US5500465A
Expired / Lapsed
US
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Biodegradable multi-component polymeric materials based on unmodified starch-like polysaccharides
Assignee: Michigan State University
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Filing: 1994-03-10
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Granted: 1996-03-19
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Expires: 2014-03-10
Abstract
Abstract Compatibilized blends of a biodegradable hydrophobic polyester, unmodified starch or other similar polysaccharide containing less than 1% water by weight, other biodegradable polymers that may be hydrophobic, plasticizer, and other additives. The blends are produced in the absence of water. The preferred polyester polymer is poly(ε-caprolactone) and the preferred starch is from corn. A small amount of a unique stretching agent is incorporated to provide high elongations at break, especially in film forming compositions containing a significant amount of starch. The starch is a discontinuous phase that may be completely or partially plasticized and the polyester polymer is the continuous phase. The preferred polymers have unique film forming properties and are resistant to water and moisture.
Inventors
- 👤 Mohan Krishnan
- 👤 Ramani Narayan
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 00:32
CPC Classifications
C; C08; C08L; C08L3/00; C08L3/02; C08L67/00; C08L67/04; C08L2201/00; C08L2201/06
Claims Analysis
Total Claims: 51
Claim 1
Independent Claim
110 words
A composition comprising a blend of an unmodified polysaccharide containing alpha-D-glucopyranosyl units containing less than about 1 percent by weight water, optionally a plasticizer for the polysaccharide, a biodegradable hydrophobic aliphatic polyester polymer, and optionally one or more other biodegradable polymers that may be hydrophobic, which has been blended in the absence of water at elevated temperatures, wherein the polysaccharide is a dispersed phase in the polyester polymer as the continuous phase and is 25 to 60% by weight of the composition and wherein an organic peroxide has been provided with the polyester polymer in an amount to provide improved melt strength as compared to the composition without the peroxide.
Claim 2
Dependent Claim
110 words
A composition comprising a blend of an unmodified polysaccharide containing alpha-D-glucopyranosyl units containing less than about 1 percent by weight water, optionally a plasticizer for the polysaccharide, a biodegradable hydrophobic aliphatic polyester polymer, and optionally one or more other biodegradable polymers that may be hydrophobic, which has been blended in the absence of water at elevated temperatures, wherein the polysaccharide is a dispersed phase in the polyester polymer as the continuous phase and is 25 to 60% by weight of the composition and wherein an organic peroxide has been provided with the polyester polymer in an amount to provide improved melt strength as compared to the composition without the peroxide.
Claim 3
Dependent Claim
31 words
The composition of claim 1, wherein the composition is physically stable in liquid water and water vapor, as in high humidities, and exhibits decreased permeability to both water and water vapor.
Claim 4
Dependent Claim
11 words
The composition of claim 1, in which the polysaccharide is starch.
Claim 5
Dependent Claim
31 words
The composition of claim 1 in which the polysaccharide is starch which is selected from the group consisting of starches derived from rice, corn, potato, tapioca, wheat, oats and mixtures thereof.
Claim 6
Dependent Claim
20 words
The composition of claim 4 in which an amylose content of the starch is up to about 95% by weight.
Claim 7
Dependent Claim
11 words
The composition of claim 4 wherein the starch is from corn.
Claim 8
Dependent Claim
31 words
The composition of claim 2 in which the polysaccharide is starch which is present in plasticized or unplasticized form in an amount of at least 30% by weight of the composition.
Claim 9
Dependent Claim
32 words
The composition of claim 2 in which the polysaccharide is starch which is present in plasticized or unplasticized form in an amount of about 30 to 45% by weight of the composition.
Claim 10
Dependent Claim
32 words
The composition of claim 5 in which the polysaccharide is starch which is present in plasticized or unplasticized form in an amount between about 30 to 45% by weight of the composition.
Claim 11
Dependent Claim
40 words
The composition of claim 1 wherein the biodegradable, hydrophobic polyester polymer is selected from the group consisting of poly(ε-caprolactone), polymers, copolymers based on poly(glycolic acid) and poly(L-lactic acid), and a copolymer of these polymers with maleic anhydride or acrylic acid.
Claim 12
Dependent Claim
33 words
The composition of claim 1 wherein the composition contains in addition a biodegradable polymer selected from the group consisting of cellulose acetate, poly(vinyl alcohol) starch esters and amylose esters and optionally includes plasticizers.
Claim 13
Dependent Claim
13 words
The composition of claim 10, wherein the biodegradable hydrophobic polyester polymer is poly(ε-caprolactone).
Claim 14
Dependent Claim
14 words
The composition of claim 10, wherein the polymer is poly(ε-caprolactone-co-maleic anhydride) as a copolymer.
Claim 15
Dependent Claim
21 words
The composition of claim 10 wherein the polymer is a mixture of the poly(ε-caprolactone) polymer and poly(ε-caprolactone-co-maleic anhydride) as a copolymer.
Claim 16
Dependent Claim
20 words
The composition of claim 13 in which the poly(ε-caprolactone-co-maleic anhydride) as a copolymer is generated in situ by the peroxide.
Claim 17
Dependent Claim
26 words
The composition of claim 13 in which the poly(ε-caprolactone-co-maleic anhydride) as a copolymer is separately synthesized by a peroxide initiation and subsequently incorporated into the composition.
Claim 18
Dependent Claim
35 words
The composition of any one of claims 15 or 16 in which the peroxide used is 2,5-dimethyl-2,5-di(t-butyl peroxy)hexane, in the amount of 0.05 to 1 part of peroxide per hundred parts of the polyester polymer.
Claim 19
Dependent Claim
32 words
The composition of any one of claims 15 or 16, wherein an amount of maleic anhydride added is from about 1 to 5 parts per hundred parts of the poly(ε-caprolactone) by weight.
Claim 20
Dependent Claim
23 words
The composition of claims 12, 13 or 14 wherein the amount of poly(ε-caprolactone) in the composition is at least about 35% by weight.
Claim 21
Dependent Claim
23 words
The composition of claims 12, 13 or 14 wherein the amount of poly(ε-caprolactone) in the composition is about 35 to 60% by weight.
Claim 22
Dependent Claim
25 words
The composition of claim 14, wherein the amount of the poly(ε-caprolactone-co-maleic anhydride) as a copolymer in the composition is at least about 0.05% by weight.
Claim 23
Dependent Claim
24 words
The composition of claim 11 wherein the amount of additional biodegradable polymers in the composition is at least 1% by weight of the composition.
Claim 24
Dependent Claim
23 words
The composition of claim 1, wherein the plasticizer is selected from the group consisting of glycerol, sorbitol, glycerol monoacetate, glycerol diacetate, glycerol triacetate.
Claim 25
Dependent Claim
18 words
The composition of claim 23 wherein the plasticizer is at least about 5% by weight of the composition.
Claim 26
Dependent Claim
19 words
The composition of claim 23 wherein the plasticizer is between about 5 and 30% by weight of the composition.
Claim 27
Dependent Claim
32 words
The composition of claim 1 wherein a polyhydric fatty acid ester is provided in the composition as a stretching agent in amount between about 0.5 to 5% by weight of the composition.
Claim 28
Dependent Claim
17 words
The composition of claim 26 wherein the polyhydric fatty acid ester is a polyglycerol fatty acid ester.
Claim 29
Dependent Claim
14 words
The composition of claim 27 wherein the polyglycerol fatty acid ester is decaglycerol tetraoleate.
Claim 30
Dependent Claim
42 words
The composition according to claim 1, in which the said peroxide is selected from the group consisting of 2,5-dimethyl-2,5-di(t-butyl peroxy)hexane, benzoyl peroxide, and di-cumyl peroxide, in the amount of 0.01 to 0.5 part of peroxide per hundred parts of the polyester polymer.
Claim 31
Dependent Claim
23 words
The composition of claim 1, in which there are fillers in an amount of up to 10% by weight based on the composition.
Claim 32
Dependent Claim
47 words
The composition of claim 1, in which there are additives that function as binders selected from the group consisting of proteins, monoglycerides, ethyleneacrylic acid polymer and mixtures thereof and wherein the additives are present in a range of 0.1 to 5 percent by weight of the composition.
Claim 33
Dependent Claim
59 words
The composition of claim 1, in which there are added colorants and additives selected from the group consisting of fatty acids, fatty acid amides, and esters, waxes, fluorinated polymers, and metal oxides, lubricants, flame retardants, viscosity modifiers, wherein the additives are present in a range of 0.1 to 5 parts by weight based on 100 parts of the composition.
Claim 34
Independent Claim
94 words
A method for preparing a biodegradable polymer composition which comprises: admixing a polysaccharide containing alpha-D-glucopyranosyl units having an available water content of less than about 1% by weight with an aliphatic polyester polymer containing formulation in the absence of water to form the biodegradable polymer composition, wherein the polysaccharide is a dispersed phase in the polyester polymer and is between about 25% and 60% by weight of the composition, and wherein an organic peroxide has been provided with the polyester polymer to provide improved melt strength as compared to the composition without the peroxide.
Claim 35
Independent Claim
94 words
A method for preparing a biodegradable polymer composition which comprises: admixing a polysaccharide containing alpha-D-glucopyranosyl units having an available water content of less than about 1% by weight with an aliphatic polyester polymer containing formulation in the absence of water to form the biodegradable polymer composition, wherein the polysaccharide is a dispersed phase in the polyester polymer and is between about 25% and 60% by weight of the composition, and wherein an organic peroxide has been provided with the polyester polymer to provide improved melt strength as compared to the composition without the peroxide.
Claim 36
Dependent Claim
12 words
The method of claim 33 wherein the aliphatic polyester polymer is poly(ε-caprolactone).
Claim 37
Dependent Claim
16 words
The method of claim 33 wherein the aliphatic polyester polymer is poly(ε-caprolactone-co-maleic anhydride) as a copolymer.
Claim 38
Dependent Claim
21 words
The method of claim 33 wherein an organic plasticizer for the starch and the polyester polymer is included in the admixture.
Claim 39
Dependent Claim
20 words
The method of claim 36 wherein the plasticizer is present in an amount between about 5 and 50% by weight.
Claim 40
Dependent Claim
19 words
The method of claim 33 wherein the admixing is at a temperature of between about 130° and 180° C.
Claim 41
Dependent Claim
20 words
The method of claim 33 wherein a polyhydric fatty acid ester is provided in the composition as a stretching agent.
Claim 42
Dependent Claim
17 words
The method of claim 39 wherein the polyhydric fatty acid ester is a polyglycerol fatty acid ester.
Claim 43
Dependent Claim
14 words
The method of claim 40 wherein the polyglycerol fatty acid ester is decaglycerol tetraoleate.
Claim 44
Dependent Claim
120 words
A composition comprising a blend of an unmodified polysaccharide containing alpha-D-glucopyranosyl units containing less than about 1 percent by weight water, optionally a plasticizer for the polysaccharide, a biodegradable hydrophobic aliphatic polyester polymer, and optionally one or more other biodegradable polymers that may be hydrophobic, which has been blended in the absence of water at elevated temperatures wherein an organic peroxide has been provided with the polyester polymer in an amount to provide improved melt strength as compared to the composition without the peroxide, wherein the polysaccharide is a dispersed phase in the polyester polymer as the continuous phase and is 25 to 60% by weight of the composition, and wherein the polyester polymer is poly(ε-caprolactone-co-maleic anhydride) as a copolymer.
Claim 45
Dependent Claim
120 words
A composition comprising a blend of an unmodified polysaccharide containing alpha-D-glucopyranosyl units containing less than about 1 percent by weight water, optionally a plasticizer for the polysaccharide, a biodegradable hydrophobic aliphatic polyester polymer, and optionally one or more other biodegradable polymers that may be hydrophobic, which has been blended in the absence of water at elevated temperatures wherein an organic peroxide has been provided with the polyester polymer in an amount to provide improved melt strength as compared to the composition without the peroxide, wherein the polysaccharide is a dispersed phase in the polyester polymer as the continuous phase and is 25 to 60% by weight of the composition, and wherein the polyester polymer is poly(ε-caprolactone-co-maleic anhydride) as a copolymer.
Claim 46
Dependent Claim
20 words
The composition of claim 42 wherein the polymer is a mixture of the poly(εcaprolactone-co-maleic anhydride) as the copolymer and poly(ε-caprolactone).
Claim 47
Independent Claim
107 words
A method for preparing a biodegradable polymer composition which comprises: admixing a polysaccharide containing alpha-D-glucopyranosyl units having an available water content of less than about 1% by weight with an aliphatic polyester polymer containing formulation in the absence of water wherein an organic peroxide has been provided with the polyester polymer in an amount to provide improved melt strength as compared to the composition without the peroxide to form the biodegradable polymer composition, wherein the polysaccharide is a dispersed phase in the polyester polymer and is between about 25% and 60% by weight of the composition and wherein the aliphatic polyester is poly(ε-caprolactone-co-maleic anhydride) as a co-polymer.
Claim 48
Independent Claim
107 words
A method for preparing a biodegradable polymer composition which comprises: admixing a polysaccharide containing alpha-D-glucopyranosyl units having an available water content of less than about 1% by weight with an aliphatic polyester polymer containing formulation in the absence of water wherein an organic peroxide has been provided with the polyester polymer in an amount to provide improved melt strength as compared to the composition without the peroxide to form the biodegradable polymer composition, wherein the polysaccharide is a dispersed phase in the polyester polymer and is between about 25% and 60% by weight of the composition and wherein the aliphatic polyester is poly(ε-caprolactone-co-maleic anhydride) as a co-polymer.
Claim 49
Dependent Claim
20 words
The method of claim 44 wherein a polyhydric fatty acid ester is provided in the composition as a stretching agent.
Claim 50
Dependent Claim
17 words
The method of claim 45 wherein the polyhydric fatty acid ester is a polyglycerol fatty acid ester.
Claim 51
Dependent Claim
14 words
The method of claim 44 wherein the polyglycerol fatty acid ester is decaglycerol tetraoleate.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1999-03-19 | 1999-09-18 | 2000-03-19 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2003-03-19 | 2003-09-18 | 2004-03-19 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2007-03-19 | 2007-09-18 | 2008-03-19 | $7700.00 | Window Closed / Lapsed |