# US 2022/0033573 A1 · Bifuran-modified polyesters

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- Number: US 2022/0033573 A1
- Document ID: US20220033573A1
- Status: Published application
- Kind: A1
- Application number: 17/227,662
- Filed: 2019-11-13
- Published: 2022-02-03
- Earliest claimed: 2018-11-20
- Assignees: ExxonMobil Chemical Patents Inc.; Virginia Tech Intellectual Properties, Inc.
- Applicants: ExxonMobil Chemical Patents Inc.; Virginia Tech Intellectual Properties, Inc.
- Inventors: Monica Lotz; S. Richard Turner; Hans Eliot Edling; Kapil Kandel; Michael Salciccioli; Stephen Cohn; Alan A. Galuska; Javier Guzman; Edward E. Paschke
- Web page: https://patentgrep.com/patent/US20220033573A1

## CPC

- C08G 63/181: Acids containing aromatic rings
- C08G 63/193: containing two or more aromatic rings
- C08G 63/78: Preparation processes
- C08G 63/80: Solid-state polycondensation
- C08G 63/85: Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof {(C08G63/823 takes precedence)}
- C08G 2120/00: Compositions for reaction injection moulding processes
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

Copolyesters such as polyethylene terephthalate (PET) or polyethylene furanoate (PEF) modified with bifuran polyacids such as dimethyl-2,2′-bifuran-5,5′-dicarboxylate (BFE), 2,2′-bifuran-5,5′-dicarboxylic acid (BDA), or bis(2-hydroxyethyl)-2,2′-bifuran-5,5′-dicarboxylate (BHEB), and/or bifuran polyhydroxyls, may have improved properties such as glass transition temperature (Tg), tensile modulus, barrier properties, crystallinity, and/or impact strength. Polyethylene terephthalate-co-bifuranoate (PETBF) has an improved Tg. Also described are polyethylene furanoate-co-bifuranoates (PEFBF).

## Claims

### Claim 1

A bifuran-modified polyester comprising:
a diacid component;
a diol component; and
a bifuran comonomer in an amount of from 1 to 50 weight percent based on the total weight of the polyester.

### Claim 2 (depends on 1)

The bifuran-modified polyester of claim 1 wherein the bifuran comonomer comprises a bifuran diacid; a bifuran diester; a diol bifuran diester; an ester-forming equivalent thereof; or a combination thereof.

### Claim 3 (depends on 1)

The bifuran-modified polyester of claim 1 wherein the bifuran comonomer comprises a polyhydroxyl bifuran.

### Claim 4 (depends on 1)

The bifuran-modified polyester of claim 1, wherein the diacid component comprises a polyfunctional carboxylic acid monomer selected from terephthalic acid, furan dicarboxylic acid, isophthalic acid, naphthalic acid, bibenzoic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid, ester forming equivalents thereof, and combinations thereof.

### Claim 5 (depends on 4)

The bifuran-modified polyester of claim 4, wherein the diol component comprises a polyhydroxyl compound selected from the group consisting of: aliphatic polyols; C4-C20 cyclic polyols; polyhydroxyl furans; and combinations thereof.

### Claim 6 (depends on 5)

The bifuran-modified polyester of claim 5, wherein the polyhdroxyl compound is selected from the group consisting of: ethylene glycol (EG), 1,4-butanediol (BD), 1,6-hexanediol (HD), 1,3-propanediol (PD), 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), 1,2-propanediol, 1,5-pentanediol, isosorbide, isoidide, isomannide, 1,3-cyclohexanedimethanol, and combinations thereof.

### Claim 7 (depends on 2)

The bifuran-modified polyester of claim 2, comprising polyethylene terephthalate (PET) incorporating the bifuran comonomer.

### Claim 8 (depends on 2)

The bifuran-modified polyester of claim 2, comprising polyethylene furanoate (PEF) incorporating the bifuran comonomer.

### Claim 9 (depends on 1)

The bifuran-modified polyester of claim 1, wherein the bifuran comonomer comprises a bifuran diacid in an amount from 2 to 25 mole percent, based on the total moles of the diacid component.

### Claim 10 (depends on 1)

The bifuran-modified polyester of claim 1, wherein the bifuran comonomer comprises a polyhydroxyl bifuran in an amount from 2 to 25 mole percent, based on the total moles of the diol component.

### Claim 11 (depends on 1)

A reinforced composition comprising 100 parts by weight of the bifuran-modified polyester of claim 1 and from 1 to 100 parts by weight of a reinforcement material.

### Claim 12 (depends on 1)

A shaped article, comprising the bifuran-modified polyester of claim 1.

### Claim 13

A method of making a bifuran-modified polyester, comprising:
esterifying or transesterifying monomers comprising a diacid component and a diol component, optionally in the presence of a catalyst;
wherein the monomers further comprise a bifuran comonomer; and
polycondensing the esterified or transesterified monomers, optionally in the presence of the catalyst, to form a bifuran-modified polyester comprising the diacid component, the diol component, and the bifuran comonomer, wherein the bifuran comonomer is present in an amount from 1 to 50 weight percent based on the total weight of the bifuran-modified polyester.

### Claim 14 (depends on 13)

The method of claim 13, wherein the diacid component comprises a polyfunctional carboxylic acid monomer selected from terephthalic acid, furan dicarboxylic acid, isophthalic acid, naphthalic acid, bibenzoic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid; ester forming equivalents thereof; and combinations thereof.

### Claim 15 (depends on 14)

The method of claim 14, wherein the diol component comprises a polyhydroxyl monomer selected from the group consisting of: aliphatic polyols; C4-C20 cyclic polyols; polyhydroxyl furans; and combinations thereof.

### Claim 16 (depends on 15)

The method of claim 15, wherein the polyhdroxyl monomer is selected from the group consisting of: ethylene glycol (EG), 1,4-butanediol (BD), 1,6-hexanediol (HD), 1,3-propanediol (PD), 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), 1,2-propanediol, 1,5-pentanediol, isosorbide, isoidide, isomannide, 1,3-cyclohexanedimethanol, and combinations thereof.

### Claim 17 (depends on 16)

The method of claim 16, wherein:
the polyfunctional carboxylic acid comprises terephthalic acid or an ester forming equivalent thereof;
the polyhdroxyl monomer comprises EG; and
the bifuran-modified polyester comprises polyethylene terephthalate (PET) incorporating the bifuran comonomer.

### Claim 18 (depends on 16)

The method of claim 16, wherein:
the polyfunctional carboxylic acid comprises 2,5-furan dicarboxylic acid or an ester forming equivalent thereof;
the polyhdroxyl monomer comprises EG; and
the bifuran-modified polyester comprises polyethylene furanoate (PEF) incorporating the bifuran comonomer.

### Claim 19 (depends on 13)

The method of claim 13, wherein:
the diacid component comprises a dicarboxylic acid monomer;
the bifuran comonomer includes a bifuran dicarboxylic acid and/or a di(hydroxyalkyl) bifuranoate; preferably wherein the bifuran comonomers comprise 2,2′-bifuran-5,5′-dicarboxylic acid (BFA), di(hydroxyalkyl)-2,2′-bifuran-5,5′-dicarboxylate, or a combination thereof; and
the catalyst, if present, comprises a Brønsted or Lewis acid.

### Claim 20 (depends on 13)

The method of claim 13, wherein:
the diacid component comprises a dialkyl dicarboxylate monomer;
the bifuran comonomer includes a bifuran diester and/or a di(hydroxyalkyl) bifuranoate; and
the catalyst is present, the catalyst comprises a metal catalyst, and the metal of the catalyst is present in an amount of from about 10 to 1500 ppm, based on the weight of theoretical yield of the bifuran-modified polyester.

### Claim 21 (depends on 13)

The method of claim 13, wherein the esterification or transesterification and polycondensation are in a melt phase.

### Claim 22 (depends on 13)

The method of claim 13, comprising:
the esterification or transesterification and polycondensation to form a prepolymer;
pelletizing and crystallizing the prepolymer; and
solid state polymerization of the crystallized prepolymer in a temperature range from a glass transition temperature of the prepolymer up to a melting temperature of the prepolymer to increase the inherent viscosity.

### Claim 23 (depends on 13)

The method of claim 13, wherein the bifuran comonomer comprises a bifuran diacid; a diol bifuran diester; an ester-forming equivalent thereof; or a combination thereof.

### Claim 24 (depends on 13)

The method of claim 13, wherein the bifuran comonomer comprises a polyhydroxyl bifuran.

### Claim 25 (depends on 13)

The method of claim 13, wherein the bifuran comonomer comprises a bifuran diacid in an amount from 2 to 25 mole percent, based on the total moles of the diacid component.

### Claim 26 (depends on 13)

The method of claim 13, further comprising reinforcing the bifuran-modified polyester.

### Claim 27 (depends on 13)

The method of claim 13, further comprising forming the bifuran-modified polyester into a shaped article.

### Claim 28 (depends on 27)

The method of claim 27 wherein the forming comprises injection molding, injection stretch blow-molding, or thermoforming.