# US 5,705,573 A · Process for preparation of water borne curing agents

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- Number: US 5,705,573 A
- Document ID: US5705573A
- Status: Granted
- Kind: A
- Application number: 08/708,677
- Filed: 1996-09-05
- Granted: 1998-01-06
- Earliest claimed: 1996-09-05
- Assignees: Michigan Molecular Institute
- Inventors: Douglas R. Swanson; Donald A. Tomalia
- Web page: https://patentgrep.com/patent/US5705573A

## CPC

- C08F 8/32: by reaction with amines
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

A novel process for preparing poly(2-isopropenyl-2-oxazoline or oxazine) and its methyl methacrylate copolymer, which are useful as water borne curing agents, particularly in the non-stick coating industry. The process converts commercially available poly(methyl methacrylate) into poly(2-isopropenyl-2-oxazoline or oxazine) polymers or copolymers with methyl methacrylate, while circumventing the use of the highly toxic monomer, 2-isopropenyl-2-oxazoline or oxazine. The process involves converting a poly(methacrylic ester) to the corresponding poly(.beta.-hydroxy-N-ethyl or propyl methacrylamide) and activating the ring-forming .beta.-hydroxy-N-ethyl or propyl methacrylamide moiety to form an oxazoline or oxazine ring.

## Claims

### Claim 1

A method of forming an oxazoline-containing polymer or copolymer by converting a poly(methacrylic ester) at least in part to a first polymer or copolymer comprising the corresponding poly(.beta.--Y--N--(CH.sub.2).sub.x methacrylamide), and activating the .beta.--Y--(CH.sub.2).sub.x amide group to form an oxazoline or oxazine ring, where Y is a leaving group and x=2 or 3.

### Claim 2 (depends on 1)

The method of claim 1 wherein said activating step comprises converting said first polymer or copolymer to the corresponding poly(2-isopropenyl-2-oxazolinium or oxazinium cation), said activating step further comprising neutralizing/deprotonating said oxazolinium or oxazinium cation to form the oxazoline or oxazine-containing polymer or copolymer.

### Claim 3 (depends on 2)

The method of claim 2 wherein said poly(methacrylic ester) is poly(methyl methacrylate).

### Claim 4 (depends on 2)

The method of claim 2 wherein said poly(methacrylic ester) is a C.sub.1 to C.sub.4 ester.

### Claim 5 (depends on 3)

The method of claim 3 wherein said poly(methyl methacrylate) is converted to said first polymer or copolymer by using ethanolamine or propanolamine, said first polymer or copolymer is converted to said corresponding poly(2-isopropenyl-2-oxazolinium or oxazinium cation) by reacting with a suitable esterifying/cyclizing agent.

### Claim 6 (depends on 5)

The method of claim 5 wherein 5-50 equivalents of ethanolamine or propanolamine are reacted per poly(methyl methacrylate) ester group.

### Claim 7 (depends on 5)

The method of claim 5 wherein 5-40 equivalents of ethanolamine or propanolamine are reacted per poly(methyl methacrylate) ester group.

### Claim 8 (depends on 5)

The method of claim 5 wherein 5-15 equivalents of ethanolamine or propanolamine are reacted per poly(methyl methacrylate) ester group.

### Claim 9 (depends on 5)

The method of claim 5 wherein said ethanolamine or propanolamine conversion is carried to at least about 80% such that the resulting oxazoline-containing copolymer has an oxazoline substitution of at least 80%.

### Claim 10 (depends on 5)

The method of claim 5 wherein said ethanolamine or propanolamine conversion is carried to at least about 60% such that the resulting oxazoline-containing copolymer has an oxazoline substitution of at least 60%.

### Claim 11 (depends on 5)

The method of claim 5 wherein said ethanolamine or propanolamine conversion is carried to about 50% such that the resulting oxazoline-containing copolymer has an oxazoline substitution of at least 50%.

### Claim 12 (depends on 5)

The method of claim 5 wherein said poly(methyl methacrylate) is converted to said first polymer or copolymer in a nonreactive aprotic solvent at reflux.

### Claim 13 (depends on 5)

The method of claim 5 wherein said poly(methyl methacrylate) is converted to said first polymer or copolymer neat at reflux.

### Claim 14 (depends on 13)

The method of claim 13 in which said esterifying/cyclizing agent used is mesyl chloride.

### Claim 15 (depends on 14)

The method of claim 14 in which said mesyl chloride is used in a solvent at an equivalents ratio of from about 1 to about 1.5 equivalents mesyl chloride per leaving group, assuming 100% conversion of said poly(methacrylic ester).

### Claim 16 (depends on 15)

The method of claim 15 in which said reaction with mesyl chloride is conducted below about 100.degree. C.

### Claim 17 (depends on 14)

The method of claim 14 in which said mesyl chloride is contained in a solvent, and said esterifying/cyclizing reaction is conducted below about 100.degree. C.

### Claim 18 (depends on 13)

The method of claim 13 in which said esterifying/cyclizing agent is thionyl chloride.

### Claim 19 (depends on 18)

The method of claim 18 in which said esterifying/cyclizing reaction is conducted with said thionyl chloride neat, at reflux.

### Claim 20 (depends on 5)

The method of claim 5 in which said esterifying/cyclizing agent used is mesyl chloride.

### Claim 21 (depends on 20)

The method of claim 20 in which said mesyl chloride is used in a solvent at an equivalents ratio of from about 1 to about 1.5 equivalents mesyl chloride per leaving group, assuming 100% conversion of said poly(methacrylic ester).

### Claim 22 (depends on 21)

The method of claim 21 in which said reaction with mesyl chloride is conducted below about 100.degree. C.

### Claim 23 (depends on 20)

The method of claim 20 in which said mesyl chloride is contained in a solvent, and said esterifying/cyclizing reaction is conducted below about 100.degree. C.

### Claim 24 (depends on 5)

The method of claim 5 in which said esterifying/cyclizing agent is thionyl chloride.

### Claim 25 (depends on 24)

The method of claim 24 in which said esterifying/cyclizing reaction is conducted with said thionyl chloride neat, at reflux.

### Claim 26 (depends on 2)

The method of claim 2 in which said first polymer or copolymer is converted to said corresponding poly(2-isopropenyl-2-oxazolinium or oxazinium cation) by reacting with a suitable esterifying/cyclizing agent.

### Claim 27 (depends on 26)

The method of claim 26 in which said esterifying/cyclizing agent used is mesyl chloride.

### Claim 28 (depends on 27)

The method of claim 27 in which said mesyl chloride is used in a solvent at an equivalents ratio of from about 1 to about 1.5 equivalents mesyl chloride per leaving group, assuming 100% conversion of said poly(methacrylic ester).

### Claim 29 (depends on 28)

The method of claim 28 in which said reaction with mesyl chloride is conducted below about 100.degree. C.

### Claim 30 (depends on 27)

The method of claim 27 in which said mesyl chloride is contained in a solvent, and said esterifying/cyclizing reaction is conducted below about 100.degree. C.

### Claim 31 (depends on 26)

The method of claim 26 in which said esterifying/cyclizing agent is thionyl chloride.

### Claim 32 (depends on 31)

The method of claim 31 in which said esterifying/cyclizing reaction is conducted with said thionyl chloride neat, at reflux.

### Claim 33 (depends on 1)

The method of claim 1 in which said activating step comprises the thermally induced cyclization-dehydration of said first polymer or copolymer.

### Claim 34 (depends on 33)

The method of claim 33 in which a cyclization catalyst is used.

### Claim 35 (depends on 34)

The method of claim 34 in which said catalyst is ZnCl.sub.2, ZnSO.sub.4, Na.sub.2 B.sub.4 O.sub.7, .gamma.-alumina or Al.sub.2 O.sub.3.

### Claim 36 (depends on 34)

The method of claim 34 in which said cyclization-dehydration is conducted at 80.degree.-200.degree. C.

### Claim 37 (depends on 34)

The method of claim 34 wherein said poly(methacrylic ester) is a C.sub.1 to C.sub.4 ester.

### Claim 38 (depends on 37)

The method of claim 37 wherein said poly(methyI methacrylate) is converted to said first polymer or copolymer by using ethanolamine or propanolamine, said first polymer or copolymer is converted to said corresponding poly(2-isopropenyl-2-oxazolinium or oxazinium cation) by reacting with a suitable esterifying/cyclizing agent.

### Claim 39 (depends on 1)

The method of claim 1 in which said conversion is less than 100%, thereby resulting in said first polymer being a copolymer having some unconverted methacrylic ester groups; said method further comprising substituting one or more modifiers for at least some of said ester groups.

### Claim 40 (depends on 39)

The method of claim 39 in which said modifier is a fluoride containing group.

### Claim 41 (depends on 39)

The method of claim 39 in which said modifier is a UV stabilizer.

### Claim 42 (depends on 39)

The method of claim 39 in which said modifier is an adhesion enhancer.

### Claim 43 (depends on 39)

The method of claim 39 in which said modifier is a cure rate enhancer.