aryl group, m is 1-4;
and x is at least 1.

2. The polymerizable composition of claim 1 wherein the (meth)acrylate copolymer comprises polymerized (meth)acryloyl oxyalkyl tosylate units.

3. The polymerizable composition of claim 2 wherein the (meth)acryloyl oxyalkyl tosylate units are derived from a monomer of the formula

wherein
R 1 is H or CH 3;
R 2 is an C 2 -C 10 alkylene, optionally containing one or more ether oxygen atoms, and
OTs is a tosylate (toluene sulfonate) group.

4. The polymerizable composition of claim 2 , wherein 1 to 100% of the monomer units of the copolymer are (meth)acryloyl oxyalkyl tosylate units.

5. The polymerizable composition of claim 3 wherein R 2 is an alkyleneoxy groups of the formula —C n H 2n —O—C m H 2m —.

6. The polymerizable composition of claim 4 wherein R 2 is an poly(alkyleneoxy) group.

7. The polymerizable composition of claim 1 wherein the a (meth)acrylate copolymer having pendent tosylate groups is used in amounts such that the molar equivalents of tosylate groups are 0.05 to 10 parts by weight, relative to 100 parts by weight of the benzoxazine.

8. The polymerizable composition of claim 1 further comprising hydroxyalkyl (meth)acrylate monomer units.

9. The polymerizable composition of claim 1 , wherein the copolymer is of the formula —[M tosyl ] a —[M ester ] b —[M OH ] c where M tosyl represents polymerized tosylate functional monomer units having subscript “a” repeat units, M ester represents polymerized acrylic ester monomer units having subscript “b” repeat units, and M OH represents polymerized hydroxyalkyl acrylate monomer units having subscript “c” repeat units.

10. The polymerizable composition of claim 9 , where subscript a is 1 to 98% of the repeat units, b is 0 to 98% of the repeat units and c is at least 1% of the monomer units.

11. The polymerizable composition of claim 1 further comprising a toughening agent, wherein said toughening agent is present at between about 3% and 35% by weight of the benzoxazine.

12. The polymerizable composition of claim 1 , further comprising a co-catalyst.

13. The polymerizable composition of claim 1 further comprising a curative, wherein the curative is selected from the group of a thiol compound, an amine compound, and a combination thereof.

14. An interpenetrating polymer network comprising a poly(benzoxazine) polymer and a crosslinked (meth)acrylate polymer, derived from the polymerizable composition of claim 1 .

15. The interpenetrating polymer network of claim 14 wherein the poly(benzoxazine)comprises units of the formula(s):

16. The interpenetrating polymer network of claim 14 comprising 0.05 to 10 parts by weight of the crosslinked acrylate copolymer, relative to 100 parts by weight of the poly(benzoxazine).

17. A method of preparing a poly(benzoxazine) comprising the step of heating the composition of claim 1 to a temperature sufficient to initiate polymerization.

Assignees

• 3M Innovative Properties Co

Inventors

• Gorodisher Ilya
• Webb Robert J
• Joly Guy D
• Griesgraber George W
• Devoe Robert J

Classifications

• C08F220/302

  and two or more oxygen atoms in the alcohol moiety · CPC title

• C08L79/02 Primary

  Polyamines · CPC title

• C08G2270/00

  Compositions for creating interpenetrating networks · CPC title

• C08G73/0233 Primary

  Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups · CPC title

• C08L33/14

  of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen · CPC title