# US 9,434,867 B2 · Bisphenol A (BPA) free epoxy resins

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- Number: US 9,434,867 B2
- Document ID: US9434867B2
- Status: Granted
- Kind: B2
- Application number: 14/860,131
- Filed: 2015-09-21
- Published: 2016-03-17
- Granted: 2016-09-06
- Earliest claimed: 2011-04-27
- Assignees: University of Massachusetts Lowell
- Applicants: University of Massachusetts Lowell
- Inventors: Daniel Schmidt
- Web page: https://patentgrep.com/patent/US9434867B2

## CPC

- C09J 163/00: Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C07D 303/28: Ethers with hydroxy compounds containing oxirane rings
- C08G 59/24: carbocyclic
- C08G 65/2609: {containing aliphatic hydroxyl groups}
- C09D 163/00: Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C08K 5/17: Amines; Quaternary ammonium compounds
- C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H)
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- 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)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

An epoxy resin is provided that includes a diglycidyl ether of a substituted cycloaliphatic diol or bis-thiol, and a thermoset epoxy polymer is provided employing the same. The epoxy resin is bisphenol A free, and capable of forming thermoset epoxy polymers with fewer associated health and environmental concerns than conventional epoxies based on phenolic compounds.

## Claims

### Claim 1

An adhesive composition comprising an epoxy resin represented by:
wherein A and A′ are each independently selected from the group consisting of 0 or S;
wherein R5, R6, R11, and R12 are each independently selected from hydrogen or a C1 - C6 straight chain or branched alkyl or alkenyl group, wherein the alkyl or alkenyl group is optionally substituted with one or more substituents, each of which is independently selected from NH2, OH, CF3, CN, CO2H, C(O)H or halogen, provided that at least one of R5, R6, R11, and R12 is not hydrogen; wherein adjacent R groups may optionally form a fused ring selected from a C5 - C7 membered aromatic ring, or a C3 - C8 cycloalkyl or heterocycle;
wherein R is derived from an aliphatic or cycloaliphatic molecule comprising at least two functional groups;
X is 1 or greater;
Y is 0 or greater; and
wherein the epoxy resin has a weight average molecular weight of less than about 2,000 Daltons and wherein the epoxy resin has a reduced potential to release endocrine disrupting compounds compared to bisphenol A and related phenolic compounds.

### Claim 2 (depends on 1)

The adhesive composition of claim 1, wherein R is derived from a diglycidyl ether of a diol selected from the group consisting of:
2,2,4,4-tetramethyl-1,3-cyclobutanediol;
3,3,4,4,5,5-hexamethyl-1,2-cyclopentanediol;
2,2,4,4,5,5-hexamethyl-1,3-cyclopentanediol;
3,3,4,4,5,5,6,6-octamethyl-1,2-cyclohexanediol;
2,2,4,4,5,5,6,6-octamethyl-1,3-cyclohexanediol;
2,2,3,3,5,5,6,6-octamethyl-1,4-cyclohexanediol;
3,3,4,4,5,5,6,6,7,7-decamethyl-1,2-cycloheptanediol;
2,2,4,4,5,5,6,6,7,7-decamethyl-1,3-cycloheptanediol;
2,2,3,3,5,5,6,6,7,7-decamethyl-1,4-cycloheptanediol;
3,3,4,4,5,5,6,6,7,7,8,8-dodecamethyl-1,2-cyclooctanediol;
2,2,4,4,5,5,6,6,7,7,8,8-dodecamethyl-1,3-cyclooctanediol;
2,2,3,3,5,5,6,6,7,7,8,8-dodecamethyl-1,4-cyclooctanediol;
2,2,3,3,4,4,6,6,7,7,8,8-dodecamethyl-1,5-cyclooctanediol;
4,4-dimethyl-l-cyclobutanone-2,3-diol;
1,2-cyclobutanedione-3,4-diol;
4,4-dimethyl-2-cyclobutanone-1,3-diol;
1,3-cyclobutanedione-2,4-diol;
cyclohexanedimethanol; and
diol derivatives of norbornane, norbornene, bicycle[2.2.2]octane, cubane and adamantine.

### Claim 3

An adhesive composition comprising an epoxy resin represented by:
wherein A and A′ are each independently selected from the group consisting of O or S;
wherein R5, R6, R11, and R12 are each independently selected from hydrogen or a C1 - C6 straight chain or branched alkyl or alkenyl group, wherein the alkyl or alkenyl group is optionally substituted with one or more substituents, each of which is independently selected from NH2, OH, CF3, CN, CO2H, C(O)H or halogen, provided that at least one of R5, R6, R11, and R12 is not hydrogen;
X is 1 or greater;
Y is 1 or greater; and
wherein the epoxy resin has a weight average molecular weight of less than about 2,000 Daltons and wherein the epoxy resin has a reduced potential to release endocrine disrupting compounds compared to bisphenol A and related phenolic compounds.

### Claim 4 (depends on 1)

The adhesive composition of claim 1, wherein A and A′ are both O; and R5, R6, R11, and R12 are each independently selected from hydrogen or a C1 - C6 straight chain or branched alkyl groups.

### Claim 5 (depends on 4)

The adhesive composition of claim 4, wherein R5, R6, R11, and R12 are each independently selected from methyl or ethyl groups.

### Claim 6 (depends on 1)

The adhesive composition of claim 1, wherein A and A′ are both O; and R5, R6, R11, and R12 are each a methyl group.

### Claim 7 (depends on 1)

The adhesive composition of claim 1, wherein the epoxy resin has a viscosity of less than about 100 poise at 25° C. measured as a 40% weight solution of resin solids in methyl ethyl ketone or equivalent solvent.

### Claim 8 (depends on 1)

The adhesive composition of claim 1, wherein the epoxy resin has the following structure:
and wherein R is derived from

### Claim 9 (depends on 1)

The adhesive composition of claim 1, wherein the epoxy resin is represented by:

### Claim 10 (depends on 1)

A cured adhesive composition comprising the reaction product of epoxy resin of claim 1 and a curative compound, wherein the cured epoxy resin has a reduced potential to release endocrine disrupting compounds compared to cured epoxy resins comprising bisphenol A and related phenolic compounds.

### Claim 11 (depends on 10)

The adhesive composition of claim 10, wherein the curative compound is a formaldehyde hardener, a polyamine hardener or a polythiol hardener.

### Claim 12 (depends on 1)

The adhesive composition of claim 1, wherein the epoxy resin is a chain extended epoxy resin prepared by:
a. reacting a first substituted 1,3-cyclobutanediol molecule with epichlorohydrin in the presence of a first catalyst to form a diglycidyl ether, and
b. reacting the diglycidyl ether with a second substituted 1,3-cyclobutanediol molecule in the presence of a second catalyst to form the chain extended epoxy resin.

### Claim 13 (depends on 12)

The adhesive composition of claim 12, wherein the first substituted 1,3-cyclobutanediol diglycidyl ether is 2,2,4,4-tetramethyl-1,3-cyclobutanediol diglycidyl ether, the second substituted 1,3-cyclobutanediol molecule is 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and the catalyst is tetrabutyl ammonium hydrogen bisulfate.