# US 11,897,987 B2 · Polymers derived from biomass

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- Number: US 11,897,987 B2
- Document ID: US11897987B2
- Status: Granted
- Kind: B2
- Application number: 17/695,008
- Filed: 2022-03-15
- Published: 2022-09-15
- Granted: 2024-02-13
- Earliest claimed: 2021-03-15
- Assignees: The Florida State University Research Foundation, Inc.
- Applicants: The Florida State University Research Foundation, Inc.
- Inventors: Justin Kennemur; Mark Yarolimek
- Web page: https://patentgrep.com/patent/US11897987B2

## CPC

- C08F 232/04: having one carbon-to-carbon double bond
- C08F 232/08: having condensed rings (coumarone-indene polymers C08F244/00)
- C08F 4/80: selected from iron group metals or platinum group metals
- C08G 61/08: of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
- C08L 65/00: Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C08L7/00 - C08L57/00, C08L61/00 take precedence); Compositions of derivatives of such polymers
- C08F 2410/01: Additive used together with the catalyst, excluding compounds containing Al or B
- C08G 2261/1412: Saturated aliphatic units
- C08G 2261/3325: derived from other polycyclic systems
- C08G 2261/418: Ring opening metathesis polymerisation [ROMP]
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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

Disclosed are polymers derived from biomass. More specifically described are δ-pinene-based polymers, copolymers and compositions comprising δ-pinene-based polymers. Also disclosed are methods of making the same.

## Claims

### Claim 1

A polymer comprising:
a repeating unit of Formula (I):
wherein R1, R2, R3, are independently selected from hydrogen, C1-C10 alkyl, C1-C10 alkoxy, C1-C6 cycloalkyl, C5-C15 aryl, C1-C13 heteroaryl, C3-C15 heterocycloalkyl, C1-C15 heteroalkyl, C6-C14 aryloxy, hydroxyl, halogen, CN, CF3, CO2H, CO2NH2, CO2NHR′, CO2R′, C(O)R′, C(O)NH2, or C(O)NHR′ wherein each of R1, R2, R3, independent of the other, is optionally substituted with C1-C10 alkyl, C1-C10 alkoxy, C1-C6 cycloalkyl, C5-C15 aryl, C1-C13 heteroaryl, C3-C15 heterocycloalkyl, C1-C15 heteroalkyl, C6-C14 aryloxy, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol;
wherein R′ is independently chosen from C1-C10 alkyl, C1-C10 alkoxy, C1-C6 cycloalkyl, C5-C15 aryl, C1-C13 heteroaryl, C3-C15 heterocycloalkyl, C1-C15 heteroalkyl, or C6-C14 aryloxy, any of which are optionally substituted with C1-C10 alkyl, C1-C10 alkoxy, C1-C6 cycloalkyl, C5-C15 aryl, C1-C13 heteroaryl, C3-C15 heterocycloalkyl, C1-C15 heteroalkyl, C6-C14 aryloxy, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol; and wherein
n is an integer from 2 to 100,000.

### Claim 2 (depends on 1)

The polymer of claim 1, wherein the polymer has an average molecular weight from about 100 to about 500,000 Dalton and/or a glass transition temperature from about 70° C. to about 140° C.

### Claim 3 (depends on 1)

The polymer of claim 1, wherein the regioregularity is greater than 50%.

### Claim 4 (depends on 1)

The polymer of claim 1, wherein the polymer comprises from 0% to 100% of a trans-isomer.

### Claim 5 (depends on 4)

The polymer of claim 4, wherein the polymer is less than about 10% of a head-to-head trans-isomer, a tail-to-tail isomer trans-isomer, or a combination thereof.

### Claim 6 (depends on 4)

The polymer of claim 4, wherein the polymer comprises less than 5% of the cis-isomer.

### Claim 7 (depends on 1)

The polymer of claim 1, wherein the polymer is crosslinkable.

### Claim 8 (depends on 1)

The polymer of claim 1, wherein the polymer is recyclable.

### Claim 9 (depends on 1)

An article comprising the polymer of claim 1, wherein the article comprises bottles, fibers, textile, gloves, components in electronic devices, components in electrical devices, containers, tableware, cutlery, tire components, construction materials, automotive and aeronautic components, sporting equipment, or any combination thereof.

### Claim 10 (depends on 1)

A composition comprising:
a) the polymer of claim 1 present in an amount from greater than 0% to less than 100% by the weight of the composition; and
b) an additive, wherein the additive reacts with a ring-opened product of the polymer.

### Claim 11 (depends on 10)

The composition of claim 10, wherein the additive comprises one or more of 3′,3″,5′,5″-tetrabromophenolsulfonephthalein (Bromophenol Blue), 3,3′-[(3-Carboxy-4-oxocyclohexa-2,5-dien-1-ylidene)methylene]bis(6-hydroxybenzoic acid) (Aurinytricaboxulic acid), ethyl-[4-[[4-[ethyl-[(3-sulfophenyl)methyl]amino]phenyl]-(4-hydroxy-2-sulfophenyl)methylidene]-1-cyclohexa-2,5-dienylidene]-[(3-sulfophenyl)methyl]azanium (Fast Green FCF), or 2,6-Dibromo-4-[7-(3,5-dibromo-4-hydroxy-2-methyl-phenyl)-9,9-dioxo-8-oxa-9λ6-thiabicyclo[4.3.0]nona-1,3,5-trien-7-yl]-3-methyl-phenol (Bromocresol green).

### Claim 12 (depends on 10)

The composition of claim 10, wherein the additive is a sensor indicating changes to the polymer.

### Claim 13 (depends on 1)

A copolymer composition comprising:
a) a unit comprising a monomer of the polymer of claim 1 present in an amount from greater than 0% to less than 100% of the copolymer composition; and
b) a unit comprising a monomer of a further polymer, wherein the further polymer is different from the polymer of a).

### Claim 14 (depends on 13)

The copolymer of claim 13, wherein the copolymer is a block copolymer, statistical copolymer, or a combination thereof.

### Claim 15 (depends on 13)

The copolymer composition of claim 13, wherein the further polymer comprises a cycloolefin comprising a substituted or unsubstituted bridged cyclic hydrocarbon.

### Claim 16 (depends on 13)

The copolymer composition of claim 13 further comprising at least one additional repeating unit that is different from a) and b).

### Claim 17

A method comprising:
polymerizing a δ-pinene in the presence of a catalyst, thereby forming a polymer having a structure of Formula (I):
wherein R1, R2, R3, are independently selected from hydrogen, C1-C10 alkyl, C1-C10 alkoxy, C1-C6 cycloalkyl, C5-C15 aryl, C1-C13 heteroaryl, C3-C15 heterocycloalkyl, C1-C15 heteroalkyl, C6-C14 aryloxy, hydroxyl, halogen, CN, CF3, CO2H, CO2NH2, CO2NHR′, CO2R′, C(O)R′, C(O)NH2, or C(O)NHR′ wherein each of R1, R2, R3, independent of the other, is optionally substituted with C1-C10 alkyl, C1-C10 alkoxy, C1-C6 cycloalkyl, C5-C15 aryl, C1-C13 heteroaryl, C3-C15 heterocycloalkyl, C1-C15 heteroalkyl, C6-C14 aryloxy, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol;
wherein R′ is independently, chosen from C1-C10 alkyl, C1-C10 alkoxy, C1-C6 cycloalkyl, C5-C15 aryl, C1-C13 heteroaryl, C3-C15 heterocycloalkyl, C1-C15 heteroalkyl, or C6-C14 aryloxy, any of which are optionally substituted with C1-C10 alkyl, C1-C10 alkoxy, C1-C6 cycloalkyl, C5-C15 aryl, C1-C13 heteroaryl, C3-C15 heterocycloalkyl, C1-C15 heteroalkyl, C6-C14 aryloxy, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol; and wherein
n is an integer from 2 to 10,000.

### Claim 18 (depends on 17)

The method of claim 17 wherein the catalyst is a ring-opening metathesis polymerization (ROMP) catalyst.

### Claim 19 (depends on 17)

The method of claim 17, wherein the catalyst comprises a Grubbs catalyst.

### Claim 20 (depends on 17)

The method of claim 17, wherein the δ-pinene is formed by converting a first composition comprising an α-pinene under conditions effective to form a second composition comprising the δ-pinene such that the second composition comprises an α-pinene from 0% to less than 100%.

### Claim 21 (depends on 20)

The method of claim 20, wherein the second composition is purified prior to the polymerizing the δ-pinene to substantially remove the α-pinene if present.

### Claim 22 (depends on 21)

The method of claim 21, wherein the second composition is purified by selectively reacting the α-pinene or separating the α-pinene from the second composition, or by a combination thereof.

### Claim 23 (depends on 22)

The method of claim 22, wherein the step of selectively reacting comprises forming a derivative of the α-pinene.

### Claim 24 (depends on 22)

The method of claim 22, wherein the step of separation comprises a silver nitrate coated silica gel, fractional distillation, or a combination thereof.

### Claim 25 (depends on 22)

The method of claim 22, wherein a yield of the δ-pinene is greater than 10% to 100% after purification step.

### Claim 26 (depends on 17)

The method of claim 17 further comprising reacting the polymer under conditions effective to form a hydrogenated olefin.

### Claim 27 (depends on 1)

A method comprising:
forming a copolymer comprising:
i) a unit comprising a monomer of the polymer of claim 1 present in an amount from greater than 0% to less than 100% of the copolymer composition; and
ii) a unit comprising a monomer of a further polymer, wherein the further polymer is different from the polymer of i);
wherein the step of forming comprises a reaction in the presence of a catalyst.

### Claim 28 (depends on 27)

The method of claim 27 wherein the formed copolymer is a block copolymer, a statistical copolymer, or a combination thereof.

### Claim 29 (depends on 27)

The method of claim 27, wherein the copolymer further comprises at least one additional repeating unit comprising a monomer that is different from i) and ii).