Chemically modified polyesters and process for making

Patent metadata

Field	Value
Publication number	US-11525045-B2
Application number	US-202016832559-A
Country	US
Kind code	B2
Filing date	Mar 27, 2020
Priority date	Mar 29, 2019
Publication date	Dec 13, 2022
Grant date	Dec 13, 2022

Abstract

Chemically modified polyesters, foamable compositions thereof that form low density foams, and methods of making the foamable compositions and foams are disclosed. The compositions comprise an amorphous copolyester, or amorphous co-polyesterpolycarbonate or amorphous co-polyesterpolyether or combination thereof. Additionally, uses for the low density foams are disclosed.

First claim

What is claimed:

1. A copolyester, co-polyesterpolycarbonate or co-polyesterpolyether copolymer comprising either differing polyester units, or comprising polyester units and polycarbonate or polyether units or both, and optionally further comprising one or more coupling agents, and being characterized by having
polymerized units of one or more aromatic diacid monomer;
from 10 mole % to 40 mole % of the sum of polymerized units of one or more aliphatic diols where the mole % is the sum of the moles of polymerized units of the one or more aliphatic diols in the copolymer expressed as a percentage of the total moles of polymerized units that make up the copolymer;
a primary Tg between 85° C. and 125° C. as measured from the inflection point on second heatup of the DSC curve using a heating/cooling rate of 10° C./min; and
a heat of melting ΔH m peak no greater than 10 J/g after exposure to hydrostatic pressure of 1000 psi CO 2 at 135° C. for 4 hours.

2. The copolyester, co-polyesterpolycarbonate or co-polyesterpolyether copolymer of claim 1 having a B[X] or B[X+X′] value of 0.20 or greater, where B is the Koenig B value for copolymer randomness, [X] is the molar fraction of comonomer polyester structural units or of comonomer polycarbonate and/or polyether structural units, and [X+X′] is the molar fraction of comonomer polyester structural units or of comonomer polycarbonate and/or polyether structural units, including any units comprising residue fragments thereof, in the copolymer.

3. The copolyester, co-polyesterpolycarbonate or co-polyesterpolyether copolymer of claim 1 having a Koenig B value of greater than 0.90 for copolymers having a ratio of polyester:polycarbonate structural units in the copolymer, or polyester:(polycarbonate+polyether) structural units in the copolymer, in a mole ratio of from 65:35 to 85:15.

4. The copolyester, co-polyesterpolycarbonate or co-polyesterpolyether copolymer of claim 1 , wherein the one or more aromatic diacid monomers are selected from phthalic acid, terephthalic acid, isophthalic acid, or 2,5-furandicarboxylic acid.

5. The copolyester, co-polyesterpolycarbonate or co-polyesterpolyether or copolymer of claim 1 wherein at least a portion of the polyester units in the copolymer are derived from recycled polyethylene terephthalate.

6. The copolyester, co-polyesterpolycarbonate or co-polyesterpolyether copolymer of claim 1 , wherein the one or more diols are selected from ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, butylene glycol, cyclohexane dimethanol, isosorbide, and spiroglycol.

7. The copolyester, co-polyesterpolycarbonate or co-polyesterpolyether copolymer of claim 1 , wherein the copolyester, co-polyesterpolycarbonate or co-polyesterpolyether comprises at least 7 mole % of polymerized units of bisphenol A.

8. The copolyester, co-polyesterpolycarbonate or co-polyesterpolyether copolymer of claim 1 , wherein the mole ratio of polyester polymer structural units to the total of polycarbonate polymer structural units and polyether polymer structural units is from 40:60 to 85:15.

9. A foamable composition comprising the copolyester, co-polyesterpolycarbonate or co-polyesterpolyether copolymer of claim 1 and one or more blowing agents, and, optionally, further comprising an immiscible polyolefin, a colorant, a filler, a flame retardant agent, an infra-red attenuator, a nucleating agent, a lubricant, an antistatic agent, or an antioxidant, or a combination thereof.

10. The foamable composition of claim 9 , wherein the blowing agent is selected from one or more pentane hydrocarbons, one or more hydrofluoroolefin, carbon dioxide, nitrogen, oxygen, water, alcohols, ketones, ethers, halogenated hydrocarbons, or olefins, or a combination thereof.

11. The foamable composition of claim 9 , wherein the blowing agent is selected from one or more chemical blowing agents.

12. A foam or foamed article obtained from the composition of claim 9 .

13. The foam or foamed article of claim 12 wherein the foam or foamed article is obtained by:
(a) extrusion foaming of the foamable composition of claim 9 , or
(b) expansion of a solid foamable bead made from the foamable composition of claim 9 .

14. The foam or foamed article of claim 12 , wherein the foam has a density of from 0.01 to 0.1 g/cm 3 .

15. A method of forming the copolyester, co-polyesterpolycarbonate or co-polyesterpolyether copolymer of claim 1 , the method comprising:
(i) melting a blend of at least two polymers selected from a first polyester polymer and one or more other polymer selected from one or more polycarbonate polymer and one or more other polyester polymer, or combination thereof, and in the presence of a transesterification catalyst, and, optionally, a chain coupling agent;
(ii) maintaining a temperature greater than 200° C. and less than 330° C. for at least 3 minutes and no more than 180 minutes, optionally with mixing; and
(iii) cooling to produce a solid copolymer.

16. The method of claim 15 , wherein the weight ratio of first polyester polymer to one or more other polymers is from 40:60 to 85:15.

17. The method of claim 15 , wherein the weight ratio of the total of all polyester polymers to polycarbonate polymers is from 40:60 to 85:15.

18. The method of claim 15 , wherein the method further comprises the step of collecting at least a portion of any ethylene carbonate produced.

19. The method of claim 15 , wherein one or more polyester polymers is recycled polyethylene terephthalate.

20. A copolyester, co-polyesterpolycarbonate or co-polyesterpolyether copolymer comprising polymerized structural units selected from:
a) one or more aliphatic diol,
b) one or more aromatic diacid,
c) one or more aromatic diol,
d) one or more organic carbonate,
wherein the copolyester copolymer comprises polymerized structural units a+b
the copolyesterpolycarbonate copolymer comprises polymerized structural units a+b+c+d, and
the copolyesterpolyether copolymer comprises polymerized structural units a+b+c+optionally d, and further comprises ether functionality in the polymer backbone;
said copolymer being characterized by:
i) the polymerized structural units of one or more aliphatic diols (a) are present in an amount totaling from 15 mol % to 40 mol %, where the mol % is the sum of the moles of polymerized structural units of the one or more aliphatic diols in the copolymer expressed as a percentage of the total moles of polymerized structural units, a+b+c+d, that make up the copolymer;
ii) a primary Tg between 85° C. and 125° C. as measured from the inflection point on second heatup of the DSC curve using a heating/cooling rate of 10° C./min; and
iii) a heat of melting ΔH m peak no greater than 10 J/g after exposure to hydrostatic pressure of 1000 psi CO 2 at 135° C. for 4 hours.

Assignees

• Ddp Specialty Electronic Materials Us Llc
• Ddp Specialty Electronic Mat Us Inc

Inventors

• Porter Michal Elizabeth
• Barger Mark Alan
• He Yiyong
• Costeux Stéphane
• Billovits Gerald F
• Huang Wenyi
• Nicoli Edoardo

Classifications

• C08J2203/142

  Halogenated saturated hydrocarbons, e.g. H3C-CF3 · CPC title

• C08G64/18

  Block or graft polymers · CPC title

• C08G63/183 Primary

  Terephthalic acids · CPC title

• C08L67/02

  Polyesters derived from dicarboxylic acids and dihydroxy compounds (C08L67/06 takes precedence) · CPC title

• C08G64/06

  not containing aliphatic unsaturation · CPC title