# US 9,517,987 B1 · Renewable bisphenols and resins from salicylic acid

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- Number: US 9,517,987 B1
- Document ID: US9517987B1
- Status: Granted
- Kind: B1
- Application number: 14/692,362
- Filed: 2015-04-21
- Granted: 2016-12-13
- Earliest claimed: 2014-04-21
- Assignees: The United States of America as represented by the Secretary of the Navy
- Applicants: The United States of America as represented by the Secretary of the Navy
- Inventors: Benjamin G. Harvey; Heather A. Meylemans; Michael E. Wright; Andrew Chafin
- Web page: https://patentgrep.com/patent/US9517987B1

## CPC

- C07C 37/20: using aldehydes or ketones
- C07C 37/002: {by transformation of a functional group, e.g. oxo, carboxyl}
- C07C 37/50: by reactions decreasing the number of carbon atoms (C07C37/04, C07C37/045, C07C37/055, C07C37/08 take precedence)
- C07C 51/353: by isomerisation; by change of size of the carbon skeleton
- C08G 8/10: with phenol
- C08G 8/12: with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
- C08G 64/06: not containing aliphatic unsaturation
- C08G 64/24: and phenols
- C08G 64/28: and phenols
- C08G 64/307: {and phenols}
- C08L 69/00: Compositions of polycarbonates; Compositions of derivatives of polycarbonates
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

A method for the selective synthesis of bisphenols, thermosetting resins, and thermoplastics from salicylic acid, the major component of wintergreen oil, and a viable target for engineered biosynthesis. Condensation of salicylic acid, structural analogs of salicylic acid, and derivatives of salicylic acid with short chain aldehydes or ketones and subsequent decarboxylation has the potential to produce bisphenols that are direct replacements for conventional resins, while the steric and electronic effects of salicylic acid improve the efficiency and selectivity of the conversion process. The utilization of renewable polyphenols as precursors to epoxies, poly carbonates, and high temperature thermosets including cyanate esters, provides an opportunity to develop full-performance resins while reducing the use of petroleum based feedstocks. This approach will then diminish the overall environmental impact of resin production while allowing for a sustainable source of phenols.

## Claims

### Claim 1

A method for synthesizing polyphenol compounds from a renewable, ortho-substituted phenol source, comprising:
a) condensing a carbonyl reactant with said renewable ortho-substituted phenol utilizing at least one acid catalyst to form a polyphenol;
said renewable ortho-substituted phenol having the formula:
where each R″ is independently selected from alkyl, cycloalkyl, arene, alkoxy, and OH;
each R3 is independently selected from hydrogen, alkyl, cycloalkyl, arene, or alkoxy;
x is 0 to 3;
y is 0 to 4;
x+y is 1 to 5; and,
where one of said x+y substituent groups is ortho to the hydroxy group on said phenol, and
said carbonyl reactant having the formula:
where R and R′ are each independently selected from the group consisting of hydrogen, an aliphatic group or an aromatic group or are mutually part of a ring system;
b) where y is greater than zero, modifying said polyphenols by reducing said (C02R3) groups to either hydrogen or a methyl group.

### Claim 2 (depends on 1)

The method of claim 1 wherein
R and R′ of said carbonyl reactant are independently selected from the group consisting of hydrogen, alkyl having from 1-100 carbon atoms, substituted alkyl having from 1-100 carbon atoms, alkene having from 1-100 carbon atoms, substituted alkene having from 1-100 carbon atoms, alkenyl having from 1-100 carbon atoms, substituted alkenyl having from 1-100 carbon atoms, alkynyl having from 1-100 carbon atoms, substituted alkynyl having from 1-100 carbon atoms, alkyne having from 1-100 carbon atoms, substituted alkyne having from 1-100 carbon atoms, cyclic alkyl, substituted cyclic alkyl, aromatic, or substituted aromatic.

### Claim 3 (depends on 1)

The method of claim 1 wherein one equivalent of a carbonyl reactant is condensed with two equivalents of said renewable ortho-substituted phenol.

### Claim 4 (depends on 3)

The method of claim 3 wherein said polyphenol compounds are bisphenols.

### Claim 5 (depends on 1)

The method according to claim 1 wherein x is 0 to 3 and y is 1 to 4.

### Claim 6 (depends on 5)

The method of claim 5 wherein said renewable, ortho-substituted phenol source is salicylic acid.

### Claim 7 (depends on 1)

The method of claim 1 wherein said renewable, ortho-substituted phenol source is methyl salicylate.

### Claim 8 (depends on 1)

The method according to claim 1 wherein x is 1 to 3 and y is 0 to 4.

### Claim 9 (depends on 8)

The method according to claim 8 wherein said renewable, ortho-substituted phenol source is o-cresol.

### Claim 10 (depends on 1)

The method according to claim 1, further comprising converting said polyphenols to polymers.

### Claim 11 (depends on 10)

The method according to claim 10, wherein said polymers are thermosetting resins or thermoplastics.

### Claim 12 (depends on 10)

The method according to claim 10, wherein said polymers are resins, epoxies, polycarbonates, polyethers, poly ether ether ketones (PEEK), polyarylates, polyesters, epoxides, polysulfones, polyester-styrene, alkylphenolic polymers, polyoxalates, polyalylates, high temperature thermosets, cyanate esters, epoxy resins, or benzoxazines.

### Claim 13 (depends on 11)

The method of claim 11 wherein said thermoplastic is a polycarbonate and wherein said polycarbonate is produced by reaction of said polyphenols with a carbonate source selected from the group consisting of carbonates, diphenyl carbonate, chloroformates, p-nitrophenyl chloroformate, phosgene, triphosgene, or phosgene surrogates.

### Claim 14 (depends on 11)

The method according to claim 11, wherein said polymers are cyanate ester resins produced by reacting said polyphenols with a soluble base and cyanogen halide or pseudohalide.

### Claim 15 (depends on 11)

The method according to claim 11, further comprising polymerizing said thermosetting resins to produce high molecular weight thermoset materials.

### Claim 16 (depends on 11)

The method according to claim 11, further comprising polymerizing said thermosetting resins with glass fibers, carbon fibers, other support materials, or combinations thereof to produce a mixture and curing said mixture to produce composite materials.

### Claim 17 (depends on 11)

The method according to claim 11, further comprising utilizing said thermoplastics in a pure state or combined with at least one support material and/or thermoset material to produce composite materials.