# US 9,040,630 B2 · Graft copolymers of polyfarnesenes with condensation polymers

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- Number: US 9,040,630 B2
- Document ID: US9040630B2
- Status: Granted
- Kind: B2
- Application number: 13/811,665
- Filed: 2011-07-29
- Published: 2013-05-16
- Granted: 2015-05-26
- Earliest claimed: 2010-08-02
- Assignees: Amyris, Inc.
- Applicants: Derek James McPhee
- Inventors: Derek James McPhee
- Web page: https://patentgrep.com/patent/US9040630B2

## CPC

- C08F 279/02: on to polymers of conjugated dienes
- C08C 19/28: Reaction with compounds containing carbon-to-carbon unsaturated bonds (graft polymers C08F279/00)
- C08F 36/22: the radical having three or more carbon-to-carbon double bonds
- C08F 283/00: Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F 283/02: on to polycarbonates or saturated polyesters {(C08F283/004 takes precedence)}
- C08F 283/10: on to polymers containing more than one epoxy radical per molecule {(C08F283/004 takes precedence)}
- C08F 287/00: Macromolecular compounds obtained by polymerising monomers on to block polymers
- C08F 293/00: Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule (on to polymers modified by introduction of unsaturated end groups C08F290/02)
- C08G 81/02: at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08C: TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

Provided herein are graft copolymers of polyfarnesenes with condensation polymers; and methods of making and using the graft copolymers disclosed herein. In certain embodiments, the condensation polymers include polyesters, polycarbonates, polyamides, polyethers, phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins and combinations thereof. In some embodiments, the polyfarnesenes include farnesene homopolymers derived from a farnesene, and farnesene interpolymers derived from a farnesene and at least a vinyl monomer. In certain embodiments, the farnesene is prepared from a sugar by using a microorganism.

## Claims

### Claim 1

A graft copolymer of a polyfarnesene with a condensation polymer, wherein the condensation polymer is a polyester, a polycarbonate, a polyamide, a polyether, a phenol-formaldehyde resin, an urea-formaldehyde resin, a melamine-formaldehyde resin or a combination thereof.

### Claim 2 (depends on 1)

The graft copolymer of claim 1, wherein the condensation polymer is a polyester, a polycarbonate, a polyamide or a combination thereof.

### Claim 3 (depends on 1)

The graft copolymer of claim 1, wherein the condensation polymer is a polyester.

### Claim 4 (depends on 3)

The graft copolymer of claim 3, wherein the polyester is a polyethylene terephthalate.

### Claim 5 (depends on 1)

The graft copolymer of claim 1, wherein the polyfarnesene has formula (A):
wherein m is from 0 to about 100,000; n is from 1 to about 100,000 with the proviso that when m is 0, n is from 2 to about 100,000;
X has one or more of formulae (I)-(VIII):
Y has formula (IX):
wherein R1 has formula (XI):
R2 has formula (XII):
R3 has formula (XIII):
and
R4 has formula (XIV):
wherein each of R5, R6, R7 and R8 is independently H, alkyl, cycloalkyl, aryl, cycloalkenyl, alkynyl, heterocyclyl, alkoxy, aryloxy, carboxy, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, acyloxy, nitrile or halo.

### Claim 6 (depends on 5)

The graft copolymer of claim 5, wherein the amount of formula (I) is at most about 80 wt. % and the amount of formula (II) is from about 5 wt. % to about 99 wt. %, based on the total weight of the polyfarnesene.

### Claim 7 (depends on 5)

The graft copolymer of claim 5, wherein the mole percent ratio of X to Y is from about 1:4 to about 100:1 when m is 1 or greater.

### Claim 8 (depends on 5)

The graft copolymer of claim 5, wherein m is 0 and n is from 2 to about 100,000.

### Claim 9 (depends on 5)

The graft copolymer of any of claim 5, wherein m is from 1 to about 100,000 and n is from 1 to about 100,000, and wherein the polyfarnesene is a random farnesene interpolymer.

### Claim 10 (depends on 5)

The graft copolymer of claim 5, wherein m is from 1 to about 100,000 and n is from 1 to about 100,000, and wherein the polyfarnesene is a block farnesene interpolymer.

### Claim 11 (depends on 1)

The graft copolymer of claim 1, wherein the polyfarnesene is prepared by polymerizing β-farnesene or α-farnesene or a combination thereof in the presence of a catalyst.

### Claim 12 (depends on 11)

The graft copolymer of claim 11, wherein the β-farnesene or α-farnesene is copolymerized with a vinyl monomer to form a farnesene interpolymer.

### Claim 13

A modified polyfarnesene prepared by reacting a polyfarnesene with at least one modifier in the presence of a grafting initiator, radiation or a combination thereof, wherein the ratio of the polyfarnesene to the modifier is from about 100,000:1 to about 100:5 by weight, and wherein the modifier has formula (XVI), (XVII), (XVIII), (XIX), or (XX):
wherein Q1 is S, NR23 or N-Q7; Q6 is O, S, NR23 or N-Q7; each of Q2, Q3 and Q4 is independently halo, Q8, or NR24R25, Q5 is halo, Q8, NR24R25, OR26 or O-Q8; Q7 and Q8 respectively have the following formulae:
wherein k is an integer from 1 to about 10; and Q9 is OH, NH2, NHR30, carboxyl, epoxy or gycidyl; and
each of R9 to R30is independently H, C1-20 alkyl, C1-20 alkenyl, C1-20 alkynyl, cycloalkyl, aryl, aralkyl, alkaryl, OH, NH2, carboxyl, epoxy or gycidyl, or R19 and R22 together form a —(CH2)m— group where m is an integer from 1 to about 6, and wherein each of the C1-20 alkyl, C1-20 alkenyl, C1-20 alkynyl, cycloalkyl, aryl, aralkyl, alkaryl, epoxy, gycidyl and —(CH2)m— is optionally substituted.

### Claim 14 (depends on 13)

The modified polyfarnesene of claim 13, wherein the modifier has formula (XVI).

### Claim 15 (depends on 14)

The modified polyfarnesene of claim 14, wherein the modifier is maleimide, citraconic anhydride, itaconic anhydride or a combination thereof.

### Claim 16 (depends on 13)

The modified polyfarnesene of claim 13, wherein the modifier has formula (XVII).

### Claim 17 (depends on 16)

The modified polyfarnesene of claim 16, wherein the modifier is mesaconic acid, maleic acid, fumaric acid, malenyl chloride, monomethyl maleate, dimethyl maleate, glycidyl maleate, dipropyl maleate, diisobutyl maleate, dihexyl maleate, dibenzyl maleate, p-chlorophenyl methyl maleate, phenylethyl maleate, dicyclopentyl meleate or a combination thereof

### Claim 18 (depends on 13)

The modified polyfarnesene of claim 13, wherein the modifier has formula (XVIII).

### Claim 19 (depends on 18)

The modified polyfarnesene of claim 18, wherein the modifier is methacrylic acid, acrylic acid, itaconic acid, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, caprolactone adduct of 2-hydroxyethyl methacrylate, ethylene oxide adduct of 2-hydroxyethyl methacrylate, propylene oxide adduct of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, caprolactone adduct of 2-hydroxyethyl acrylate, ethylene oxide adduct of 2-hydroxyethyl acrylate, propylene oxide adduct of 2-hydroxyethyl acrylate, 2-hydroxyethyl crotonate, 2-hydroxypropyl crotonate, 3-hydroxypropyl crotonate, 3-hydroxybutyl crotonate, 4-hydroxybutyl crotonate, 5-hydroxypentyl crotonate, 6-hydroxyhexyl crotonate, glycidyl methacrylate, glycidyl acrylate, glycidyl ethacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate or a combination thereof.

### Claim 20 (depends on 13)

The modified polyfarnesene of claim 13, wherein the modifier has formula (XIX).

### Claim 21 (depends on 20)

The modified polyfarnesene of claim 20, wherein the modifier is allyl alcohol, hydroxymethyl vinyl ether, hydroxyehtyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxypentyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyheptyl vinyl ether, hydroxycyclohexyl vinyl ether, allylglycidyl ether, p-glycidyloxy styrene, p-glycidyloxy-α-methyl styrene, p-(3,4-epoxycyclohexylmethyloxy) styrene, p-(3,4-epoxycyclohexylmethyloxy)-α-methyl styrene, glycidyl ethylene, 3,4-epoxycyclohexylmethylethylene, glycidylvinyl ether, 3,4-epoxycyclohexylmethyl vinyl ether, 3,4-epoxycyclohexylmethyl allyl ether or a combination thereof.

### Claim 22 (depends on 13)

The modified polyfarnesene of claim 13, wherein the modifier has formula (XX).

### Claim 23 (depends on 22)

The modified polyfarnesene of claim 22, wherein the modifier is bicyclo[2,2,2]-oct-5-ene-2,3-dicarboxylic acid anhydride, bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid anhydride or a combination thereof.

### Claim 24 (depends on 13)

The modified polyfarnesene of claim 13, wherein the reaction is carried out in the presence of the grafting initiator at a temperature from about 50 ° C. to about 300 ° C.

### Claim 25 (depends on 24)

The modified polyfarnesene of claim 24, wherein the grafting initiator is a dialkyl peroxide, a diacyl peroxide, a peroxyester, a peroxyketone, azobisisobutyronitrile or a combination thereof.

### Claim 26 (depends on 13)

The modified polyfarnesene of claim 13, wherein the polyfarnesene has formula (A):
wherein m is from 0 to about 100,000; n is from 1 to about 100,000 with the proviso that when m is 0, n is from 2 to about 100,000;
X has one or more of formulae (I)-(VIII):
Y has formula (IX):
wherein R1 has formula (XI):
R2 has formula (XII):
R3 has formula (XIII):
and
R4 has formula (XIV):
wherein each of R5, R6, R7 and R8 is independently H, alkyl, cycloalkyl, aryl, cycloalkenyl, alkynyl, heterocyclyl, alkoxy, aryloxy, carboxy, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, acyloxy, nitrile or halo.

### Claim 27 (depends on 26)

The modified polyfarnesene of claim 26, wherein the amount of formula (I) is at most about 80 wt. % and the amount of formula (II) is from about 5 wt. % to about 99 wt. %, based on the total weight of the polyfarnesene.

### Claim 28 (depends on 26)

The modified polyfarnesene of claim 26, wherein the mole percent ratio of X to Y is from about 1:4 to about 100:1 when m is 1 or greater.

### Claim 29 (depends on 26)

The modified polyfarnesene of claim 26, wherein m is 0 and n is from 2 to about 100,000.

### Claim 30 (depends on 26)

The modified polyfarnesene of claim 26, wherein m is from 1 to about 100,000 and n is from 1 to about 100,000, and wherein the polyfarnesene is a random farnesene interpolymer.

### Claim 31 (depends on 26)

The modified polyfarnesene of claim 26, wherein m is from 1 to about 100,000 and n is from 1 to about 100,000, and wherein the polyfarnesene is a block farnesene interpolymer.

### Claim 32 (depends on 13)

A graft copolymer prepared by reacting the modified polyfarnesene of claim 13 with a condensation polymer at a temperature from about 50 ° C. to about 300 ° C., wherein the condensation polymer is a polyester, a polycarbonate, a polyamide, a polyether, a phenol-formaldehyde resin, an urea-formaldehyde resin, a melamine-formaldehyde resin or a combination thereof.

### Claim 33 (depends on 32)

The graft copolymer of claim 32, wherein the condensation polymer is a polyester, a polycarbonate, a polyamide or a combination thereof.

### Claim 34 (depends on 32)

The graft copolymer of claim 32, wherein the condensation polymer is a polyester.

### Claim 35 (depends on 34)

The graft copolymer of claim 34, wherein the polyester is a hydroxyl-terminated polyester.

### Claim 36 (depends on 34)

The graft copolymer of claim 34, wherein the polyester is a carboxyl-terminated polyester.

### Claim 37 (depends on 34)

The graft copolymer of claim 34, wherein the polyester is an epoxy-terminated polyester.

### Claim 38 (depends on 34)

The graft copolymer of claim 34, wherein the polyester is a polyethylene terephthalate.

### Claim 39 (depends on 38)

The graft copolymer of claim 38, wherein the polyethylene terephthalate is a hydroxyl-terminated polyethylene terephthalate.

### Claim 40 (depends on 38)

The graft copolymer of claim 38, wherein the polyethylene terephthalate is a carboxyl-terminated polyethylene terephthalate.

### Claim 41 (depends on 38)

The graft copolymer of claim 38, wherein the polyethylene terephthalate is an epoxy-terminated polyethylene terephthalate.

### Claim 42 (depends on 32)

The graft copolymer of claim 32, wherein the condensation polymer is a polycarbonate.

### Claim 43 (depends on 42)

The graft copolymer of claim 42, wherein the polycarbonate is a hydroxyl-terminated polycarbonate.

### Claim 44 (depends on 42)

The graft copolymer of claim 42, wherein the polycarbonate is an epoxy-terminated polycarbonate.

### Claim 45 (depends on 32)

The graft copolymer of claim 32, wherein the condensation polymer is a polyamide.

### Claim 46 (depends on 34)

The graft copolymer of claim 34, wherein the polyamide is an amino-terminated polyamide.

### Claim 47 (depends on 34)

The graft copolymer of claim 34, wherein the polyamide is a carboxyl-terminated polyamide.

### Claim 48 (depends on 34)

The graft copolymer of claim 34, wherein the polyamide is an epoxy-terminated polyamide.

### Claim 49 (depends on 1)

A polymer composition comprising the graft copolymer of claim 1; and at least an additive.

### Claim 50 (depends on 49)

The polymer composition of claim 49, wherein the additive is a filler, tackifier, slip agent, anti-blocking agent, plasticizer, antioxidant, blowing agent, blowing agent activator, UV stabilizer, acid scavenger, colorant or pigment, coagent, lubricant, antifogging agent, flow aid, processing aid, extrusion aid, coupling agent, cross-linking agent, stability control agent, nucleating agent, surfactant, flame retardant, antistatic agent or a combination thereof.

### Claim 51 (depends on 49)

The polymer composition of claim 49, wherein the additive is a filler.

### Claim 52 (depends on 49)

The polymer composition of claim 49, wherein the additive is a colorant.

### Claim 53 (depends on 49)

The polymer composition of claim 49, further comprising a second polymer.

### Claim 54 (depends on 53)

The polymer composition of claim 53, wherein the ratio of the graft copolymer to the second polymer is from about 1:99 to about 99:1.

### Claim 55 (depends on 54)

The polymer composition of claim 54, wherein the second polymer is a polyolefin, polyurethane, polyester, polyamide, styrenic polymer, phenolic resin, polyacrylate, polymethacrylate or a combination thereof.

### Claim 56 (depends on 1)

An article comprising the graft copolymer of claim 1.

### Claim 57 (depends on 56)

The article of claim 56, wherein the article is a molded article, film, sheet or foam.

### Claim 58 (depends on 57)

The article of claim 57, wherein the article is a molded article selected from toys, grips, soft touch handles, bumper rub strips, floorings, auto floor mats, wheels, casters, furniture and appliance feet, tags, seals, gaskets, automotive doors, bumper fascia, grill components, rocker panels, hoses, linings, office supplies, seals, liners, diaphragms, tubes, lids, stoppers, plunger tips, delivery systems, kitchen wares, shoes, shoe bladders, and shoe soles.

### Claim 59 (depends on 49)

An article comprising the polymer composition of claim 49.

### Claim 60 (depends on 59)

The article of claim 59, wherein the article is a molded article, film, sheet or foam.

### Claim 61 (depends on 60)

The article of claim 60, wherein the article is a molded article selected from toys, grips, soft touch handles, bumper rub strips, floorings, auto floor mats, wheels, casters, furniture and appliance feet, tags, seals, gaskets, automotive doors, bumper fascia, grill components, rocker panels, hoses, linings, office supplies, seals, liners, diaphragms, tubes, lids, stoppers, plunger tips, delivery systems, kitchen wares, shoes, shoe bladders, and shoe soles.