Degradable polymer composition

• US 5,502,158 A
• Filed: 09/22/1992
• Issued: 03/26/1996
• Est. Priority Date: 08/08/1988
• Status: Expired due to Term

• Current Assignee: Battelle Memorial Institute, BioPak, Inc., NatureWorks LLC (Cargill Incorporated)
• Original Assignee: Ecopol, LLC
• Inventors: Lipinsky, Edward S., Sinclair, Richard G.
• Primary Examiner(s): Cain, Edward J.
• Application Number:
  US07/950,854
• Time in Patent Office: 1,281 Days
• Field of Search: 524/306, 524/310, 524/315, 524/317, 524/320, 528/354, 528/361, 523/124
• US Class Current: 528/354
• CPC Class Codes: A61L 15/26 Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof A61L15/225 takes precedence
• CPC Class Codes: A61L 15/62 Compostable, hydrosoluble or hydrodegradable materials
• CPC Class Codes: B01J 2219/1942 spherical
• CPC Class Codes: C08G 63/08 Lactones or lactides
• CPC Class Codes: C08J 2367/04 Polyesters derived from hydroxy carboxylic acids, e.g. lactones C08J2367/06 takes precedence
• CPC Class Codes: C08J 5/18 Manufacture of films or sheets
• CPC Class Codes: C08K 5/10 Esters; Ether-esters
• CPC Class Codes: C08K 5/101 of monocarboxylic acids
• CPC Class Codes: C08L 101/00 Compositions of unspecified macromolecular compounds
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: C08L 2666/18 Polyesters or polycarbonates according to C08L67/00 - C08L69/00; 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 2666/28 Non-macromolecular organic substances
• CPC Class Codes: C08L 29/00 Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 53/00 Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 57/00 Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
• 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: C09D 167/04 : Polyesters derived from hydroxycarboxylic acids, e.g. lactones C09D167/06 takes precedence
• CPC Class Codes: C09J 167/00 : Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain based on polyester-amides C09J177/12; based on polyester-imides C09J179/08; Adhesives based on derivatives of such polymers
• CPC Class Codes: C09J 167/04 : Polyesters derived from hydroxycarboxylic acids, e.g. lactones C09J167/06 takes precedence
• CPC Class Codes: D21H 17/53 : Polyethers; Polyesters

Abstract

Disclosed are degradable materials which include a nontoxic hydrolytically degradable polymer and nontoxic modifier, wherein the modifier is compatible with the polymer and the modifier is nonvolatile and nonfugitive. Also disclosed are processes for forming the various degradable materials, which include films, molded products, laminates, foams, powders, nonwovens, adhesives and coatings. The disclosed materials and processes are particularly useful for the production of commercial and consumer products in high volumes which are suitable for recycling after use or which are discarded into the environment in large volumes.

Claims

1. A degradable film material comprising:

a) a nontoxic hydrolytically degradable polymer comprising repeating monomer or comonomer units selected from the group consisting of;

##STR6## wherein X is the same or different and is O or NR'"'"' R'"'"' being the same, or different and being H, hydrocarbyl, or substituted hydrocarbyl;

R₁, R₂, R₃ R₄ can be the same or different and are hydrogen, hydrocarbyl containing 1 to 24 carbon atoms, or substituted hydrocarbyl containing 1 to 24 carbon atoms, and where n₁ and n₂ can be the same or different and are an integer of from 1-12;

b) a nontoxic modifier, wherein said modifier is compatible with said polymer such that the film material has a uniform appearance and said modifier is nonvolatile and nonfugitive; and

c) wherein said film material has a tensile strength of less than about 20,000 psi.

2. The film material of claim 1, wherein said polymer has a weight average molecular weight from about 5,000 to about 1,500,000.

3. The film material of claim 1, wherein said polymer is biodegradable.

4. The film material of claim 1, wherein said polymer comprises repeating monomer or comonomer units selected from the group consisting of:

##STR7## wherein X is the same or different and is O or NR'"'"' with R'"'"' being the same or different and being H, hydrocarbyl, or substituted hydrocarbyl;

R₁ and R₂ can be the same or different and are hydrogen, hydrocarbyl containing 1 to 24 carbon atoms, or substituted hydrocarbyl containing 1 to 24 carbon atoms, and where n₁ and n₂ can be the same or different and are an integer of from 1-12.

5. The film material of claim 4, wherein said polymer has a weight average molecular weight from about 100,000 to about 500,000.

6. The film material of claim 4, wherein said repeating monomer or comonomer units comprise repeating monomer or comonomer units derived from monomers selected from the group consisting of alpha-hydroxycarboxylic acids, beta-hydroxycarboxylic acids, gamma-hydroxycarboxylic acids, delta-hydroxycarboxylic acids, epsilon-hydroxycarboxylic acids, beta-lactones, gamma-lactones, delta-lactones, epsilon-lactones, beta-lactams, gamma-lactams, delta-lactams, epsilon-lactams, cyclic diesters of alpha-hydroxycarboxylic acids, dioxanones, substituted variations of the foregoing compounds, and combinations thereof.

7. The film material of claim 4, wherein said repeating units comprise repeating units derived from monomers selected from the group consisting of lactic acid, glycolic acid, epsilon-hydroxycaproic acid, lactide, glycolide, epsilon-caprolactone, delta-valerolactone, substituted variations of the foregoing compounds, and combinations thereof.

8. The film material of claim 4, wherein said polymer is produced by polymerization of monomers, at least 50% by weight of which are monomers selected from the group consisting of lactic acid, lactide, and combinations thereof.

9. The film material of claim 8, wherein said lactide monomers comprise a preponderance of optically active lactide and a lesser amount of optically inactive lactide selected from the group consisting of racemic L,D-lactide and meso L,D-lactide.

10. The film material of claim 4, wherein said polymer is produced by polymerization of monomers, at least 75% of which are monomers selected from the group consisting of lactic acid, lactide and combinations thereof.

11. The film material of claim 1, wherein said polymer does not bioaccumulate.

12. The film material of claim 1, wherein said polymer and modifier are generally regarded as safe.

13. The film material of claim 1, wherein said modifier is intimately dispersible in said polymer, and wherein said polymer is swellable in said modifier.

14. The film material of claim 1, wherein said modifier has a solubility parameter within about 2.0 calories per cubic centimeter of the solubility parameter of said polymer.

15. The film material of claim 1, wherein said modifier has a solubility parameter within about 1.0 calories per cubic centimeter of the solubility parameter of said polymer.

16. The film material of claim 1, wherein said modifier has a solubility parameter within about 0.5 calories per cubic centimeter of the solubility parameter of said polymer.

17. The film material of claim 4, wherein said solubility parameter of said modifier is from about 7.5 to about 16.5 calories per cubic centimeter.

18. The film material of claim 4, wherein said solubility parameter of said modifier is from about 8.0 to about 12.0 calories per cubic centimeter.

19. The film material of claim 4, wherein said polymer has a solubility parameter of from about 9.0 to about 11.0 calories per cubic centimeter.

20. The film material of claim 1, wherein said polymer and modifier have hydrogen bonding indices within about 10 units of each other.

21. The film material of claim 20, wherein said polymer and modifier have hydrogen bonding indices within about 5 units of each other.

22. The film material of claim 1, wherein said polymer and modifier dielectric constants are within about 20 units of each other.

23. The film material of claim 1, wherein said polymer and modifier dielectric constants are within about 5 units of each other.

24. The film material of claim 1, wherein said polymer and modifier have dipole moments within about 6 units of each other.

25. The film material of claim 1, wherein said polymer and modifier have dipole moments within about 2 units of each other.

26. The film material of claim 1, wherein said polymer and modifier have HLB values within about 5 and about 8 HLB units of each other.

27. The film material of claim 1, wherein said polymer and modifier have HLB values within about 3 and about 6 HLB units of each other.

28. The film material of claim 1, wherein said polymer is less than about 20% crystalline.

29. The film material of claim 1, wherein the polymer is a copolymer in which no one monomer constitutes more than about 95 weight percent of the polymer.

30. The film material of claim 1, wherein said modifier has a vapor pressure of less than about 50 Torr at 180°

C.

31. The film material of claim 1, wherein said modifier has a boiling temperature above about 280°

C. at 1 atmosphere pressure.

32. The film material of claim 1, wherein said modifier is thermally and chemically stable at temperatures below about 130°

C.

33. The film material of claim 1, wherein said modifier comprises modifier selected from the group consisting of dicarboxylic acids, derivatives of dicarboxylic acids, polyesters of dicarboxylic acids, tricarboxylic acids, derivatives of tricarboxylic acids, polyesters of tricarboxylic acids, cyclic diesters of alpha-hydroxycarboxylic acids, derivatives of cyclic diesters of alpha-hydroxycarboxylic acids, oligomers of cyclic diesters of alpha-hydroxycarboxylic acids, beta-lactones, delta-lactones, gamma-lactones, ε

-lactones, oligomers of alpha-hydroxycarboxylic acids, esters of oligomers of alpha-hydroxycarboxylic acids, benzoic acid derivatives, epoxy derivatives, glycol derivatives, phthalic acid derivatives, phosphoric acid derivatives, ketones, amides, nitriles, and combinations of the foregoing.

34. The film material of claim 33, wherein said modifier comprises modifier selected from the group consisting of adipic acid derivatives, azelaic acid derivatives, cyclic esters of oligomers of lactic acid, esters of oligomers of lactic acid, citric acid derivatives, polyesters of adipic acid, polyesters of azelaic acid, polyesters of sebacic acid, sebacic acid derivatives, benzoic acid derivatives, epoxy derivatives, glycol derivatives, phthalic acid derivatives, phosphoric acid derivatives, and combinations thereof.

35. The film material of claim 33, wherein said modifier comprises modifier selected from the group consisting of di-n-hexyl adipate, bis(2-ethylhexyl)adipate, diisodecyl adipate, bis(2-butoxyethyl) adipate, bis(2-ethylhexyl)azelate, lactide, epsilon-caprolactone, glycolide, delta-valerolactone, oligomeric lactic acid, oligomeric lactic acid ethyl ester, acetylated lactoyllactate ethyl ester, tri-n-butyl citrate, tri-n-butyl acetylcitrate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, epoxidized soy oil, 2-ethylhexyl epoxy tallate, diethylene glycol dinonanoate, triethylene glycol di(2-ethylbutyrate), pentaerythritol esters, alkoxy sucrose and glucose, acylated sucrose and glucose, alkylated and acylated glycols, starch esters, N-acylated amino acid esters, amide derivatives and oligomers of N-acylated amino acid esters, polyethylene glycol ethers, sulfonamides and derivatives, tri(2-ethylhexyl)phosphate, dimethyl phthalate, diethyl phthalate, butyl 2-ethylhexyl phthalate, bis(2-ethylhexyl)phthalate, dicyclohexyl phthalate, diphenyl phthalate, adipic acid polyester with molecular weight from about 190 to about 6000, azelaic acid polyester with molecular weight from about 232 to about 7500, sebacic acid polyester with molecular weight from about 232 to about 7500, di-n-butyl sebacate, and bis(2-ethylhexyl)sebacate, and combinations thereof.

36. The film material of claim 33, wherein said modifier comprises modifier selected from the group consisting of di-n-hexyl adipate, bis(2-butoxyethyl)adipate, bis(2-ethylhexyl)azelate, lactide, epsilon-caprolactone, glycolide, delta-valerolactone, oligomeric lactic acid, oligomeric lactic acid ethyl ester, tri-n-butyl citrate, tri-n-butyl acetylcitrate, dipropylene glycol dibenzoate, epoxidized soy oil, 2-ethylhexyl epoxy tallate, diethylene glycol dinonanoate, triethylene glycol di(2-ethylbutyrate), butyl 2-ethylhexyl phthalate, bis(2-ethylhexyl)phthalate, dicyclohexyl phthalate, adipic acid polyester with molecular weight from about 190 to about 6000, azelaic acid polyester with molecular weight from about 232 to about 7500, sebacic acid polyester with molecular weight from about 246 to about 8000, di-n-butyl sebacate, and combinations thereof.

37. The film material of claim 1, wherein said modifier comprises modifier selected from the group consisting of dicarboxylic acids, derivatives of dicarboxylic acids, polyesters of dicarboxylic acids, tricarboxylic acids, derivatives of tricarboxylic acids, polyesters of tricarboxylic acids, cyclic diesters of alpha-hydroxycarboxylic acids, derivatives of cyclic diesters of alpha-hydroxycarboxylic acids, oligomers of cyclic diesters of alpha-hydroxycarboxylic acids, beta-lactones, delta-lactones, gamma-lactones, epsilon-lactones, oligomers of alpha-hydroxycarboxylic acids, esters of oligomers of alpha-hydroxycarboxylic acids, and combinations of the foregoing.

38. The film material of claim 1, wherein said modifier comprises modifier selected from the group consisting of adipic acid derivatives, azelaic acid derivatives, cyclic esters, oligomers of lactic acid, esters of oligomers of lactic acid, citric acid derivatives, polyesters of adipic acid, polyesters of azelaic acid, polyesters of sebacic acid, sebacic acid derivatives, and combinations thereof.

39. The film material of claim 1, wherein said modifier comprises modifier selected from the group consisting of di-n-hexyl adipate, lactide, epsilon-caprolactone, glycolide, delta-valerolactone, oligomeric lactic acid, oligomeric lactic acid ethyl ester, tri-n-butyl acetylcitrate, adipic acid polyester with molecular weight from about 190 to about 6000, azelaic acid polyester with molecular weight from about 232 to about 7500, and combinations thereof.

40. The film material of claim 1, wherein said modifier comprises modifiers selected from the group consisting of lactic acid, lactide, oligomers of lactic acid, oligomers of lactide and mixtures thereof, wherein said oligomers of lactic acid and oligomers of lactide are defined by the formula:

##STR8## where m is an integer;

2≦

m≦

75.

41. The film material of claim 1, wherein said modifier comprises oligomeric derivatives of lactic acid and lactide selected from the group defined by the formula:

##STR9## where R=H, alkyl, aryl, alkylaryl or acetyl or acyl, and R is saturated, where R'"'"'=H, alkyl, aryl, alkylaryl or acyl, and R'"'"' is saturated, where R and R'"'"' cannot both be H, where q is an integer;

2≦

q≦

75.

42. The film material of claim 1, wherein said modifier comprises modifiers selected from the group consisting of acetyl tributyl citrate, lactide, glycolide, lactic acid esters, dimethyl adipate, diethyl adipate, caprolactone, acetyl triethyl citrate, bis 2-ethyl hexyl sebacate, and bis 2-ethyl hexyl adipate.

43. The film material of claim 1, wherein said modifier comprises modifiers selected from the group consisting of dibutyl sebacate and triethyl citrate.

44. The film material of claim 1, wherein said polymer is polylactic acid and said modifier is 1-methyl-2-pyrrolidone.

45. The film material of claim 1, wherein said polymer is polylactic acid and said modifier is N-ethyl o,p-toluene sulfonamide.

46. The film material of claim 1, wherein said material comprises between about 1% to about 60% by weight of said modifier.

47. The film material of claim 1, wherein said modifier is hydrolytically degradable.

49. The film material of claim 1, wherein said modifier does not bioaccumulate.

50. The film material of claim 1, wherein said modifier is intimately dispersed in said polymer.

51. The film material of claim 1, wherein said film material is a packaging material.

52. The film material of claim 1, wherein said film material is an extruded film.

53. The film material of claim 1, wherein said film material is a blown film.

54. The film material of claim 1, wherein said film material is a compression molded film.

55. The film material of claim 1, wherein said film material has a thickness of less than about 50 mil.

56. The film material of claim 1, wherein said film material has a thickness sufficient to be designated a sheet material.

69. The film material of claim 8, wherein said lactide monomers comprise a preponderance of optically inactive lactide and a lesser amount of plasticizer to form an amorphous, but orientable, pliable, packaging composition.

70. The film material of claim 52, wherein said film is extruded and oriented.

71. The film material of claim 52, wherein said film is extruded, oriented, and heat-set.

72. The film material of claim 52, wherein said film is extruded, oriented, heat-set, and transparent.

73. The film material of claim 52, wherein said film is extruded and crystalline.

48. The film material of claim wherein said modifier is biodegradable.

57. A plasticized polylactic acid film packaging material having a tensile strength of less than about 20,000 psi.

58. A process for producing a degradable film material, comprising:

forming a composition comprising a nontoxic hydrolytically degradable polymer comprising repeating monomer or comonomer units selected from the group consisting of;

##STR10## wherein X is the same or different and is O or NR'"'"' with R'"'"' being the same or different and being H, hydrocarbyl, or substituted hydrocarbyl;

R₁, R₂, R₃ and R₄ can be the same or different and are hydrogen, hydrocarbyl containing 1 to 24 carbon atoms, or substituted hydrocarbyl containing 1 to 24 carbon atoms, and where n₁ and n₂ can be the same or different and are an integer of from 1-12, and a nontoxic modifier, wherein said modifier is compatible with said polymer, such that the material has a uniform appearance, into a film having a tensile strength of less than about 20,000 psi under conditions such that said modifier is substantially nonvolatile.

59. A process as claimed in claim 58, wherein less than about 25 percent by weight of said modifier is volatilized during said step of forming.

60. A process as claimed in claim 58, wherein said step of forming comprises compression molding said composition.

61. A process as claimed in claim 58, wherein said step of forming comprises extruding said composition.

62. A process as claimed in claim 58, wherein said film has a thickness of less than about 50 mil.

63. A process as claimed in claim 58, wherein said modifier is substantially nonextractable.

64. A process as claimed in claim 58, wherein said modifier has low extractability.

65. A degradable molded material comprising:

a) a nontoxic hydrolyrically degradable polymer, comprising repeating monomer comonomer units selected from the group consisting of;

##STR11## wherein X is the same or different and is O or NR'"'"' with R'"'"' being the same or different and being H, hydrocarbyl, or substituted hydrocarbyl;

R₁, R₂, R₃ and R₃ can be the same or different and are hydrogen, hydrocarbyl containing 1 to 24 carbon atoms, or substituted hydrocarbyl containing 1 to 24 carbon atoms, and where n₁ and n₂ can be the same or different and are an integer of from 1-12;

b) a nontoxic modifier, wherein said modifier is compatible with said polymer such that the material has a uniform appearance and said modifier is nonvolatile and nonfugitive; and

c) wherein said material has a tensile strength of less than about 20,000 psi.

66. A degradable foam material comprising:

a) a nontoxic hydrolytically degradable polymer comprising repeating monomer or comonomer units selected from the group consisting of;

##STR12## wherein X is the same or different and is O or NR'"'"' with R'"'"' being the same or different and being H, hydrocarbyl, or substituted hydrocarbyl;

R₁, R₂, R₃ and R₄ can be the same or different and are hydrogen, hydrocarbyl containing 1 to 24 carbon atoms, or substituted hydrocarbyl containing 1 to 24 carbon atoms, and where n₁ and n₂ can be the same or different and are an integer of from 1-12;

b) a nontoxic modifier, wherein said modifier is compatible with said polymer such that the material has a uniform appearance and said modifier is nonvolatile and nonfugitive.

67. A degradable spun-bonded nonwoven material comprising:

a) a nontoxic hydrolytically degradable polymer comprising repeating monomer or comonomer units selected from the group consisting of;

##STR13## wherein X is the same or different and is O or NR'"'"' with R'"'"' being the same or different and being H, hydrocarbyl, or substituted hydrocarbyl;

R₁, R₂, R₃ and R₄ can be the same or different and are hydrogen, hydrocarbyl containing 1 to 24 carbon atoms, or substituted hydrocarbyl containing 1 to 24 carbon atoms, and wherein n₁ and n₂ can be the same or different and are an integer of from 1-12;

b) a nontoxic modifier, wherein said modifier is compatible with said polymer such that the material has a uniform appearance and said modifier is nonvolatile and nonfugitive.

68. A degradable adhesive material comprising:

a) a nontoxic hydrolytically degradable polymer comprising repeating monomer or comonomer units selected from the group consisting of;

##STR14## wherein X is the same or different and is O or NR'"'"' with R'"'"' being the same or different and being H, hydrocarbyl, or substituted hydrocarbyl;

R₁, R₂, R₃ and R₄ can be the same or different and are hydrogen, hydrocarbyl containing 1 to 24 carbon atoms, or substituted hydrocarbyl containing 1 to 24 carbon atoms, and where n₁ and n₂ can be the same or different and are an integer of from 1-12;

b) a nontoxic modifier, wherein said modifier is compatible with said polymer such that the material has a uniform appearance and said modifier is nonvolatile and nonfugitive.