Aliphatic-aromatic polyetherester compositions, articles, films, coating and laminates and processes for producing same

• US 7,144,632 B2
• Filed: 06/11/2003
• Issued: 12/05/2006
• Est. Priority Date: 06/11/2003
• Status: Active Grant

• Current Assignee: DuPont Industrial Biosciences USA, LLC (DuPont de Nemours, Inc.)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Hayes, Richard Allen
• Primary Examiner(s): BOYKIN, TERRESSA M
• Application Number:
  US10/459,161
• Publication Number:
  US 20040254332A1
• Time in Patent Office: 1,273 Days
• Field of Search: 428/411.1, 428/423.7, 442/76, 442/86, 528/272
• US Class Current: 428/423.7
• CPC Class Codes: B32B 2439/70 Food packaging
• CPC Class Codes: B32B 27/06 as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to a layer of a particular substance B32B9/045; next to a bituminous or tarry layer B32B11/046; next to a water setting substance layer B32B13/12; next to a metal layer B32B15/08; next to a glass layer B32B17/10; next to a layer formed of natural mineral fibres or particles B32B19/045; next to a wood layer B32B21/08; next to a cellulosic plastic layer B32B23/08; next to a natural or synthetic rubber layer B32B25/08
• CPC Class Codes: B32B 27/28 comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
• CPC Class Codes: B32B 27/36 comprising polyesters
• CPC Class Codes: C08G 63/6886 Dicarboxylic acids and dihydroxy compounds
• CPC Class Codes: C08L 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: C08L 2666/26 Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00
• CPC Class Codes: C08L 3/02 Starch; Degradation products thereof, e.g. dextrin
• CPC Class Codes: C08L 67/00 Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 67/025 containing polyether sequences
• CPC Class Codes: C08L 67/04 Polyesters derived from hydroxycarboxylic acids, e.g. lactones C08L67/06 takes precedence
• CPC Class Codes: C08L 69/00 Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• CPC Class Codes: C08L 77/12 Polyester-amides
• CPC Class Codes: C09D 167/00 Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain based on polyester-amides C09D177/12; based on polyester-imides C09D179/08; Coating compositions based on derivatives of such polymers
• CPC Class Codes: D21H 19/28 Polyesters
• CPC Class Codes: D21H 27/10 Packing paper packaging materials of special type or form B65D65/38
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31565 Next to polyester [polyethylene terephthalate, etc.]
• CPC Class Codes: Y10T 428/31786 Of polyester [e.g., alkyd, etc.]
• CPC Class Codes: Y10T 442/2139 Coating or impregnation specified as porous or permeable to a specific substance [e.g., water vapor, air, etc.]
• CPC Class Codes: Y10T 442/2221 : Coating or impregnation is specified as water proof

Abstract

Aliphatic-aromatic polyetherester compositions, articles made from the aliphatic-aromatic polyetherester compositions, and processes for producing the aliphatic-aromatic polyetherester compositions and articles are provided. Articles that can be made from the aliphatic-aromatic polyetherester compositions include films, coatings and laminates. Some of the compositions and articles are biocompostable. The films can further be used to form shaped articles such as sheets, food packaging such as sandwich wraps, thermoformed containers, and coatings for, for example, films and other substrates. The aliphatic-aromatic polyetheresters are based on copolyesters produced from a mixture of aromatic dicarboxylic acids, aliphatic dicarboxylic acids, poly(alkyene ether) glycols, and glycols.

Claims

1. An aliphatic-aromatic copolyetherester comprising an acid component, a glycol component, and 0 to about 5.0 mole percent based on 100 mole % acid component of a polyfunctional branching agent selected from polyfunctional acid, glycol or mixtures thereof, wherein the acid component comprises

a. about 90.0 to about 20.0 mole percent of an aromatic dicarboxylic acid component based on 100 mole percent total acid component, and

b. about 10.0 to about 80.0 mole percent of an aliphatic dicarboxylic acid component based on 100 mole percent total acid component, and wherein

the glycol component comprises

a. about 99.9 to about 92.0 mole percent of a single glycol component selected from a first glycol component group consisting of ethylene glycol, 1,3-propanediol and 1,4-butanediol,

b. about 0.1 to 3.0 about mole percent of a poly(alkylene ether) glycol component,

c. 0 to about 5.0 mole percent of one or more of a second glycol component that is different than the single component selected from the first glycol component group based on 100 mole percent total glycol component, provided that said poly(alkylene ether) glycol component comprises a poly(alkylene ether) glycol other than poly (1,2-propylene glycol).

2. The aliphatic-aromatic copolyetherester of claim 1 wherein said second glycol component is selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, dimer diol, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0/2.6]decane, 1,4-cyclohexanedimethanol, isosorbide, di(ethylene glycol), and tri(ethylene glycol) and mixtures derived therefrom.

3. The aliphatic-aromatic copolyetherester of claim 1 wherein said poly(alkylene ether) glycol component is selected from the group consisting of:

poly(ethylene glycol);

poly(1,3-propylene glycol);

poly(1,4-butylene glycol);

polytetrahydrofuran;

poly(pentmethylene glycol);

poly(hexamethylene glycol);

poly(hepthamethylene glycol);

poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol);

4,4′

-isopropylidenediphenol ethoxylate;

4,4′

-(1-phenylethylidene)bisphenol ethoxylate;

4,4′

-ethylidenebisphenol ethoxylate;

bis(4-hydroxyphenyl)methane ethoxylate;

4,4′

-(1,3-phenylenediisopropylidene)bisphenol ethoxylate;

4,4′

-(1,4-phenylenediisopropylidene)bisphenol ethoxylate;

sulfonyldiphenol ethoxylate;

4,4′

-cyclohexylidenebisphenol ethoxylate; and

mixtures derived therefrom.

4. The aliphatic-aromatic copolyetherester of claim 1 wherein said aromatic dicarboxylic acid component is selected from the group consisting of:

terephthalic acid, dimethyl terephthalate, bis(2-hydroxyethyl)terephthalate, bis(3-hydroxypropyl)terephthalate, bis(4-hydroxybutyl)terephthalate, isophthalic acid, dimethyl isophthalate, bis(2-hydroxyethyl)isophthalate, bis(3-hydroxypropyl)isophthalate, bis(4-hydroxybutyl)isophthalate;

2,6-napthalene dicarboxylic acid, dimethyl-2,6-naphthalate, 2,7-naphthalenedicarboxylic acid, dimethyl-2,7-naphthalate, 3,4′

-diphenyl ether dicarboxylic acid, dimethyl-3,4′

diphenyl ether dicarboxylate, 4,4′

-diphenyl ether dicarboxylic acid, dimethyl-4,4′

-diphenyl ether dicarboxylate, 3,4′

-diphenyl sulfide dicarboxylic acid, dimethyl-3,4′

-diphenyl sulfide dicarboxylate, 4,4′

-diphenyl sulfide dicarboxylic acid, dimethyl-4,4′

-diphenyl sulfide dicarboxylate, 3,4′

-diphenyl sulfone dicarboxylic acid, dimethyl-3,4′

-diphenyl sulfone dicarboxylate, 4,4′

-diphenyl sulfone dicarboxylic acid, dimethyl4,4′

-diphenyl sulfone dicarboxylate, 3,4′

-benzophenonedicarboxylic acid, dimethyl-3,4′

-benzophenonedicarboxylate, 4,4′

-benzophenonedicarboxylic acid, dimethyl-4,4′

-benzophenonedicarboxylate, 1,4-naphthalene dicarboxylic acid, dimethyl-1,4-naphthalate, 4,4′

-methylene bis(benzoic acid), dimethyl-4,4′

-methylenebis(benzoate), and mixtures derived therefrom.

5. The aliphatic-aromatic copolyetherester of claim 1, wherein the acid component comprises about 85 to about 30 mole percent aromatic dicarboxylic acid component and about 15 to about 70 mole percent of said aliphatic dicarboxylic acid component.

6. The aliphatic-aromatic copolyetherester of claim 1, wherein the acid component comprises about 80 to about 40 mole percent aromatic dicarboxylic acid component and about 20 to about 60 mole percent aliphatic dicarboxylic acid component.

7. The aliphatic-aromatic copolyetherester of claim 1, wherein said aliphatic dicarboxylic acid component is selected from the group consisting of oxalic acid, dimethyl oxalate, malonic acid, dimethyl malonate, succinic acid, dimethyl succinate, methylsuccinc acid, glutaric acid, dimethyl glutarate, bis(2-hydroxyethyl)glutarate, bis(3-hydroxypropyl)glutarate, bis(4-hydroxybutyl)glutarate, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, dimethyl adipate, bis(2-hydroxyethyl)adipate, bis(3-hydroxypropyl)adipate, bis(4-hydroxybutyl)adipate, 3-methyladipic acid, 2,2,5,5-tetramethylhexanedioic acid, pimelic acid, suberic acid, azelaic acid, dimethyl azelate, sebacic acid, 1,11-undecanedicarboxylic acid, 1,10-decanedicarboxylic acid, undecanedioic acid, 1,12-dodecanedicarboxylic acid, hexadecanedioic acid, docosanedioic acid, tetracosanedioic acid, dimer acid, and mixtures derived therefrom.

8. The aliphatic-aromatic copolyetherester of claim 1 wherein said aliphatic dicarboxylic acid component is selected from the group consisting of succinc acid, dimethyl succinate, glutaric acid, dimethyl glutarate, bis(2-hydroxyethyl)glutarate, bis(3-hydroxypropyl)glutarate, bis(4-hydroxybutyl)glutarate, adipic acid, dimethyl adipate, bis(2-hydroxyethyl)adipate, bis(3-hydroxypropyl)adipate, bis(4-hydroxybutyl)adipate and mixtures derived therefrom.

9. The aliphatic-aromatic copolyetherester of claim 1, wherein said branching agent is selected from the group consisting of:

1,2,4-benzenetricarboxylic acid;

trimethyl-1,2,4-benzenetricarboxylate;

tris(2-hydroxyethyl)-1,2,4-benzenetricarboxylate;

tris(3-hydroxypropyl)-1,2,4-benzenetricarboxylate;

tris(4-hydroxybutyl)-1,2,4-benzenetricarboxylate;

1,2,4-benzenetricarboxylic anhydride;

1,3,5-benzenetricarboxylic acid;

1,2,4,5-benzenetetracarboxylic acid;

1,2,4,5-benzenetetracarboxylic dianhydride;

3,3′

,4,4′

-benzophenonetetracarboxylic dianhydride;

1,4,5,8-naphthalenetetracarboxylic dianhydride;

citric acid;

tetrahydrofuran-2,3,4,5-tetracarboxylic acid;

1,3,5-cyclohexanetricarboxylic acid;

pentaerythritol;

glycerol;

2-(hydroxymethyl)-1,3-propanediol;

2,2-bis(hydroxymethyl)propionic acid; and

mixtures derived therefrom.

10. The aliphatic-aromatic copolyetherester of claim 1, having an inherent viscosity of at least about 0.15 dL/g.

11. The aliphatic-aromatic copolyetherester of claim 10, having an inherent viscosity of at least about 0.35 dL/g.

12. The aliphatic-aromatic copolyetherester of claim 11, having an inherent viscosity of at least about 0.65 dL/g.

13. The aliphatic-aromatic copolyetherester of claim 1, further comprising a filler.

14. The aliphatic-aromatic copolyetherester of claim 13, wherein said filler comprises a first set of particles having a first average particle size, and a second set of particles having a second average particle size, and wherein second average particle size is at least about 2 times that of said first average particle size.

15. The aliphatic-aromatic copolyetherester of claim 13, wherein said filler consists essentially of particles having an average-diameter less than about 40 microns.

16. The aliphatic-aromatic copolyetherester of claim 13, wherein said filler consists essentially of particles having an average diameter less than about 20 microns.

17. A blend comprising an aliphatic-aromatic copolyetherester of claim 1 and at least one other polymer.

18. The blend of claim 17 wherein said other polymer is biodegradable.

19. The blend of claim 18 wherein said biodegradable polymer is selected from the group consisting of poly(hydroxy alkanoates), polycarbonates, poly(caprolactone), aliphatic polyesters, aliphatic-aromatic copolyesters, aliphatic-aromatic copolyetheresters, aliphatic-aromatic copolyamideesters, sulfonated aliphatic-aromatic copolyesters, sulfonated aliphatic-aromatic copolyetheresters, sulfonated aliphatic-aromatic copolyamideesters, and mixtures derived therefrom.

20. The blend of claim 17 wherein said other polymer is nonbiodegradable.

21. The blend of claim 17 wherein said other polymer is a natural polymer.

22. The blend of claim 21 wherein said natural polymer is a starch.

23. A shaped article formed from an aliphatic-aromatic copolyetherester of claim 1 or claim 13.

24. A shaped article of claim 23 selected from the group consisting of films, sheets, fiber, melt blown containers, molded parts, and foamed parts.

25. A film comprising the aliphatic-aromatic copolyetherester of claim 1 or claim 13.

26. The film of claim 25, having a thickness from about 0.025 mm to about 0.15 mm.

27. An oriented film according to claim 25.

28. An oriented film comprising the aliphatic-aromatic copolyetherester of claim 1 wherein said film is biaxially oriented.

29. An oriented film comprising the aliphatic-aromatic copolyetherester of claim 1 wherein said film is uniaxially oriented.

30. A multilayer film comprising a layer comprising an aliphatic-aromatic copolyetherester of claim 1 or claim 13.

31. An article comprising a substrate and a coating on said substrate, said coating comprising an aliphatic-aromatic copolyetherester of claim 1 or claim 13.

32. The article of claim 31 wherein said coating has a thickness from about 0.2 to about 15 mils.

33. The article of claim 32 wherein said coating has a thickness from about 0.5 to about 2 mils.

34. The article of claim 31 wherein said substrate is selected from the group consisting of textiles, nonwovens, foil, paper, paperboard, and metals.

35. An article comprising a substrate having laminated thereon an aliphatic-aromatic copolyetherester of claim 1.

36. The article of claim 35 wherein said substrate is selected from the group consisting of paper, paperboard, cardboard, fiberboard, cellulose, starch, plastic, polystyrene foam, glass, metals, polymeric foams, organic foams, inorganic foams, organic-inorganic foams, and polymeric films.

37. A package comprising an article of claim 35.

38. A wrap comprising an aliphatic-aromatic copolyetherester of claim 1 or claim 13.

39. A sheet comprising an aliphatic-aromatic copolyetherester of claim 1.

40. The sheet of claim 39, having a thickness of at least about 0.50 mm.

41. A fiber comprising an aliphatic-aromatic copolyetherester of claim 1.

42. The fiber of claim 41 having a denier from about 0.1 to about 100.

43. The fiber of claim 42 having a denier from about 0.5 to 20.

44. A fiber comprising an aliphatic-aromatic copolyetherester of claim 1 and at least one other polymer.

45. The fiber of claim 44 wherein said fiber comprises a blend of said aliphatic-aromatic copolyester and one or more natural fibers.

46. The fiber of claim 45 wherein said fiber is a heterogeneous fiber.

47. A foamed article comprising an aliphatic-aromatic copolyetherester of claim 13.

48. An article comprising a substrate having laminated thereon an aliphatic-aromatic copolyetherester of claim 13.

49. A sheet comprising an aliphatic-aromatic copolyetherester of claim 13.

50. A foamed article comprising an aliphatic-aromatic copolyetherester of claim 17.

51. A shaped article formed from an aliphatic-aromatic copolyetherester of claim 17.

52. A shaped article of claim 51 selected from the group consisting of films, sheets, fiber, melt blown containers, molded parts, and foamed parts.

53. A film comprising the aliphatic-aromatic copolyetherester of claim 19.

54. The film of claim 53, having a thickness from about 0.025 mm to about 0.15 mm.

55. An oriented film according to claim 54.

56. A multilayer film comprising a layer comprising an aliphatic-aromatic copolyetherester of claim 17.

57. An article comprising a substrate and a coating on said substrate, said coating comprising an aliphatic-aromatic copolyetherester of claim 17.

58. An article comprising a substrate having laminated thereon an aliphatic-aromatic copolyetherester of claim 17.

59. A wrap comprising an aliphatic-aromatic copolyetherester of claim 17.

60. A sheet comprising an aliphatic-aromatic copolyetherester of claim 17.

61. A foamed article comprising an aliphatic-aromatic copolyetherester of claim 18.

62. A shaped article formed from an aliphatic-aromatic copolyetherester of claim 18.

63. A shaped article of claim 62 selected from the group consisting of films, sheets, fiber, melt blown containers, molded parts, and foamed parts.

64. A film comprising the aliphatic-aromatic copolyetherester of claim 18.

65. The film of claim 64, having a thickness from about 0.025 mm to about 0.15 mm.

66. An oriented film according to claim 65.

67. A multilayer film comprising a layer comprising an aliphatic-aromatic copolyetherester of claim 18.

68. An article comprising a substrate and a coating on said substrate, said coating comprising an aliphatic-aromatic copolyetherester of claim 18 or claim 21.

69. An article comprising a substrate having laminated thereon an aliphatic-aromatic copolyetherester of claim 18 or claim 21.

70. A wrap comprising an aliphatic-aromatic copolyetherester of claim 18 or claim 21.

71. A sheet comprising an aliphatic-aromatic copolyetherester of claim 18 or claim 21.

72. A foamed article comprising an aliphatic-aromatic copolyetherester of claim 21.

73. A shaped article formed from an aliphatic-aromatic copolyetherester of claim 21.

74. A shaped article of claim 73 selected from the group consisting of films, sheets, fiber, melt blown containers, molded parts, and foamed parts.

75. A film comprising the aliphatic-aromatic copolyetherester of claim 21.

76. The film of claim 75, having a thickness from about 0.025 mm to about 0.15 mm.

77. An oriented film according to claim 75.

78. A multilayer film comprising a layer comprising an aliphatic-aromatic copolyetherester of claim 21.

79. A process for producing a package, comprising (1) providing a substrate;

(2) forming said substrate into a desired package form;

(3) providing an aliphatic-aromatic copolyetherester comprising an acid component, a glycol component, and 0 to about 5.0 mole percent based on 100 mole % acid component of a polyfunctional branching agent selected from polyfunctional acid, glycol or mixtures thereof, wherein the acid component comprises

a. about 90.0 to about 20.0 mole percent of an aromatic dicarboxylic acid component based on 100 mole percent total acid component, and

b. about 10.0 to about 80.0 mole percent of an aliphatic dicarboxylic acid component based on 100 mole percent total acid component, and wherein

the glycol component comprises

a. about 99.9 to about 92.0 mole percent of a single glycol component selected from a first glycol component group consisting of ethylene glycol, 1,3-propanediol and 1,4-butanediol,

b. about 0.1 to 3.0 about mole percent of a poly(alkylene ether) glycol component a poly(alkylene ether) glycol other than poly (1,2-propylene glycol),

c. 0 to about 5.0 mole percent of one or more of a second glycol component that is different than the single component selected from the first glycol component group based on 100 mole percent total glycol component; and

 

(4) laminating or coating said substrate with said aliphatic-aromatic copolyetherester to form said package.

80. The process of claim 79 wherein said substrate comprises a material selected from the group consisting of paper, paperboard, inorganic foams, organic foams, and inorganic-organic foams.

81. The process of claim 79 wherein said package form is selected from the group consisting of wrappers, stretch wrap films, bags, cups, trays, cartons, boxes, bottles, crates, packaging films, blister pack wrappers, skin packaging, and hinged containers.