ELASTOMER BLENDS OF POLYESTERS AND COPOLYETHERESTERS DERIVED FROM POLYETHYLENE TEREPHTHALATE, METHOD OF MANUFACTURE, AND ARTICLES THEREFROM

• US 20080023887A1
• Filed: 07/23/2007
• Published: 01/31/2008
• Est. Priority Date: 07/26/2006
• Status: Active Grant

• Current Assignee: SHPP Global Technologies BV
• Original Assignee: Sabic Innovative Plastics IP BV (Government of Saudi Arabia)
• Inventors: Miller, Kenneth F., Shah, Dhaval, Vollenberg, Peter H.
• Granted Patent: US 7,799,838 B2
• Time in Patent Office: Days
• US Class Current: 264/500
• CPC Class Codes: C08J 11/24 containing hydroxyl groups
• CPC Class Codes: C08J 2367/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds; C08J2367/06 takes precedence
• CPC Class Codes: C08L 2666/18 Polyesters or polycarbonates according to C08L67/00 - C08L69/00; Derivatives thereof
• CPC Class Codes: C08L 67/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds C08L67/06 takes precedence
• CPC Class Codes: C08L 67/025 containing polyether sequences
• CPC Class Codes: Y02W 30/62 Plastics recycling; Rubber recycling

Abstract

A composition comprising:

• • (1) from 50 to 99 wt % of a modified, random copolyetherester containing:
    • (i) a modified, random polybutylene terephthalate copolymer block that is derived from a polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers and combinations thereof; and that contains at least one residue derived from the polyethylene terephthalate component; and
    • (ii) a polyalkylene oxide copolymer block that is derived from a polyethylene terephthalate component and polyalkylene oxide glycol, and contains polyalkylene oxide and at least one residue derived from the polyethylene terephthalate component; and
  • (2) from 1 to 50 wt % of a polyester;
  • wherein the copolyetherester, the polyester, and optionally any additives, are present in a total amount of 100 wt %.

Claims

1. A composition comprising

(1) from 50 to 99 wt % of a modified, random copolyetherester containing:

(i) a modified, random polybutylene terephthalate copolymer block that is derived from a polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers and combinations thereof; and

that contains at least one residue derived from the polyethylene terephthalate component; and

(ii) a polyalkylene oxide copolymer block that is derived from a polyethylene terephthalate component and polyalkylene oxide glycol, and contains polyalkylene oxide and at least one residue derived from the polyethylene terephthalate component; and

(2) from 1 to 50 wt % of a polyester;

wherein the copolyetherester, the polyester, and optionally any additives, are present in a total amount of 100 wt %.

2. The composition of claim 1, wherein the copolyetherester comprises from 5 to 95-wt % of the polyalkylene oxide block, based on the total weight of the of the copolyetherester.

3. The composition of claim 1, wherein the copolyetherester comprises from 20 to 80 wt % of the modified, polybutylene terephthalate random copolymer block, based on the total weight of the copolyetherester.

4. The composition of claim 1, wherein the polyalkylene oxide glycol is selected from the group consisting of polyethylene oxide glycol, polypropylene oxide glycol, polybutylene oxide glycol, and combinations thereof.

5. The composition of claim 4, wherein the polyalkylene oxide copolymer block comprises poly(1,4-butylene oxide).

6. The composition of claim 5, wherein the poly(1,4-butylene oxide) is derived from a poly(1,4-butylene oxide) glycol component having a number average molecular weight of 100 to 5000 daltons and a poly(1,4-butylene oxide) component having a molecular weight of less than 2500 daltons.

7. The composition of claim 1, wherein the thermoplastic copolyetherester elastomer comprises from 20 to 95 mole percent of the modified, random polybutylene terephthalate copolymer block.

8. The composition of claim 7, wherein the thermoplastic copolyetherester elastomer comprises from 5 to 80 weight percent of the polyalkylene oxide block, based on the total weight of the copolyetherester.

9. The composition of claim 1, wherein each of the residues derived from the recycled polyethylene terephthalate component is selected from the group consisting of ethylene glycol groups, diethylene glycol groups, isophthalic acid groups, cobalt-containing compounds, antimony-containing compounds, germanium-containing compounds, tin containing compounds, aluminum, aluminum salts, 1,3-cyclohexane dimethanol isomers, 1,4-cyclohexane dimethanol isomers, the cis isomer of 1,3-cyclohexane dimethanol, the cis isomer of 1,4-cyclohexane dimethanol, the trans isomer of 1,3-cyclohexane dimethanol, the trans isomer of 1,4-cyclohexane dimethanol, alkali salts, alkaline salts, napthalene dicarboxylic acids, 1,3-propane diol groups, and combinations thereof.

10. The composition of claim 9, wherein at least one of the residues derived from the polyethylene terephthalate component is selected from the group consisting of ethylene glycol groups, diethylene glycol groups, isophthalic acid groups, the cis isomer of 1,3-cyclohexane dimethanol, the trans isomer of 1,3-cyclohexane dimethanol, the cis isomer of 1,4-cyclohexane dimethanol, the trans isomer of 1,4-cyclohexane dimethanol, and combinations thereof.

11. The composition of claim 10, wherein at least one of the residues derived from the recycled polyethylene terephthalate component is selected from the group consisting of the cis isomer of 1,3-cyclohexane dimethanol, the cis isomer of 1,4-cyclohexane dimethanol, the trans isomer of 1,3-cyclohexane dimethanol, the trans isomer of 1,4-cyclohexane dimethanol, and combinations thereof.

12. The composition of claim 11, wherein at least one of the residues derived from the recycled polyethylene terephthalate component comprises a combination of ethylene glycol groups, diethylene glycol groups, and cobalt-containing compounds.

13. The composition of claim 12, wherein at least one of the residues derived from the polyethylene terephthalate component further comprises an isophthalic acid group.

14. The composition of claim 12, wherein at least one of the residues derived from the polyethylene terephthalate component comprises a combination of an ethylene glycol group and a diethylene glycol group.

15. The composition of claim 14, wherein at least one of the residues derived from the polyethylene terephthalate component further comprises an isophthalic acid group.

16. The composition of claim 15, wherein at least one of the residues derived from the polyethylene terephthalate component is selected from the group consisting of the cis isomer of 1,3-cyclohexane dimethanol, cis isomer of 1,4-cyclohexane dimethanol, a trans isomer of 1,3-cyclohexane dimethanol, a trans isomer of 1,4-cyclohexane dimethanol, or combinations thereof.

17. The composition of claim 1, wherein at least one of the residues derived from the polyethylene terephthalate component is selected from the group consisting of ethylene glycol groups, diethylene glycol groups, and cyclohexane dimethanol groups and is in an amount from 0.1 to 10 mole %, based on 100 mole % of glycol in the composition.

18. The composition of claim 17, wherein the residue derived from the polyethylene terephthalate component further comprises isophthalic acid groups in an amount ranging from 0 to 10 mole %, based on 100 mole % of acid functionality in the polybutylene terephthalate random copolymer.

19. The composition of claim 1, wherein the copolyetherester has

(1) a long chain ester having the formula:

20. An article molded or extruded from the composition of claim 1.

21. The composition of claim 1, wherein a residue of the modified, random copolyetherester is derived from a member selected from the group consisting of 1,4-butane diol, 1,3-propane diol, polyalkylene oxide, and combinations thereof, which are derived from a biomass.

22. The composition of claim 21, wherein the biomass is selected from the group consisting of cellulosic materials, grains, and combinations thereof.

23. The composition of claim 22, wherein the grain is selected from the group consisting of corn, wheat, or and combinations thereof.

24. The composition of claim 1, wherein the composition further comprises a carboxy reactive component in an amount from 0.01 to 5 wt %, based on the total weight of the composition.

25. The composition of claim 1, wherein the composition further comprises a flame retardant in an amount from 0.01 to 30 wt %, based on the total weight of the composition.

26. The composition of claim 1, wherein the polyester is a polyalkylene terephthalate selected from the group consisting of polyethylene terephthalate, polycyclohexane terephthalate, copolyesters of terephthalate esters with comonomers containing cyclohexyl dimethanol and ethylene glycol, copolyesters of terephthalate acid with comonomers containing cyclohexyl dimethanol and ethylene glycol, polytrimethylene terephthalate, poly-xylylene terephthalate, polydianol terephthalates, polybutylene terephthalate, polyester naphthalates, and combinations thereof.

27. The composition of claim 1, wherein the polyester further comprises a member selected from the group consisting of (1) modified polybutylene terephthalate random copolymers derived from a polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers and containing at least one residue derived from the polyethylene terephthalate component and (2) polytrimethylene terephthalate random copolymers that are (A) derived from polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers and (B) contain at least one residue derived from the polyethylene terephthalate component.

28. A process comprising for making the copolyetherester of claim 1, the process comprising:

(a) depolymerizing a polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers by reacting the

(i) polyethylene terephthalate component with

(ii) 1,4-butane diol at a pressure that is at least atmospheric pressure in the presence of a catalyst component, under an inert atmosphere conditions sufficient to depolymerize the polyethylene terephthalate component into a molten mixture containing oligomers, 1,4-butane diol, ethylene glycol, and mixtures thereof;

wherein the polyethylene terephthalate component and the diol are combined in the liquid phase under agitation and the diol is refluxed back into the reactor; and

(b) agitating the molten mixture under subatmospheric pressure and removing excess diol, ethylene glycol, tetrahydrofuran;

wherein the polyalkylene oxide glycol is added during the process in an amount and under conditions that are sufficient to form the copolyetherester.

29. The process of claim 28, wherein the polyalkylene oxide glycol is selected from the group consisting polyethylene oxide glycols, polypropylene oxide glycols, polybutylene oxide glycols, and combinations thereof.

30. The process of claim 28, wherein the polyethylene terephthalate component is depolymerized at a temperature ranging from 180°

C. to 260°

C.

31. The process of claim 28, wherein the temperature of the molten mixture is increased to a temperature ranging from 240 C to 270 C.

32. The process of claim 28, wherein the polyalkylene oxide glycol is added during the depolymerization of the polyethylene terephthalate component.

33. The process of claim 28, wherein the polyalkylene oxide glycol is added during the agitation of the molten mixture under subatmospheric pressure.

34. The process of claim 28, wherein a member selected from the group consisting of 1,4-butane diol, 1,3-propane diol, polyalkylene oxide glycol, and combinations thereof is derived from biomass.

35. The process of claim 34, wherein the biomass is a grain selected from the group consisting of corn, wheat, and combinations thereof.

36. The process of claim 1, wherein the process further comprises adding a polyester and in sufficient amounts to form the composition of claim 1.

37. A process for making the copolyetherester of the composition of claim 1, the process comprising:

(a) depolymerizing a polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers by agitating the polyethylene terephthalate component with member selected from the group consisting of ethylene glycol, 1,3 propane diol, and combinations thereof, in a reactor at a pressure that is at least atmospheric pressure in the presence of a catalyst component under conditions sufficient to depolymerize the polyethylene terephthalate component into a first molten mixture containing components selected from the group consisting of oligomers containing ethylene terephthalate moieties, oligomers containing ethylene isophthalate moieties, oligomers containing diethylene terephthalate moieties, oligomers containing diethylene isophthalate moieties, oligomers containing trimethylene terephthalate moieties, oligomers containing trimethylene isophthalate moieties, covalently bonded oligomeric moieties containing at least two of the foregoing moieties, ethylene glycol, propylene glycol, and combinations thereof;

(b) adding 1,4-butane diol to the first molten mixture in a reactor in the presence of a catalyst component, under conditions that are sufficient to form a second molten mixture containing a component selected from the group consisting of oligomers containing ethylene terephthalate moieties, oligomers containing terephthalate moieties, propylene glycol, 1,4 butane diol, ethylene glycol, and combinations thereof; and

(c) subjecting the second molten mixture to subatmospheric conditions and agitation sufficient to form the copolyetherester of the composition of claim 1;

wherein the polyalkylene oxide glycol is added during the process in an amount and under conditions that are sufficient to form the copolyetherester and oligomers containing terephthalate moieties, propylene glycol, and ethylene glycol are removed during formation of the copolyetherester.

38. The process of claim 37, wherein the polyethylene terephthalate component is depolymerized at a temperature ranging from 190°

C. to 250°

C., under an inert atmosphere.

39. The process of claim 37, wherein step (b) is conducted at a temperature ranging from 190°

C. to 240°

C.

40. The process of claim 37, wherein during step (c), the temperature is increased to a temperature ranging from 240°

C. to 260°

C.

41. The process of claim 37, wherein the polyalkylene oxide glycol is added during the depolymerization of the polyethylene terephthalate component.

42. The process of claim 37, wherein the polyalkylene oxide glycol is added during the agitation of the first molten mixture.

43. The process of claim 37, wherein the polyalkylene oxide glycol is added during the agitation of the second molten mixture.

44. The process of claim 37, wherein the member selected from the group consisting of 1,4-butane diol, 1,3-propane diol, polyalkylene oxide glycol, and combinations thereof is derived from biomass.

45. The process of claim 44, wherein the biomass is a grain selected from the group consisting of corn, wheat, and combinations thereof.

46. The process of claim 37, wherein the polyalkylene oxide glycol is selected from the group consisting of polyethylene oxide glycols, polypropylene oxide glycols, polybutylene oxide glycols, and combinations thereof.

47. The process of claim 37, wherein the process further adding a polyester and forming the composition of claim 1.

49. An article comprising the composition of claim 1.

50. The article of claim 49, wherein the article is in the form of a constant velocity joint boot, a prop shaft boot, a rear wheel drive boot, an air duct, a hose or a tube.

51. A method of forming a composition with improved heat stability, comprising melt blending the components of the composition of claim 1.

52. A method of forming an article, comprising shaping, extruding, blow molding, or injection molding the composition of claim 1 to form an article.

48. A composition comprising

(a) from 55 to 99 wt % of a modified, random copolyetherester containing:

(i) a modified, random polybutylene terephthalate copolymer block that is derived from a polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers and combinations thereof; and

contains at least one residue derived from the polyethylene terephthalate component; and

(ii) a polyalkylene oxide copolymer block that is derived from a polyethylene terephthalate component and polyalkylene oxide glycol, and contains polyalkylene oxide and at least one residue derived from the polyethylene terephthalate component; and

(b) from 10 to 45 wt % a polyester;

(c) from 0.01 to 5 wt % of a carboxy reactive material,

(d) from 0.01 to 2 wt % of a stabilizer composition selected from the group consisting of hindered diol stabilizers, thioester stabilizers, amine stabilizers, phosphite stabilizers, and combinations thereof,

(e) from 0 to 5 wt % of at least one colorant.

wherein ingredients (a) to (e) are present in a total amount of 100 wt %.

53. An article comprising the composition of claim 48.

54. The article of claim 53, wherein the article is selected from the group consisting of constant velocity joint boots, prop shaft boots, rear wheel drive boots, air ducts, hoses, tubes, and combinations thereof.

55. A method of forming a composition with improved heat stability, comprising melt blending the components of the composition of claim 48.

56. A method of forming an article, comprising shaping, extruding, blow molding, or injection molding the composition of claim 48 to form an article.