Bibenzoate copolyesters and methods to produce them

Patent metadata

Field	Value
Publication number	US-10767005-B2
Application number	US-201615571025-A
Country	US
Kind code	B2
Filing date	Oct 7, 2016
Priority date	Dec 22, 2015
Publication date	Sep 8, 2020
Grant date	Sep 8, 2020

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.

First claim

What is claimed is:

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.

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

3. 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.

4. 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.

5. 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.

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.

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.

8. 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.

9. 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.

10. 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.

11. 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 D79

Assignees

• Exxonmobil Chemical Patents Inc
• Virginia Tech Intellectual Properties Inc

Inventors

• Mondschein Ryan J
• Liu Haoyu
• Chen Ting
• Long Timothy E
• Turner S Richard

Classifications

• C08J5/18 Primary

  Manufacture of films or sheets · CPC title

• C08G63/199

  Acids or hydroxy compounds containing cycloaliphatic rings · CPC title

• C08G63/85

  Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof {(C08G63/823 takes precedence)} · CPC title

• C08G63/83

  Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof {(C08G63/823 takes precedence)} · CPC title

• C08G63/20

  Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups · CPC title