# US 10,767,005 B2 · Bibenzoate copolyesters and methods to produce them

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- Number: US 10,767,005 B2
- Document ID: US10767005B2
- Status: Granted
- Kind: B2
- Application number: 15/571,025
- Filed: 2016-10-07
- Published: 2018-10-04
- Granted: 2020-09-08
- Earliest claimed: 2015-12-22
- Assignees: ExxonMobil Chemical Patents Inc.; Virginia Tech Intellectual Properties, Inc.
- Applicants: ExxonMobil Chemical Patents Inc.; Virginia Tech Intellectual Properties, Inc.
- Inventors: Ryan J. Mondschein; Haoyu Liu; Ting Chen; Timothy E. Long; S. Richard Turner
- Web page: https://patentgrep.com/patent/US10767005B2

## CPC

- C08G 63/185: containing two or more aromatic rings
- C08G 63/199: Acids or hydroxy compounds containing cycloaliphatic rings
- C08G 63/20: Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
- C08G 63/83: Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof {(C08G63/823 takes precedence)}
- C08G 63/85: Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof {(C08G63/823 takes precedence)}
- C08J 5/00: Manufacture of articles or shaped materials containing macromolecular substances (manufacture of semi-permeable membranes B01D67/00 - B01D71/00)
- C08J 5/18: Manufacture of films or sheets
- C08J 2367/02: Polyesters derived from dicarboxylic acids and dihydroxy compounds; (C08J2367/06 takes precedence)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)

## Abstract

Bibenzoate copolyesters are based on (4,4′-biphenyl dicarboxylic acid-co-3,4′-biphenyl dicarboxylic acid) as the diacid component, and on an alicyclic diol compound such as 1,4-cyclohexanedimethanol as a portion of the diol component. Copolyesters are based on 4,4′-biphenyl dicarboxylic acid, and/or 3,4′-biphenyl dicarboxylic acid as the diacid component and may include a multifunctional acid. Copolymers may optionally base an essentially amorphous morphology, high glass transition temperature, high elongation at break, and/or high melting temperature. A method to make the copolymers controls the characteristics of the copolyester selected from one or a combination of amorphous morphology or degree of crystallinity, Tg, Tm, tensile modulus, flexural modulus, elongation at break, and so on, by selecting the proportions of the 4,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof, 3,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof, and/or the proportion of the 1,4-cyclohexanedimethanol in the diol component.

## Claims

### Claim 1

A copolyester comprising:
a diol component comprising from about 10 to 90 mole percent ethylene glycol and from about 90 to 10 mole percent 1,4-cyclohexanedimethanol, based on the total moles of the diol component in the copolyester; and
a diacid component comprising 4,4′-biphenyl dicarboxylate and 3,4′-biphenyl dicarboxylate, wherein the diacid component comprises from about 50 to 90 mole percent of the 4,4′-biphenyl dicarboxylate and from about 50 to 10 mole percent of the 3,4′ biphenyl dicarboxylate, based on the total moles of the diacid component in the copolyester;
wherein the copolyester has an essentially amorphous morphology and a glass transition temperature equal to or greater than about 110° C. determined by differential scanning calorimetry (DSC) analysis from a second heating ramp at a heating rate of 10° C./min; or
wherein the copolyester has a semicrystalline morphology, a melting temperature of equal to or less than 250° C. determined by DSC analysis from a second heating ramp at a heating rate of 10° C./min, and a glass transition temperature equal to or greater than 120° C. determined by DSC analysis from a second heating ramp at a heating rate of 10° C./min.

### Claim 2 (depends on 1)

The copolyester of claim 1, further comprising a branching agent.

### Claim 3 (depends on 1)

The copolyester of claim 1, further comprising an average number molecular weight of equal to or greater than about 20,000 g/mol and a polydispersity from about 1.8 to 3.

### Claim 4 (depends on 1)

The copolyester of claim 1, comprising a glass transition temperature equal to or greater than about 115° C., determined by differential scanning calorimetry (DSC) analysis from a second heating ramp at a heating rate of 10° C./min.

### Claim 5 (depends on 4)

The copolyester of claim 4, comprising a melting temperature of less than or equal to about 240° C., determined by differential scanning calorimetry (DSC) analysis from a second heating ramp at a heating rate of 10° C./min.

### Claim 6

A copolyester, comprising:
a diol component comprising from about 10 to 90 mole percent ethylene glycol and from about 90 to 10 mole percent 1,4-cyclohexanedimethanol, based on the total moles of the diol component in the copolyester; and
a diacid component comprising 4,4′-biphenyl dicarboxylate and 3,4′-biphenyl dicarboxylate, wherein the diacid component comprises from about 50 to 80 mole percent of the 4,4′-biphenyl dicarboxylate and from about 50 to 20 mole percent of the 3,4′ biphenyl dicarboxylate, based on the total moles of the diacid component in the copolyester;
an essentially amorphous morphology; and
a glass transition temperature equal to or greater than about 110° C. determined by differential scanning calorimetry (DSC) analysis from a second heating ramp at a heating rate of 10° C./min;
optionally from about 0.05 to 0.5 mole percent of a branching agent, based on the total moles of repeating units in the copolyester.

### Claim 7

A copolyester, comprising:
a diol component comprising from about 10 to 90 mole percent ethylene glycol and from about 90 to 10 mole percent 1,4-cyclohexanedimethanol, based on the total moles of the diol component in the copolyester; and
a diacid component comprising 4,4′-biphenyl dicarboxylate and 3,4′-biphenyl dicarboxylate, wherein the diacid component comprises from about 50 to 90 mole percent of the 4,4′-biphenyl dicarboxylate and from about 50 to 10 mole percent of the 3,4′ biphenyl dicarboxylate, based on the total moles of the diacid component in the copolyester;
a semicrystalline morphology;
a melting temperature of less than or equal to 250° C., determined by differential scanning calorimetry (DSC) analysis from a second heating ramp at a heating rate of 10° C./min; and
a glass transition temperature equal to or greater than 120° C. determined by DSC analysis.

### Claim 8 (depends on 1)

The copolyester of claim 1, comprising:
an elongation at break of equal to or greater than about 85 percent, determined according to ASTM D638; and/or
a tensile strength of equal to or greater than about 60 MPa determined according to ASTM D638; and/or
a tensile modulus of equal to or greater than about 1700 MPa, determined according to ASTM D638; and/or
a flexural strength of equal to or greater than about 80 MPa, determined according to ASTM D790; and/or
a flexural modulus of equal to or greater than about 2500 MPa, determined according to ASTM D790; and/or
a heat distortion temperature at 455 kPa of equal to or greater than about 90° C. determined according to ASTM D648; and/or
a heat distortion temperature at 1.82 MPa of equal to or greater than about 70° C., determined according to ASTM D648;
or a combination thereof.

### Claim 9 (depends on 6)

The copolyester of claim 6, comprising:
wherein the diol component consists essentially of ethylene glycol and from about 20 to 80 mole percent 1,4-cyclohexanedimethanol, based on the total moles of the diol component in the copolyester;
a wherein the diacid component consists essentially of from about 50 to 80 mole percent of 4,4′-biphenyl dicarboxylate, and from about 50 to 20 mole percent of 3,4′-biphenyl dicarboxylate, based on the total moles of the diacid component in the copolyester;
optionally from about 0.1 to 0.5 mole percent trimellitic or pyromellitic anhydride, based on the total moles of repeating units in the copolyester;
a glass transition temperature equal to or greater than about 115° C. determined by differential scanning calorimetry (DSC) analysis from a second heating ramp at a heating rate of 10° C./min; and
one or more of the properties selected from:
an elongation at break greater than about 85 percent determined according to ASTM D638; and/or
a tensile strength of equal to or greater than about 60 MPa determined according to ASTM D638; and/or
a tensile modulus of equal to or greater than about 1700 MPa determined according to ASTM D638; and/or
a flexural strength of equal to or greater than about 80 MPa determined according to ASTM D790; and/or
a flexural modulus of equal to or greater than about 2500 MPa determined according to ASTM D790; and/or
a heat distortion temperature at 455 kPa of equal to or greater than about 90° C. determined according to ASTM D648; and/or
a heat distortion temperature at 1.82 MPa of equal to or greater than about 70° C. determined according to ASTM D648.

### Claim 10 (depends on 9)

The copolyester of claim 9, wherein the 1,4-cyclohexanedimethanol comprises from about 30 to 80 mole percent of the diol component, and the glass transition temperature is equal to or greater than about 120° C.

### Claim 11 (depends on 7)

The copolyester of claim 7, comprising:
wherein the diol component consists essentially of ethylene glycol and from about 20 to 80 mole percent 1,4-cyclohexanedimethanol, based on the total moles of the diol component in the copolyester;
wherein the diacid component consists essentially of from about 60 to 90 mole percent of 4,4′-biphenyl dicarboxylate, and from about 40 to 10 mole percent of 3,4′-biphenyl dicarboxylate, based on the total moles of the diacid component in the copolyester;
a melting temperature less than or equal to about 240° C., determined by differential scanning calorimetry (DSC) analysis from a second heating ramp at a heating rate of 10° C./min; and
one or more of the properties selected from:
an elongation at break greater than about 85 percent determined according to ASTM D638; and/or
a tensile strength of equal to or greater than about 60 MPa determined according to ASTM D638; and/or
a tensile modulus of equal to or greater than about 1700 MPa determined according to ASTM D638; and/or
a flexural strength of equal to or greater than about 80 MPa determined according to ASTM D790; and/or
a flexural modulus of equal to or greater than about 2500 MPa determined according to ASTM D790; and/or
a heat distortion temperature at 455 kPa of equal to or greater than about 90° C. determined according to ASTM D648; and and/or
a heat distortion temperature at 1.82 MPa of equal to or greater than about 70° C. determined according to ASTM D648.

### Claim 12 (depends on 1)

The copolyester of claim 1, comprising branching agent in an amount of from about 0.001 to 1 mole percent, based on the total moles of repeating units in the copolyester.

### Claim 13 (depends on 1)

The copolyester of claim 1, wherein the glass transition temperature is equal to or greater than about 120° C., determined by DSC analysis from a second heating ramp at a heating rate of 10° C./min.

### Claim 14 (depends on 13)

The copolyester of claim 13, comprising a melting temperature less than or equal to about 240° C., determined by DSC analysis from a second heating ramp at a heating rate of 10° C./min.

### Claim 15 (depends on 1)

A shaped article comprising the copolyester according to claim 1.

### Claim 16 (depends on 15)

The article of claim 15, wherein the copolyester is in the form of a fiber, a nonwoven fabric, a film, or a molded article.

### Claim 17

A method, comprising:
contacting (i) a diol component comprising ethylene glycol and 1,4-cyclohexanedimethanol, with (ii) a diacid component comprising 4,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof and 3,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof, in the presence of (iii) a catalyst; and
forming a copolyester comprising the ethylene glycol, 1,4-cyclohexanedimethanol, 4,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof and 3,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof;
wherein the diol component in the copolyester comprises ethylene glycol and from about 10 to 90 mole percent 1,4 cyclohexanedimethanol, based on the total moles of the diol component in the copolyester;
wherein the diacid component in the copolyester comprises from about 50 to 90 mole percent of 4,4′-biphenyl dicarboxylate, and from about 50 to 10 mole percent of 3,4′ biphenyl dicarboxylate, based on the total moles of the diacid component in the copolyester;
wherein the copolyester has an essentially amorphous morphology and a glass transition temperature equal to or greater than about 110° C. determined by differential scanning calorimetry (DSC) analysis from a second heating ramp at a heating rate of 10° C./min; or
wherein the copolyester has a semicrystalline morphology, a melting temperature of equal to or less than 250° C., determined by DSC analysis from a second heating ramp at a heating rate of 10° C./min, and a glass transition temperature equal to or greater than 120° C. determined by DSC analysis from a second heating ramp at a heating rate of 10° C./min.

### Claim 18 (depends on 17)

The method of claim 17, wherein the contacting further comprises a branching agent wherein the copolyester comprises branching and or an amorphous morphology.

### Claim 19 (depends on 17)

The method of claim 17, wherein a proportion of the 1,4-cyclohexanedimethanol in the diol component, and a proportion of the 4,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof in the diacid component, are selected wherein the copolyester comprises:
an essentially amorphous morphology; and
a glass transition temperature equal to or greater than about 115° C., determined by differential scanning calorimetry (DSC) analysis from a second heating ramp at a heating rate of 10° C./min.

### Claim 20 (depends on 17)

The method of claim 17, wherein a proportion of the 1,4-cyclohexanedimethanol in the diol component, and a proportion of the 4,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof in the diacid component, are selected wherein the copolyester comprises:
a semicrystalline morphology;
a melting temperature less than or equal to 250° C. determined by differential scanning calorimetry (DSC) analysis from a second heating ramp at a heating rate of 10° C./min; and
a glass transition temperature equal to or greater than 120° C., determined by DSC analysis from a second heating ramp at a heating rate of 10° C./min.

### Claim 21 (depends on 17)

The method of claim 17, further comprising:
selecting relative proportions of the diacid component wherein the copolyester comprises from about 50 to 80 mole percent 4,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof and from about 50 to 20 mole percent 3,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof, based on the total moles of the diacid components;
wherein the selections of the relative proportions of the diol and diacid components are made to control morphology, glass transition temperature, melting temperature and/or toughness.

### Claim 22 (depends on 17)

The method of claim 17, wherein:
the relative proportions of the diol component comprise from about 20 to 80 mole percent CHDM, based on the total moles of the diol component in the copolyester;
the relative proportions of the diacid component comprises from about 50 to 80 mole percent 4,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof, and from about 50 to 20 mole percent 3,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof, based on the total moles of the diacid component; and
the copolyester comprises: an essentially amorphous morphology and a glass transition temperature equal to or greater than about 120° C., as determined by differential scanning calorimetry (DSC) analysis from a second heating ramp at a heating rate of 10° C./min.

### Claim 23 (depends on 17)

The method of claim 17, wherein:
the relative proportions of the diol component comprise from about 20 to 80 mole percent 1,4-cyclohexanedimethanol, based on the total moles of the diol component in the copolyester;
the relative proportions of the diacid component comprises from about 50 to 90 mole percent 4,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof, and from about 50 to 10 mole percent 3,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof, based on the total moles of the diacid component; and
the copolyester comprises: a semicrystalline morphology, a melting temperature of less than or equal to about 230° C., and a glass transition temperature equal to or greater than 120° C., as determined by differential scanning calorimetry (DSC) analysis from a second heating ramp at a heating rate of 10° C./min.

### Claim 24

A method to control the morphology, glass transition temperature, melting temperature and/or toughness of a copolyester, comprising:
contacting (i) a diacid component comprising from about 50 to 90 mole percent 4,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof, from about 50 to 10 mole percent 3,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof, based on the total moles of the diacid component in the copolyester, with (ii) a diol component comprising from 10 to 90 mole percent 1,4-cyclohexanedimethanol and from about 90 to 10 mole percent ethylene glycol, based on the total moles of the diol component in the copolyester, and (iii) optionally a multifunctional carboxylic acid or ester producing equivalent thereof, and if the multifunctional carboxylic acid or ester is present, in the presence of (iv) a catalyst; and
selecting a proportion of the 1,4-cyclohexanedimethanol in the diol component, a proportion of the 4,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof in the diacid component, and a proportion of the multifunctional carboxylic acid or ester producing equivalent thereof in total repeating units, to produce a copolyester comprising:
wherein the copolyester has an essentially amorphous morphology and a glass transition temperature equal to or greater than about 110° C. determined by differential scanning calorimetry (DSC) analysis from a second heating ramp at a heating rate of 10° C./min; or
wherein the copolyester has a semicrystalline morphology, a melting temperature of equal to or less than 250° C., determined by DSC analysis from a second heating ramp at a heating rate of 10° C./min, and a glass transition temperature equal to or greater than 120° C. determined by DSC analysis from a second heating ramp at a heating rate of 10° C./min.

### Claim 25 (depends on 24)

The method of claim 24 wherein:
the diol component comprises from about 20 to 80 mole percent 1,4-cyclohexanedimethanol;
the diacid component comprises from about 50 to 80 mole percent 4,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof;
the morphology is essentially amorphous; and
the glass transition temperature is equal to or greater than about 115° C., determined by DSC analysis from a second heating ramp at a heating rate of 10° C./min.

### Claim 26 (depends on 24)

The method of claim 24, wherein:
the diol component comprises from about 20 to 80 mole percent 1,4-cyclohexanedimethanol;
the diacid component comprises from about 60 to 90 mole percent 4,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof;
the morphology is semicrystalline;
the glass transition temperature is equal to or greater than 120° C., determined by DSC analysis from a second heating ramp at a heating rate of 10° C./min; and
the melting temperature is less than or equal to 250° C., determined by DSC analysis from a second heating ramp at a heating rate of 10° C./min.

### Claim 27 (depends on 26)

The method of claim 26, wherein:
the diol component comprises from about 30 to 70 mole percent 1,4-cyclohexanedimethanol;
the diacid component comprises from about 65 to 85 mole percent 4,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof; and
the melting temperature is less than about 200° C., determined by DSC analysis from a second heating ramp at a heating rate of 10° C./min.

### Claim 28 (depends on 26)

The method of claim 26, wherein:
the diol component comprises from about 30 to 70 mole percent 1,4-cyclohexanedimethanol;
the diacid component comprises from about 70 to 90 mole percent 4,4′-biphenyl dicarboxylic acid or ester producing equivalent thereof;
the glass transition temperature is equal to or greater than about 125° C., determined by DSC analysis from a second heating ramp at a heating rate of 10° C./min; and
the melting temperature is less than about 240° C., determined by DSC analysis from a second heating ramp at a heating rate of 10° C./min.

### Claim 29 (depends on 17)

The method of claim 17, further comprising forming the copolyester into a shaped article.

### Claim 30 (depends on 29)

The method of claim 29, further comprising forming the copolyester into a fiber, a nonwoven fabric, a film, or a molded article.

### Claim 31 (depends on 17)

The method of claim 17, wherein the catalyst is selected from systems including one or more compounds of Ti, Ti/P, Mn/Ti/Co/P, Mn/Ti/P, Zn/Ti/Co/P, Zn/Al, Sb, and Sn.

### Claim 32 (depends on 17)

The copolyester produced according to method of claim 17.