POLYMER BLENDS

• US 20130209775A1
• Filed: 10/11/2011
• Published: 08/15/2013
• Est. Priority Date: 10/11/2010
• Status: Active Grant

• Current Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Original Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Inventors: Allen, Scott D., Naik, Sanjeev
• Granted Patent: US 9,738,784 B2
• Time in Patent Office: Days
• US Class Current: 428/220
• CPC Class Codes: B29C 48/0018 combined with shaping by orienting, stretching or shrinking, e.g. film blowing B29C48/0017 takes precedence
• CPC Class Codes: C08J 5/18 Manufacture of films or sheets
• CPC Class Codes: C08L 23/02 not modified by chemical after-treatment
• CPC Class Codes: C08L 23/04 Homopolymers or copolymers of ethene
• CPC Class Codes: C08L 23/06 Polyethene
• CPC Class Codes: C08L 23/10 Homopolymers or copolymers of propene
• CPC Class Codes: C08L 23/12 Polypropene
• 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: Y10T 428/31507 Of polycarbonate

Abstract

The present invention provides, among other things, extruded blends of aliphatic polycarbonates and polyolefins. In one aspect, provided blends comprise aliphatic polycarbonates such as poly(propylene carbonate) and a lesser amount of a crystalline or semicrystalline polymer. In certain embodiments, provided blends are characterized in that they exhibit unexpected improvements in their elongation properties. In another aspect, the invention provides methods of making such materials and applications of the materials in applications such as the manufacture of consumer packaging materials.

Claims

1. An extruded polymer blend comprising at least one aliphatic polycarbonate and at least one polyolefin.

2. The extruded polymer blend of claim 1, wherein the aliphatic polycarbonate comprises a copolymer of carbon dioxide and one or more epoxides.

3. The extruded polymer blend of claim 2, wherein the aliphatic polycarbonate is selected from the group consisting of poly(propylene carbonate);

poly(ethylene carbonate);

poly(propylene carbonate)-co-poly(ethylene carbonate);

a poly(propylene carbonate) co-polymer with one or more additional aliphatic polycarbonates, a poly(ethylene carbonate) co-polymer with one or more additional aliphatic polycarbonates, a physical blend of any two or more of the above, and a copolymer comprising any of the above.

4. The extruded polymer blend of claim 1, comprising poly(propylene carbonate).

5. The extruded polymer blend of claim 1, comprising poly(ethylene carbonate).

6. The extruded polymer blend of claim 1, wherein the polyolefin is selected from the group consisting of:

polyethylene, polypropylene, polystyrene, poly(alpha olefins), polyvinyl chloride, and mixtures or copolymers of any two or more of these.

7. The extruded polymer blend of claim 1, wherein the polyolefin is selected from the group consisting of LDPE, LLDPE, HDPE, polypropylene, or any combination of the above.

8. The extruded polymer blend of claim 1, wherein the polyolefin comprises polyethylene.

9. The extruded polymer blend of claim 1, wherein the polyolefin comprises polypropylene.

10. The extruded polymer blend of claim 1, further comprising at least one compatibilizer.

11. The extruded polymer blend of claim 1, wherein the aliphatic polycarbonate represents less than 50% of the weight of the blend.

12. The extruded polymer blend of claim 11, wherein the aliphatic polycarbonate represents between about 5% and about 50% of the blend.

13. The extruded polymer blend of claim 11, wherein the aliphatic polycarbonate represents between about 5% and about 30% of the blend.

14. The extruded polymer blend of claim 11, wherein the aliphatic polycarbonate represents between about 10% and about 25% of the blend.

15. The extruded polymer blend of claim 1, wherein the polyolefin represents less than 50% of the weight of the blend.

16. The extruded polymer blend of claim 11, wherein the polyolefin represents between about 5% and about 50% of the blend.

17. The extruded polymer blend of claim 11, wherein the polyolefin represents between about 5% and about 30% of the blend.

18. The extruded polymer blend of claim 11, wherein the polyolefin represents between about 10% and about 25% of the blend.

19. The extruded polymer blend of any one of claims 1-18, wherein the blend has been extruded at a temperature above 160°

C.

20. The extruded polymer blend of claim 19, wherein the blend has been extruded at a temperature above 170°

C.

21. The extruded polymer blend of claim 19, wherein the blend has been extruded at a temperature above 180°

C.

22. The extruded polymer blend of claim 19, wherein the blend has been extruded at a temperature above 200°

C.

23. A plastic film comprising an extruded polymer blend of any one of claims 1-18.

24. A food package comprising a plastic film of claim 23.

25. An injection molded plastic article comprising an extruded polymer blend of any one of claims 1-18.

26. A polymer blend barrier film comprising an aliphatic polycarbonate in combination with one or more non aliphatic polycarbonate polymers characterized in that the measured oxygen permeability that is less than expected from the predicted permeability calculated using the oxygen permeability values of the polymers in the blend using a method selected from:

a volume additive model and a Maxwell model.

27. The polymer blend barrier film of claim 26, wherein the measured oxygen permeability is less than half of the value predicted from a volume additive model.

28. The polymer blend barrier film of claim 26, wherein the measured oxygen permeability is less than one fifth of the value predicted from a volume additive model.

29. The polymer blend barrier film of claim 26, wherein the measured oxygen permeability is less than half of the value predicted from a Maxwell model.

30. The polymer blend barrier film of claim 26, wherein the measured oxygen permeability is less than one fifth of the value predicted from a Maxwell model.

31. The polymer blend barrier film of claim 26, wherein the aliphatic polycarbonate comprises a copolymer of carbon dioxide and one or more epoxides.

32. The polymer blend barrier film of claim 31, wherein the aliphatic polycarbonate is selected from the group consisting of poly(propylene carbonate);

poly(ethylene carbonate);

poly(propylene carbonate)-co-poly(ethylene carbonate);

a poly(propylene carbonate) co-polymer with one or more additional aliphatic polycarbonates, a poly(ethylene carbonate) co-polymer with one or more additional aliphatic polycarbonates, a physical blend of any two or more of the above, and a copolymer comprising any of the above.

33. The polymer blend barrier film of claim 26, comprising poly(propylene carbonate).

34. The polymer blend barrier film of claim 26, comprising poly(ethylene carbonate).

35. The polymer blend barrier film of claim 26, wherein the non aliphatic polycarbonate polymer is selected from the group consisting of:

LDPE, LLDPE, HDPE, polypropylene, polystyrene, polyvinyl chloride, poly(lactic acid), thermoplastic starch, poly(3-hydroxylbutyrate), poly(3-hydroxyvalerate), poly(3-hydroxylbutyrate-co-3-hydroxyvalerate), poly(ethylene terephthalate) (PET), biodegradable polyesters like poly(butylene adipate), poly(butylene succinate), poly(butylene adipate-co-terephtalate), poly(butylene adipate-co-butylene succinate), other aliphatic and aromatic polyesters, poly(vinyl alcohol), poly(vinyl acetate), ethylene vinyl alcohol polymer (EVOH), poly(caprolactone), poly(ethylene glycol)dimethacrylates, polyesteramide, or any combination of the above.

36. The polymer blend barrier film of claim 26, wherein the non aliphatic polycarbonate polymer comprises a polyester.

37. The polymer blend barrier film of claim 36, wherein the polyester comprises PLA.

38. The polymer blend barrier film of claim 36, wherein the polyester comprises PHB.

39. The polymer blend barrier film of claim 26, wherein the non aliphatic polycarbonate polymer comprises a polyolefin.

40. The polymer blend barrier film of claim 39, wherein the polyolefin comprises polyethylene.

41. The polymer blend barrier film of claim 39, wherein the polyolefin comprises polypropylene.

42. The polymer blend barrier film of claim 39, wherein the polyolefin is selected from the group consisting of LDPE, LLDPE, HDPE, polypropylene, polystyrene, poly(lactic acid), thermoplastic starch, poly(3-hydroxylbutyrate), poly(3-hydroxyvalerate), poly(3-hydroxylbutyrate-co-3-hydroxyvalerate), poly(ethylene terephthalate) (PET), biodegradable polyesters like poly(butylene adipate), poly(butylenes succinate), poly(butylene adipate-co-butylene succinate), poly(butylene adipate-co-terephtalate), other aliphatic and aromatic polyesters, poly(vinyl alcohol), poly(vinyl acetate), ethylene vinyl alcohol polymer (EVOH), poly(caprolactone), poly(ethylene glycol)dimethacrylates, polyesteramide, and any combination of the above.

43. The polymer blend film of claim 42, wherein the polycarbonate is selected from the group consisting of poly(ethylene carbonate), poly(propylene carbonate), a poly(ethylene-propylene carbonate)terpolymer, and any combination of the above.

44. The polymer blend film of claim 26, wherein the polycarbonate comprises poly(propylene carbonate), wherein, on average in the poly(propylene carbonate), at least 80% of adjacent monomer units are oriented head-to-tail.

45. The polymer blend film of claim 26, wherein the polycarbonate comprises at least about 10% by weight of the total weight of the polycarbonate and the polyolefin.

46. The polymer blend film of claim 26, wherein the polyolefin comprises at least about 10% by weight of the total weight of the polycarbonate and the polyolefin.

47. A polymer blend film comprising:

a) a polycarbonate having a first oxygen permeability;

b) a polyolefin having a second oxygen permeability;

wherein the polymer blend film has a third oxygen permeability less than an oxygen permeability value calculated from a volume additive model using a value of the first oxygen permeability and a value of the second oxygen permeability.

48. The polymer blend film of claim 47, wherein the third oxygen permeability is less than an oxygen permeability value calculated from a Maxwell model using the value of the first oxygen permeability and the value of the second oxygen permeability.

49. The polymer blend film of claim 47, wherein the polymer blend film is extruded from a single polymer blend.

50. The polymer blend film of claim 47, wherein the polymer blend film has a thickness of about 100 mils or less.

51. The polymer blend film of claim 47, further comprising at least one compatibilizer.

52. The polymer blend film of claim 47, wherein the polyolefin is selected from the group consisting of LDPE, LLDPE, HDPE, polypropylene, polystyrene, poly(lactic acid), thermoplastic starch, poly(3-hydroxylbutyrate), poly(3-hydroxyvalerate), poly(3-hydroxylbutyrate-co-3-hydroxyvalerate), poly(ethylene terephthalate) (PET), biodegradable polyesters like poly(butylene adipate), poly(butylenes succinate), poly(butylene adipate-co-butylene succinate), poly(butylene adipate-co-terephtalate), other aliphatic and aromatic polyesters, poly(vinyl alcohol), poly(vinyl acetate), ethylene vinyl alcohol polymer (EVOH), poly(caprolactone), poly(ethylene glycol)dimethacrylates, polyesteramide, and any combination of the above.

53. The polymer blend film of claim 47, wherein the polycarbonate is selected from the group consisting of poly(ethylene carbonate), poly(propylene carbonate), a poly(ethylene-propylene carbonate)terpolymer, and any combination of the above.

54. The polymer blend film of claim 47, wherein the polycarbonate comprises poly(propylene carbonate), wherein, on average in the poly(propylene carbonate), at least 80% of adjacent monomer units are oriented head-to-tail.

55. The polymer blend film of claim 47, wherein the polycarbonate comprises at least about 10% by weight of the total weight of the polycarbonate and the polyolefin.

56. The polymer blend film of claim 47, wherein the polyolefin comprises at least about 10% by weight of the total weight of the polycarbonate and the polyolefin.

57. A polymer blend comprising:

a) poly(propylene carbonate); and

b) a polyolefin.

58. The polymer blend of claim 57, wherein the polymer blend is a single polymer blend extruded to form a polymer blend film.

59. The polymer blend of claim 58, wherein the polymer blend film has a thickness of about 100 mils or less.

60. The polymer blend of claim 57, further comprising at least one compatibilizer.

61. The polymer blend of claim 57, wherein the polyolefin is selected from the group consisting of LDPE, LLDPE, HDPE, polypropylene, polystyrene, poly(lactic acid), thermoplastic starch, poly(3-hydroxylbutyrate), poly(3-hydroxyvalerate), poly(3-hydroxylbutyrate-co-3-hydroxyvalerate), poly(ethylene terephthalate) (PET), biodegradable polyesters like poly(butylene adipate), poly(butylenes succinate), poly(butylene adipate-co-terephtalate), poly(butylene adipate-co-butylene succinate), other aliphatic and aromatic polyesters, poly(vinyl alcohol), poly(vinyl acetate), ethylene vinyl alcohol polymer (EVOH), poly(caprolactone), poly(ethylene glycol)dimethacrylates, polyesteramide, and any combination of the above.

62. The polymer blend of claim 57, wherein on average in the poly(propylene carbonate), at least 80% of adjacent monomer units are oriented head-to-tail.

63. The polymer blend of claim 57, wherein the poly(propylene carbonate) comprises at least about 5% by weight of the total weight of the poly(propylene carbonate) and the polyolefin.

64. The polymer blend of claim 57, wherein the polyolefin comprises at least about 5% by weight of the total weight of the poly(propylene carbonate) and the polyolefin.

65. A plastic film comprising at least 70 weight percent aliphatic polycarbonate, characterized in that the film has elongation before break value as measured with ASTM D882 of at least 100%.

66. The plastic film of claim 65, wherein the aliphatic polycarbonate comprises one or more of poly(propylene carbonate) and poly(ethylene carbonate).

67. The plastic film of claim 65, wherein the aliphatic polycarbonate comprises poly(propylene carbonate).

68. The plastic film of claim 65, wherein the aliphatic polycarbonate comprises poly(ethylene carbonate).

69. The plastic film of claim 65, comprising at least 80 weight percent aliphatic polycarbonate.

70. The plastic film of claim 65, comprising at least 85 weight percent aliphatic polycarbonate.

71. The plastic film of claim 65, comprising at least 90 weight percent aliphatic polycarbonate.

72. The plastic film of claim 65, comprising at least 95 weight percent aliphatic polycarbonate.

73. The plastic film of claim 65, further comprising one or more semicrystalline polymers.

74. The plastic film of claim 65, further comprising one or polyolefin polymers.

75. The plastic film of claim 74, comprising from about 0.5 to about 30 weight percent of one or more polyolefin polymers.

76. The plastic film of claim 74, comprising from about 0.5 to about 30 weight percent of one or more polyolefin polymers.

77. The plastic film of claim 74, comprising from about 1 to about 25 weight percent of one or more polyolefin polymers.

78. The plastic film of claim 74, comprising from about 1 to about 10 weight percent of one or more polyolefin polymers.

79. The plastic film of claim 74, comprising from about 2 to about 8 weight percent of one or more polyolefin polymers.

80. The plastic film of claim 74, comprising about 5 weight percent of one or more polyolefin polymers.

81. The plastic film of claim any one of claims 74-80, wherein a polyolefin polymer comprises one or more of:

polyethylene, polypropylene, and polyethylene-co-propylene.

82. The plastic film of claim 81, comprising polyethylene.

83. The plastic film of claim 82, wherein the polyethylene is LDPE.

84. The plastic film of claim 81, comprising polypropylene.

85. The plastic film of claim 65, further comprising one or more compatibilizers.

86. The plastic film of claim 65, wherein the film has been stretched.

87. The plastic film of claim 86, wherein the film has been biaxially stretched.

88. The plastic film of claim 65, wherein the film has been made by a blown film process.

89. The plastic film of claim 86, wherein the elongation before break value as measured with ASTM method D882 of the film prior to stretching is less than 50%.

90. A plastic film comprising at least 70 weight percent aliphatic polycarbonate characterized in that the film has been stretched and that the elongation before break value as measured using ASTM D882, prior to stretching is less than 50% and that the elongation before break value as measured using ASTM D882 after stretching is greater than 100%.

91. A method comprising the steps of:

a) providing an aliphatic polycarbonate characterized in that when the aliphatic polycarbonate is made into a film, the film has an inherent elongation before break value as measured using ASTM D882 of less than 50%;

b) admixing up to about 30 weight percent of a semicrystalline polymer to provide a mixture comprising at least 70 weight percent aliphatic polycarbonate;

c) forming a film from the mixture of step (b); and

d) stretching the film from step (c) to provide a film having an elongation before break value as measured using ASTM D882 of greater than 100%.

92. The method of claim 91, wherein steps (c) and (d) are performed simultaneously by using a blown film process to make the film.

93. The method of claim 91, wherein the step of forming a film comprises extruding the film.

94. The method of claim 91, wherein the step of stretching the film comprises uniaxially stretching the film.

95. The method of claim 91, wherein the step of stretching the film comprises biaxially stretching the film.

96. The method of claim 91, wherein the aliphatic polycarbonate is characterized in that it has a Tg greater than 35°

C.

97. The method of claim 91, wherein the aliphatic polycarbonate is characterized in that the polycarbonate chains contain, on average, greater than 98% carbonate linkages.

98. The method of any one of claims 91-97, wherein the aliphatic polycarbonate comprises poly(propylene carbonate).

99. The method of claim 91, wherein the semicrystalline polymer admixed in step (b) comprises a polyolefin.

100. The method of claim 99, wherein the polyolefin comprises LDPE.

101. The method of claim 91, wherein step (b) comprises admixing from about 1% to about 10% of a semicrystalline polymer.

102. The method of claim 91, wherein a ratio of the elongation before break value of a film made only from the aliphatic polycarbonate provided in step (a) and the elongation before break value of the final film from step (d) is greater than 2.

103. The method of claim 102, wherein the ratio is greater than 3.

104. The method of claim 103, wherein the ratio is greater than 5.

105. The method of claim 104, wherein the ratio is greater than 10.

106. A composition comprising a blend of an aliphatic polycarbonate and between about 1 and about 10% of a polyolefin characterized in that blend has an elongation before break value as measured by ASTM D882 at least 4 times higher than the aliphatic polycarbonate in an unblended state.

107. The composition of claim 106, wherein the aliphatic polycarbonate comprises a copolymer between carbon dioxide, propylene oxide and optionally one or more additional epoxides.

108. The composition of claim 106, wherein the aliphatic polycarbonate comprises poly(propylene carbonate).

109. The composition of any one of claims 106-108, characterized in that the aliphatic polycarbonate contains greater than 98% carbonate linkages.

110. The composition of claim 109, wherein the aliphatic polycarbonate contains greater than 99% carbonate linkages.

111. The composition of any one of claims 106-108, characterized in that the aliphatic polycarbonate has an Mn between about 50,000 and about 500,000 g/mol.

112. The composition of claim 111, wherein the aliphatic polycarbonate has an Mn between about 50,000 and about 250,000 g/mol.

113. The composition of claim 111, wherein the aliphatic polycarbonate has an Mn between about 120,000 and about 220,000 g/mol.

114. The composition of any one of claims 106-108, characterized in that the aliphatic polycarbonate has a polydispersity index less than 2.

115. The composition of claim 114, wherein the aliphatic polycarbonate has a polydispersity index less than 1.5.

116. The composition of claim 114, wherein the aliphatic polycarbonate has a polydispersity index less than 1.2.

117. The composition of any one of claims 106-108, characterized in that the aliphatic polycarbonate contains less than about 5 weight percent cyclic carbonate.

118. The composition of claim 114, wherein the aliphatic polycarbonate contains less than about 3 weight percent cyclic carbonate.

119. The composition of claim 117, wherein the aliphatic polycarbonate is substantially free of cyclic carbonate.

120. The composition of claim 106, wherein the polyolefin comprises polyethylene.

121. The composition of claim 120, wherein the polyethylene comprises LDPE.

122. The composition of claim 106, wherein the polyolefin comprises polypropylene.

123. The composition of claim 106, wherein the composition comprises a film.

124. The composition of claim 123, wherein the film has been stretched.

125. A packaging film comprising a composition of any one of claims 106-108, 110, 112-113, 115-116, or 118-124.

126. The packaging film of claim 125, wherein the film comprises a monolayer film.

127. The packaging film of claim 125, wherein the film comprises a multilayer film.

128. The packaging film of claim 125, wherein the film comprises a food packaging material.