# US 2019/0169370 A1 · Benzoxazine composition

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- Number: US 2019/0169370 A1
- Document ID: US20190169370A1
- Status: Published application
- Kind: A1
- Application number: 16/323,568
- Filed: 2017-09-14
- Published: 2019-06-06
- Earliest claimed: 2016-09-15
- Assignees: 3M Innovative Properties Company
- Applicants: 3M Innovative Properties Company
- Inventors: Gregory P. Sorenson; Ilya Gorodisher; Robert J. Webb
- Web page: https://patentgrep.com/patent/US20190169370A1

## CPC

- C08G 73/0233: {Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups}
- C08G 14/06: and monomers containing hydrogen attached to nitrogen
- C09D 161/34: Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09D161/04, C09D161/18 and C09D161/20
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)

## Abstract

The disclosure provides a catalyst for use with a benzoxazine resins which imparts accelerated curing at reduced temperatures. The catalyst is selected from elemental halogen or onium polyhalide compounds.

## Claims

### Claim 1

A polymerizable composition comprising:
a) a benzoxazine, and
b) an elemental halogen or an onium polyhalide catalyst, wherein the onium polyhalide is of the formula
Q+X(2n+1)−,
where 1≤n≤4,
Q is onium group, selected from ammonium, sulfonium and phosphonium; and
each X is a halide, and when the composition is heated, produces a poly(benzoxazine.

### Claim 2 (depends on 1)

The composition of claim 1 wherein the elemental halogen is used in amounts of 0.5 to 20% by mass relative to the total composition.

### Claim 3 (depends on 1)

The composition of claim 1 wherein the onium polyhalide is used in 0.5 to 20% by mass relative to the total composition.

### Claim 4 (depends on 1)

The composition of claim 1 wherein the onium polyhalide is of the formula
Q+X(2n+1)−,
where 1≤n≤4,
Q is onium group, selected from ammonium, sulfonium and phosphonium; and
each X is a halide.

### Claim 5 (depends on 4)

The composition of claim 4 wherein Q is selected from ammonium groups of the formula (R1)4N+, sulfonium groups of the formula (R1)3S+ or phosphonium groups of the formula (R1)4P+,
wherein each R1 is independently H, alkyl, aryl, or combinations thereof with the proviso that no more than one R1 is H.

### Claim 6 (depends on 4)

The composition of claim 4 wherein Q is a pyridinium, pyrrolidiniun or imidazolium group.

### Claim 7 (depends on 6)

The composition of claim 6 wherein Q is a pyridinium, pyrrolidiniun or imidazolium group of the formulas:
wherein each R1 is independently H, alkyl, aryl, or combinations thereof with the proviso that no more than one R1 is H.

### Claim 8 (depends on 6)

The composition of claim 6 wherein Q is (R1)4N+, wherein each R1 is independently H, alkyl, aryl, or combinations thereof with the proviso that no more than one R1 is H.

### Claim 9 (depends on 4)

The composition of claim 4 wherein subscript n is 2.

### Claim 10 (depends on 1)

The composition of claim 1 wherein said benzoxazine compound comprises at least one ring of the formula:
where R is a (hetero)hydrocarbyl group.

### Claim 11 (depends on 10)

The polymerizable composition of claim 10 wherein said benzoxazine is of the formula:
wherein
each R1 is H or an alkyl group, and is the residue of an aliphatic aldehyde,
R2 is H, a covalent bond, or a polyvalent (hetero)hydrocarbyl group, preferably H, a covalent bond or a divalent alkyl group;
R5 is the (hetero)hydrocarbyl residue of a primary amino compound;
R5 is the residue of a primary amino compound;
z is at least 1.

### Claim 12 (depends on 10)

The polymerizable composition of claim 10 where the benzoxazine is of the formula:
wherein
each R1 is H or an alkyl group, and is the residue of an aliphatic aldehyde,
R2 is H, a covalent bond, a phenol or a polyvalent (hetero)hydrocarbyl group, preferably H, a covalent bond or a divalent alkyl group;
R5 is (hetero)hydrocarbyl residue of a primary amino compound, with the proviso that R2 is not H when subscript x is >1; and
subscript m is 1 to 4.

### Claim 13 (depends on 1)

The polymerizable composition of claim 1 comprising a mixture of two or more benzoxaxines.

### Claim 14 (depends on 1)

The polymerizable composition of claim 1 comprising a benzoxazines derived from poly(alkyleneoxy) diamines.

### Claim 15 (depends on 1)

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

### Claim 16 (depends on 15)

The polymerizable composition of claim 15 wherein the co-curative is of the formula:
R30—(ZH)p (XII)
wherein, in Formula (XII):
R30 is a (hetero)hydrocarbyl group;
each Z is independently —S— or —NR31, where R31 is H or a hydrocarbyl group, including aryl and alkyl; and
p is 1 to 6 (in certain embodiments, p is at least 2).

### Claim 17 (depends on 16)

The polymerizable composition of claim 16, wherein the ratio of the sum of amine and/or thiol groups from the compound R30—(ZH)p, to the benzoxazine groups is about 3:1 to 100:1.

### Claim 18 (depends on 15)

The polymerizable composition of claim 15 wherein the co-curative is of the formula:
R30(NHR31)p
wherein, R30 is a (hetero)hydrocarbyl group;
R31 is H or a hydrocarbyl group, including aryl and alkyl; and
p is 1 to 6.

### Claim 19 (depends on 15)

The polymerizable composition of claim 15 wherein the co-curative is of the formula:
R30—(SH)p
wherein, R30 is a (hetero)hydrocarbyl group; and
p is 1 to 6.

### Claim 20 (depends on 4)

The composition of claim 4 where Q is ferrocenium.