Articles derived from compositions containing modified polybutylene terephthalate (PBT) random copolymers derived from polyethylene terephthalate (PET)

• US 7,935,737 B2
• Filed: 01/29/2007
• Issued: 05/03/2011
• Est. Priority Date: 01/27/2006
• Status: Active Grant

• Current Assignee: SHPP Global Technologies BV (Government of Saudi Arabia)
• Original Assignee: Sabic Innovative Plastics IP BV (Government of Saudi Arabia)
• Inventors: Gopal, Vikram, Kannan, Ganesh, Miller, Kenneth Frederick, Shah, Dhaval
• Primary Examiner(s): Seidleck; James
• Assistant Examiner(s): Tischler; Frances
• Application Number:
  US11/668,189
• Publication Number:
  US 20070275242A1
• Time in Patent Office: 1,555 Days
• Field of Search: 521/40, 521/40.5, 521/41, 521/42, 521/42.5, 521/47, 521/48, 521/49.5, 528/480, 528/489, 528/491, 528/495, 528/271, 528/272, 528/274, 528/275, 528/278, 528/279, 528/280, 528/282, 528/308.1, 528/308.2, 528/308.3, 528/308.5, 525/50, 525/55, 525/88, 525/165, 525/166, 525/167, 525/168, 525/326.1, 525/339, 525/360, 264/5, 264/37.1, 264/219, 264/23, 264/239, 524/474, 524/540
• US Class Current: 521/48.5
• 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 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 67/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds C08L67/06 takes precedence
• CPC Class Codes: Y02W 30/62 Plastics recycling; Rubber recycling
• CPC Class Codes: Y10T 428/298 Physical dimension

Abstract

Compositions of matter including articles derived from (a) from 5 to 99.99 wt % of a modified polybutylene terephthalate random copolymer that (1) is derived from polyethylene terephthalate and (2) contains a at least one residue derived from polyethylene terephthalate selected from the group consisting of antimony, germanium, diethylene glycol groups, isophthalic acid groups, cis isomer of cyclohexane dimethanol, trans isomer of cyclohexane dimethanol, sodium benzoate, alkali salts, napthalane dicarboxylic acids, 1,3-propane diols, cobalt, cobalt-containing compounds, and combinations thereof, and (b) from 0.01 to 95 wt. % of a member selected from the group consisting of (1) fillers, (2) a carboxy reactive component, (3) polyethyelene terephthalate, (4) a component including a polycarbonate and an impact modifier. The articles may be derived from various conversion processes, e.g., injection molding processes, extrusion processes, thermoforming processes, melt-blown process.

Claims

1. A composition of matter comprising an article derived from a molding composition containing:

(a) from 5 to 99.99 wt % of a modified polybutylene terephthalate random copolymer that (1) is derived from a polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers and (2) comprises at least one residue derived from the polyethylene terephthalate component, and

(b) from 0.01 to 95 wt % of a component member selected from the group consisting of (1) fillers, (2) carboxy reactive materials, (3) polyalkylene terephthalates, (4) combinations of polycarbonates and impact modifiers, (5) impact modifiers, (6) polycarbonates, and (7) combinations thereof;

wherein the modified polybutylene terephthalate random copolymer, the component member selected from the group consisting of (1) fillers, (2) carboxy reactive materials, (3) polyalkylene terephthalates, (4) combinations of polycarbonates and impact modifiers, (5) impact modifiers, (6) polycarbonates, and (7) combinations thereof, and optionally at least one additive, are present in a total amount of 100 wt %; and

wherein the at least one residue derived from the polyethylene terephthalate component is diethylene glycol groups in an amount ranging from 0.1 to 10 mole % based on 100 mole % of glycol in the molding composition.

2. The composition of matter of claim 1, wherein the residue derived from the polyethylene terephthalate component is selected from the group consisting of ethylene glycol groups, diethylene glycol groups, isophthalic acid groups, antimony-containing compounds, germanium-containing compounds, titanium-containing compounds, cobalt-containing compounds, tin containing compounds, aluminum, aluminum salts, 1,3-cyclohexane dimethanol isomers, 1,4-cyclohexane dimethanol isomers, alkali salts, alkaline earth metal salts, phosphorous-containing compounds and anions, sulfur-containing compounds and anions, naphthalene dicarboxylic acids, 1,3-propanediol groups, and combinations thereof.

3. The composition of matter of claim 1, wherein the at least one residue derived from the polyethylene terephthalate component comprises a mixture of ethylene glycol and diethylene glycol.

4. The composition of matter of claim 3, wherein the residue derived from the polyethylene terephthalate component further comprises isophthalic acid.

5. The composition of matter of claim 3, wherein the residue derived from the polyethylene terephthalate component further comprises a cis isomer of the 1,3-cyclohexane dimethanol, cis isomer of 1,4-cyclohexane dimethanol, trans isomer of 1,3-cyclohexane dimethanol, trans isomer of 1,4-cyclohexane dimethanol and combinations thereof.

6. The composition of matter of claim 1, wherein the residue 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, trans isomer of 1,3-cyclohexane dimethanol, trans isomer of 1,4-cyclohexane dimethanol and combinations thereof.

7. The composition of matter of claim 1, wherein the residue derived from the polyethylene terephthalate component is selected from the group consisting of ethylene glycol groups, diethylene glycol groups, isophthalic acid groups, cis isomer of cyclohexane dimethanol, trans isomer of cyclohexane dimethanol, and combinations thereof.

8. The composition of matter of claim 1, wherein the at least one residue derived from the polyethylene terephthalate component comprises a mixture of ethylene glycol, diethylene glycol, and a cobalt-containing compound.

9. The composition of matter of claim 8, wherein the at least one residue derived from the polyethylene terephthalate component further comprises isophthalic acid groups.

10. The composition of matter of claim 1, wherein the residue derived from the polyethylene terephthalate component further comprises a group selected from the group consisting of ethylene glycol groups and cyclohexane dimethanol groups and is in an amount ranging from 0.1 to 10 mole %, based on 100 mole % of glycol in the molding composition.

11. The composition of matter of claim 10, 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 modified polybutylene terephthalate random copolymer.

12. The composition of matter of claim 1 wherein the component member comprises a filler.

13. The composition of matter of claim 12, wherein the filler is present in an amount that is at least 0.5 wt %, and the filler is selected from the group consisting of glass fillers, ceramic fillers, carbon fillers, metal fillers, mineral fillers, nano-fillers, nano-composites, nanotubes, talc, and combinations thereof.

14. The composition of matter of claim 12, wherein the filler is a nanofiller, nanotube, or combination thereof in an amount that is less than 0.5 wt %.

15. The composition of matter of claim 1, wherein the component member comprises the carboxy reactive material that is present in an amount of at least 0.01 wt %, and the carboxy reactive material is selected from the group consisting of polymeric carboxy reactive materials, non-polymeric carboxy-reactive materials, and combinations thereof.

16. The composition of matter of claim 1, wherein the component member comprises the polyalkylene terephthalate, wherein the polyalkylene terephthalate is 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.

17. The composition of matter of claim 1, wherein the component member comprises polycarbonate and an impact modifier;

and the polybutylene terephthalate random copolymer is present in an amount ranging from 5 to 90 wt %, the polycarbonate is present in an amount ranging from 5 to 90 wt %; and

the impact modifier is present in an amount that is at least 1 wt %;

wherein the combined wt % of the polycarbonate and the impact modifier, the polybutylene terephthalate random copolymer, and optionally at least one additive, is 100 wt %.

18. The composition of matter of claim 1, wherein the component member comprises at least one impact modifier.

19. The composition of matter of claim 1, wherein the component member comprises at least one polycarbonate.

20. The composition of matter of claim 1, wherein the article further comprises an additive, and the additive is selected from the group consisting of flame retardants, stabilizers, quenchers, mold release agents, teflon-styrene acrylonitrile mixtures, and combinations thereof.

21. The composition of matter of claim 1, wherein the article is selected from the group consisting of injected molded articles, thermoformed articles, blow molded articles, extruded articles, pultruded articles, rotationally molded articles.

22. The composition of matter of claim 1, wherein the article comprises at least one fiber having a diameter ranging from 5 μ

m to 2000 μ

m.

23. The composition of matter of claim 1, wherein the article is a member selected from the group consisting of melt blown fibers, spun fibers, cold drawn fibers, electrostatic spun fibers, and extruded fibers.

24. The composition of matter of claim 1, wherein the article is a composite selected from the group consisting of (i) composites comprising polybutylene terephthalate random copolymers and glass fillers, (ii) composites comprising polybutylene terephthalate random copolymers and carbon fibers, (iii) composites comprising polycarbonate, polybutylene terephthalate random copolymers and carbon fibers, and (iv) composites comprising polycarbonate, polybutylene terephthalate random copolymers and glass fibers.

25. The composition of matter of claim 1, wherein the modified polybutylene terephthalate random copolymer is further derived from biomass-based 1,4-butanediol.

26. The composition of matter of claim 1, wherein an article derived from the composition has a CO₂ reduction index that of at least 0.06 kg.

28. The composition of matter of claim 26, 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 modified polybutylene terephthalate random copolymer;

and wherein the article has at least one wall having a thickness ranging from 0.1 mm to 2000 mm;

wherein the article is selected from the group consisting of injection molded articles, thermoformed articles, extruded articles, pultruded articles, rotationally molded articles, and blow molded articles.

29. The composition of matter of claim 26, wherein the modified polybutylene terephthalate random copolymer is further derived from biomass-based 1,4-butanediol.

30. The composition of matter of claim 26, wherein an article derived from the composition has a CO₂ reduction index that is 0.06 to 2.5 kg.

31. The composition of matter of claim 1, wherein the article is a bezel.

32. The composition of matter of claim 1, wherein the article is an energy absorber.

33. The composition of matter of claim 1, wherein the article is a connector.

34. An article comprising a bezel of claim 31, wherein the bezel is derived from a composition comprising:

(a) a polyester component comprising from 50 to 99.99 wt % of a modified polybutylene terephthalate random copolymer that (1) is derived from a polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers and (2) comprises at least one residue derived from the polyethylene terephthalate component;

(b) from 2 to 40 wt % of a filler component,

(c) from 0.01 to 3 wt % of a stabilizer,

(d) from 0 to 40 wt % of a polyalkylene terephthalate selected from the group consisting of polyethylene terephthalates, polycyclohexane terephthalates, copolyesters of terephthalic acid with comonomers containing cyclohexyl dimethanol and ethylene glycol, copolyesters of terephthalic acid with comonomers containing cyclohexyl dimethanol and ethylene glycol, polytrimethylene terephthalates, poly-xylylene terephthalates, polydianol terephthalate, polybutylene terephthalates, polyester naphthalates, and combinations thereof;

wherein components (a), (b), (c), (d), and optionally at least one additive, are present in a total amount of 100 wt %.

35. The article of claim 34, wherein the polyester component comprises

(a) a first polyester component having an intrinsic viscosity ranging from 0.5 to 1.0 dL/g and comprising the modified polybutylene terephthalate random copolymer that (1) is derived from a polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers and (2) comprises at least one residue derived from the polyethylene terephthalate component, and

(b) a second polyester component having an intrinsic viscosity ranging from 1.1 to 1.4 dL/g and comprising the modified polybutylene terephthalate random copolymer that (1) is derived from polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers and (2) at least one residue derived from the polyethylene terephthalate component.

36. An article comprising an energy absorber of claim 32, wherein the composition comprises:

a polyester component comprising from 20 to 70 wt % of a modified polybutylene terephthalate random copolymer that (1) is derived from a polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers and (2) comprises at least one residue derived from the polyethylene terephthalate component;

(a) from 20 to 70 wt %, a polycarbonate component;

(b) from 1 to 30 wt % of an impact modifier; and

(c) from 0.001 to 1 wt % of a quencher;

wherein components (a), (b), (c), and optionally at least one additive, are present in a total amount of 100 wt %.

37. The article of claim 36, wherein the composition contains less than 5 wt % of a filler component.

38. The article of claim 36, wherein the polyester component comprises

(a) a first polyester component having an intrinsic viscosity ranging from 0.5 to 1.0 dL/g and comprising the modified polybutylene terephthalate random copolymer that (1) is derived from a polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers and (2) comprises at least one residue derived from the polyethylene terephthalate component, and

(b) a second polyester component having an intrinsic viscosity ranging from 1.1 to 1.4 dL/g and comprising the modified polybutylene terephthalate random copolymer that (1) is derived from polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers and (2) at least one residue derived from the polyethylene terephthalate component.

39. An article comprising a connector of claim 33, wherein the connector is derived from a composition comprising:

(a) a polyester component comprising from 60 to 99.99 wt % of a modified polybutylene terephthalate random copolymer that (1) is derived from a polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers and (2) comprises at least one residue derived from the polyethylene terephthalate component;

(b) from 0 to 20 wt % copolyetherester;

(c) from 0 to 40 wt % of a filler,

(d) from 0 to 20 wt % of a flame retarding component;

(e) from 0.01 to 2 wt % of a stabilizer,

wherein components (a), (b), (c), (d), (e), and optionally at least one additive, are present in a total amount of 100 wt %.

40. The article of claim 39, wherein the composition comprises from 1 to 10 wt % of the copolyetherester.

41. The article of claim 40, wherein the composition comprises less than 5 wt % of the filler.

42. The article of claim 39, wherein the composition comprises from 5 to 40 wt % of the filler.

43. The article of claim 42, wherein the composition comprises less than 5 wt % of the copolyetherester.

27. A composition of matter comprising an article containing:

(a) from 5 to 99.99 wt % of a modified polybutylene terephthalate random copolymer that (1) is derived from polyethylene terephthalate and (2) comprises at least one residue derived from polyethylene terephthalate selected from the group consisting of ethylene glycol groups, isophthalic acid groups, antimony-containing compounds, germanium-containing compounds, titanium-containing compounds, cobalt-containing compounds, tin containing compounds, aluminum, aluminum salts, 1,3-cyclohexane dimethanol isomers, 1,4-cyclohexane dimethanol isomers, alkali salts, alkaline earth metal salts, phosphorous-containing compounds and anions, sulfur-containing compounds and anions, naphthalene napthalene dicarboxylic acids, 1,3-propanediol groups, and combinations thereof;

(b) from 0.01 to 95 wt % of a component member selected from the group consisting of (1) fillers, (2) carboxy reactive materials, (3) polyethylene terephthalates, (4) combinations of polycarbonates and impact modifiers, (5) impact modifiers, (6) polycarbonates, and (7) combinations thereof;

wherein the residue derived from the polyethylene terephthalate is diethylene glycol groups in an amount ranging from 0.1 to 10 mole %, based on 100 mole % of glycol the molding composition; and

wherein the modified polybutylene terephthalate random copolymer, the component member selected from the group consisting of (1) fillers, (2) carboxy reactive materials, (3) polyethylene terephthalates, (4) combinations of polycarbonates and impact modifiers, (5) impact modifiers, (6) polycarbonates, and (7) combinations thereof, and optionally at least one additive, are present in a total amount of 100 wt %.