Process for preparing poly(benzoxazines)

Patent metadata

Field	Value
Publication number	US-9896599-B2
Application number	US-201414776087-A
Country	US
Kind code	B2
Filing date	Apr 22, 2014
Priority date	Apr 30, 2013
Publication date	Feb 20, 2018
Grant date	Feb 20, 2018

Abstract

A polymerizable composition is described comprising a benzoxazine, and a tosylate, which when thermolyzed, forms a (meth)acrylamide, a (meth)acrylate, a vinyl ketone, a vinyl ether or a styrenic compound.

First claim

The invention claimed is:

1. A polymerizable composition comprising:
a) a benzoxazine, and
b) a sulfonate compound of the formula:

wherein
R 11 is an alkyl or aryl or combination thereof;
X 1 is —O— or —NR 15 — where R 15 is H or C 1 -C 4 alkyl
n is 0 or 1;
R 12 is H or an alkyl;
R 13 is H or an alkyl;
R 14 is H or an alkyl.

2. The polymerizable composition of claim 1 wherein said sulfonate compound is of the formula:

wherein
R 11 is an alkyl or aryl or combination thereof;
X 1 is —O— or —NR 15 — where R 15 is H or C 1 -C 4 alkyl
n is 0 or 1;
R 12 is H or an alkyl;
R 13 is H or an alkyl;
R 14 is H or an alkyl.

3. The polymerizable composition of claim 1 wherein said sulfonate compound is of the formula:

wherein
R 11 is an alkyl or aryl or combination thereof;
X 1 is —O— or —NR 15 — where R 15 is H or C 1 -C 4 alkyl
n is 0 or 1;
R 12 is H or an alkyl;
R 13 is H or an alkyl;
R 14 is H or an alkyl.

4. The polymerizable composition of claim 1 comprising 0.05 to 10 parts by weight of said sulfonate compound relative to 100 parts by weight of said benzoxazine.

5. The polymerizable composition of claim 1 wherein said benzoxazine compound comprises at least one ring of the formula:

where R is an aryl group.

6. The polymerizable composition of claim 5 wherein said 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, a covalent bond, or a polyvalent (hetero)hydrocarbyl group;
R 5 is the aryl residue of a primary amino compound;
z is at least 1.

7. The polymerizable composition of claim 5 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.

8. The polymerizable composition of claim 1 further comprising a toughening agent.

9. The polymerizable composition of claim 8 , wherein said toughening agent is present at between about 3% and 35% by weight of the benzoxazine.

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

11. 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.

12. A poly(benzoxazine) prepared from the polymerizable composition of claim 1 of the formula:

wherein
R alkyl is the residue of the sulfonate compound; and
“Poly(benzoxazine)” comprises one or more of the following repeat units:

where each R 1 is independently H or an alkyl group, and
“˜” represents attachment to another repeat unit.

13. An article comprising a substrate having a polymerized coating of the poly(benzoxazine) of claim 12 on a surface thereof.

Assignees

• 3M Innovative Properties Co

Inventors

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

Classifications

• C08K5/0025

  Crosslinking or vulcanising agents; including accelerators · CPC title

• C09J179/04

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title

• C08L79/04

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title

• C08K5/42

  Sulfonic acids; Derivatives thereof · CPC title

• C09D179/04 Primary

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title