Bifuran-modified polyesters

Patent metadata

Field	Value
Publication number	US-11970573-B2
Application number	US-201917227662-A
Country	US
Kind code	B2
Filing date	Nov 13, 2019
Priority date	Nov 20, 2018
Publication date	Apr 30, 2024
Grant date	Apr 30, 2024

Abstract

Bifuran-modified polyester, polyethylene-terephthalate-co (2,2′-bifuran-5,5′-dicarboxylate), prepared by esterifying or transesterifying a diacid component comprising from 2 to 10 mole percent 2,2′-bifuran-5,5′-dicarboxylate and a diol component with a catalyst compound comprising metal present in an amount of from about 10 to about 450 ppm and polycondensation to form the polyester wherein the polyester has an inherent viscosity of at least 0.5 g/dL, a glass transition temperature (Tg) of 82° C. or more, a semicrystalline melting peak (Tm) with ΔHf equal to or greater than 5 J/g on the second heating ramp, and melting temperature (T m ) between 229° C. and 246° C. Reinforced compositions and shaped articles comprising bifuran-modified polyethylene terephthalate and methods of their production are also disclosed.

First claim

What is claimed is:

1. A bifuran-modified polyester wherein the bifuran-modified polyester is polyethylene-terephthalate-co-(2,2′-bifuran-5,5′-dicarboxylate) prepared by a method comprising: esterifying or transesterifying a diacid component comprising from 2 to 10 mole percent 2,2′-bifuran-5,5′-dicarboxylate and a diol component with a catalyst compound comprising metal present in an amount of from about 10 to about 450 ppm, based on the weight of the modified bifuran polyester; and polycondensation to form the modified bifuran polyester; and wherein the bifuran modified polyester has:
an inherent viscosity of at least 0.5 g/dL,
a melting temperature (Tm) between 229° C. and 246° C.,
a glass transition temperature (Tg) of 82° C. or more, and
a semicrystalline melting peak (Tm) with ΔHf equal to or greater than 5 J/g on the second heating ramp in a heat/cool/reheat differential scanning calorimetry (DSC) scan over a temperature range from 30° C. to 300° C. with heating and cooling rates of 10° C./min and holding the sample at temperature for 3 min before and after the cooling ramp.

2. The bifuran-modified polyester of claim 1 , wherein the metal comprises titanium present in an amount up to about 100 ppm, based on the weight of the bifuran-modified polyester.

3. The bifuran-modified polyester of claim 1 , wherein the metal comprises antimony, zinc, and manganese, in amounts up to about 250 ppm, about 100 ppm, and about 100 ppm, respectively, based on the weight of the bifuran-modified polyester.

4. The bifuran-modified polyester of claim 1 , comprising from 5 to 10 mole percent 2,2′-bifuran-5,5′-dicarboxylate, based on the total moles of the diacid component.

5. 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.

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

7. A method of making the bifuran-modified polyester of claim 1 , comprising:
esterifying or transesterifying monomers comprising the diacid component and the diol component in the presence of the catalyst compound comprising metal present in an amount of from about 10 to about 450 ppm, based on the weight of the modified bifuran polyester;
wherein the diacid component comprises terephthalate and from 2 to 10 mole percent of the 2,2′-bifuran-5,5′-dicarboxylate comonomer; and
polycondensing the esterified or transesterified monomers to form the bifuran-modified polyester having:
an inherent viscosity of at least 0.5 d/dL,
a glass transition temperature (Tg) of 82° C. or more, and
a semicrystalline melting peak (Tm) with ΔHf equal to or greater than 5 J/g on the second heating ramp in a heat/cool/reheat differential scanning calorimetry (DSC) scan over a temperature ran e from 30° C. to 300° C. with heating and cooling rates of 10° C./min and holding the sample at temperature for 3 min before and after the cooling ramp.

8. The method of claim 7 , wherein the esterification or transesterification and polycondensation are in a melt phase.

9. The method of claim 7 , 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.

10. The method of claim 7 , wherein the 2,2′-bifuran-5,5′-dicarboxylate comprises from 5 to 10 mole percent of the diacid component, based on the total moles of the diacid component.

11. The method of claim 7 , further comprising reinforcing the bifuran-modified polyester.

12. The method of claim 7 , further comprising forming the bifuran-modified polyester into a shaped article.

13. The method of claim 12 wherein the forming comprises injection molding, injection stretch blow-molding, or thermoforming.

14. The method of claim 7 , wherein the metal comprises titanium in an amount up to about 40 ppm, based on the weight of the bifuran-modified polyester.

15. The method of claim 7 , wherein the metal comprises antimony, zinc, and manganese, in amounts up to about 250 ppm, about 100 ppm, and about 100 ppm, respectively, based on the weight of the bifuran-modified polyester.

Assignees

• Exxonmobil Chemical Patents Inc
• Virginia Tech Intellectual Properties Inc

Inventors

• Lotz Monica
• Turner S Richard
• Edling Hans Eliot
• Kandel Kapil
• Salciccioli Michael
• Cohn Stephen
• Galuska Alan A
• Guzman Javier
• Paschke Edward E

Classifications

• C08G63/193 Primary

  containing two or more aromatic rings · CPC title

• C08G63/80

  Solid-state polycondensation · 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

• C08G2120/00

  Compositions for reaction injection moulding processes · CPC title

• C08G63/181 Primary

  Acids containing aromatic rings · CPC title