Biodegradable polymeric compositions based on starch and thermoplastic polymers

• US 5,412,005 A
• Filed: 04/30/1992
• Issued: 05/02/1995
• Est. Priority Date: 05/03/1991
• Status: Expired due to Term

• Current Assignee: Novamont S.p.a.
• Original Assignee: Novamont S.p.a.
• Inventors: Montino, Alessandro, Tredici, Gianfranco D., Bastioli, Catia, Bellotti, Vittorio, Lombi, Roberto, Ponti, Roberto
• Primary Examiner(s): Michl, Paul R.
• Assistant Examiner(s): DEWITT, LAVONDA R
• Application Number:
  US07/876,474
• Time in Patent Office: 1,097 Days
• Field of Search: 523/126, 524/47, 524/48, 524/52, 524/53, 524/366, 524/377
• US Class Current: 524/47
• CPC Class Codes: A61L 15/225 Mixtures of macromolecular compounds
• CPC Class Codes: A61L 15/62 Compostable, hydrosoluble or hydrodegradable materials
• CPC Class Codes: B01D 71/08 Polysaccharides
• CPC Class Codes: B01D 71/381 Polyvinylalcohol
• CPC Class Codes: B29B 7/007 for continuous mixing
• CPC Class Codes: B29B 7/46 with more than one shaft
• CPC Class Codes: B29B 7/823 Temperature control
• CPC Class Codes: B29B 7/845 Venting, degassing or removing evaporated components in devices with rotary stirrers
• CPC Class Codes: B29B 7/88 Adding charges , i.e. additives
• CPC Class Codes: B29C 48/40 using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
• CPC Class Codes: C08L 2201/06 Biodegradable
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• 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 29/04 Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• CPC Class Codes: C08L 3/02 Starch; Degradation products thereof, e.g. dextrin
• CPC Class Codes: C08L 5/00 Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
• CPC Class Codes: C08L 67/04 Polyesters derived from hydroxycarboxylic acids, e.g. lactones C08L67/06 takes precedence
• CPC Class Codes: C08L 75/04 Polyurethanes
• CPC Class Codes: C08L 75/06 from polyesters
• CPC Class Codes: C08L 87/00 Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds

Abstract

The biodegradable polymeric compositions comprise a starch based component and a polymeric component comprising polymers of hydroxyacids or mixtures thereof with polymers deriving from ethylenically unsaturated monomers, particularly polymers of ethylene-vinylalcohol or polyvinylalcohol.

Claims

1. A polymeric composition obtainable from a melt comprising a starch component, a plasticizer and a synthetic thermoplastic polymer component, wherein the synthetic component comprises at least one polymer or mixture of polymers selected from the group consisting of:

(a) homopolymers of aliphatic hydroxyacids having from 2 to 24 carbon atoms, the corresponding lactones or lactides;

(b) copolymers of a first monomer selected from the group consisting of aliphatic hydroxyacids having from 2 to 24 carbon atoms, the corresponding lactones or lactides with a second monomer selected from the group consisting of aliphatic hydroxyacids having from 2 to 24 carbon atoms other than that constituting the first monomer, corresponding lactones or lactides, aromatic hydroxyacids, aliphatic or aromatic isocyanates;

(c) block or graft copolymers between the homopolymers and copolymers (a) or (b) with one or more of the following components;

(i) cellulose or modified cellulose;

(ii) amylose, amylopectin, natural or modified starches;

(iii) polymers deriving from reaction of diols, polyester prepolymers or polymers having diol terminal groups with;

aromatic or aliphatic bifunctional isocyanates,

aromatic or aliphatic bifunctional epoxydes,

aliphatic bicarboxylic acids,

bicarboxylic cycloaliphatic acids,

aromatic acids or anhydrides,

(iv) polyurethanes, polyamide-urethanes from diisocyanates and aminoalcohols, polyamides, polyesteramides from bicarboxylic acids and aminoalcohols, polyester-urea from aminoacids and diesters of glycols,

(v) polyhydroxylated polymers selected from the group consisting of polyvinylalcohol, ethylenevinylalcohol copolymers, totally or partially hydrolyzed, and polysaccharides up to dextrins,

(vi) polyvinylpyrrolidone, polyvinylpyrrolidonevinylacetate copolymers, polyethyloxazolines;

(vii) ionomeric polymers selected from polyacrylates and polymetacrylates;

(d) polyesters obtained from monomers or comonomers as defined above at (a) and (b) upgraded with chain extenders selected from the group consisting of isocyanates, epoxides, phenylesters and aliphatic carbonates;

(e) polyesters obtained from monomers and comonomers defined at (a) and (b) above partially crosslinked by means of polyfunctional acids selected from the group consisting of trimellitic acid, pyromellitic acid, polyisocyanates and polyepoxides, said starch component and said synthetic polymer component being present in a ratio of from 1;

9 to 9;

1.

2. A composition according to claim 1, wherein the starch component and the synthetic polymeric component are in a weight ratio of from 1:

4 to 4;

1.

3. A composition according to claim 1, wherein the synthetic component comprises a polymer of an epsilon-hydroxyacid or a corresponding lactone selected from the group consisting of 6-hydroxycaproic, 6-hydroxyoctanoic and 3,7-dimetyl-6-hydroxyoctanoic acid.

4. A composition according to claim 3, wherein the synthetic component is a copolymer of an epsilon-hydroxyacid and an isocyanate selected from the group consisting of 4,4'"'"'-diphenylmethane-diisocyanate, toluilenediisocyanate, isophorondiisocyanate and hexanmetylenediisocyanate.

5. A composition according to claim 1, wherein the synthetic component comprises poly-epsilon-caprolactone or a copolymer of epsilon-caprolactone and an aliphatic or aromatic isocyanate or a mixture thereof.

6. A composition according to claim 5, wherein the synthetic component comprises poly-epsilon-caprolactone having a molecular weight above 40,000.

7. A composition according to claim 6, wherein the synthetic component comprises a mixture of poly-epsilon-caprolactone and copolymer of epsilon-caprolactone with an aliphatic or aromatic isocyanate in a weight ratio of from 5:

1 to 1;

1.

8. A composition according to claim 1, wherein the polymeric synthetic component comprises a component A selected from polymers (a) to (e) and mixtures thereof and a component B comprising a polymer derived from ethylenically unsaturated monomers, said polymer having repeating units provided with at least one functional polar group selected from the group consisting of hydroxyl, carboxyl, carboxyalkyl, alkylcarboxyl, pyrrolidyl, and acetal.

11. A composition according to claim 8, wherein components A and B are present in a weight ratio of from 1:

6 and 6;

1.

12. A composition according to claim 8, comprising:

from about 20 to about 60% by wt of the starch component,

from about 10 to about 80% by wt of component A, and

from 0 to about 45% by wt of component B, the percent amounts being expressed with reference to the sum of the starch and total synthetic component.

13. A composition according to claim 12, comprising from about 10 to about 50% by wt of component A and from about 2 to about 30% by wt of component B.

14. A composition according to claim 8, comprising:

from about 5 to about 60% by wt of the starch component,

from about 40 to about 80% by wt of component A, and

from 0 to about 35% by wt of component B, the percent amounts being expressed with reference to the sum of the starch and total synthetic component.

15. A composition according to claim 14, comprising from about 5 to about 30% by wt of component B.

16. A composition according to claim 1 or 8, comprising from 1 to 50% by weight, based on the weight of the starch/synthetic polymer system, of a plasticizer selected from the group consisting of glycerine, polyglycerol, glycerol ethoxylate, ethylene or propylene glycol, ethylene or propylene diglycol, ethylene or propylene triglycol, polyethylene or polypropylene glycol, 1,2-propandiol, 1,3-propandiol, 1,2-, 1,3-, 1,4-butandiol, 1,5-pentandiol, 1,6-, 1,5-hexandiol, 1,2,6-, 1,3,5-hexantriol, neopentylglycol, trimethylolpropane, pentaerythritol, sorbitol, sorbitol acetate, sorbitol diacetate, sorbitol monoethoxylate, sorbitol dipropoxylate, sorbitol diethoxylate, sorbitol hexaethoxylate, aminosorbitol, trihydroxymethylaminomethane, glucose/PEG, the product of reaction of ethylene oxide with glucose, trimethylolpropane monoethoxylate, mannitol monoacetate, mannitol monoethoxylate, butyl glucoside, glucose monoethoxylate, alphamethyl glucoside, the sodium salt of carboxymethylsorbitol, polyglycerol monoethoxylate and mixtures thereof.

17. A composition according to claim 16, wherein the plasticizer is present in the amount of from 5 to 25% by weight with reference to the weight of the total composition consisting of the starch and polymeric component (s).

18. A composition according to claim 16, wherein the plasticizer is selected from glycerine, sorbitol and sorbitol monoethoxylate and mixtures thereof.

19. A composition according to claim 16, comprising urea in the amount of from 0.5 to 20% by wt with reference to the weight of the total composition.

20. A composition according to claim 1 or 8, comprising up to 5% by wt with reference to the overall composition of a hydrophobic polymer selected from the group consisting of polyethylene, polypropylene and polystyrene.

21. A composition according to claim 1 or 8, having a water content of from 1.5 to 5% by wt with reference to the overall composition.

22. A composition according to claim 1 or 8, wherein the starch component comprises more than 78% by wt of amylopectin.

23. A composition according to claim 1 or 8, comprising of from 0.01 to 10% by wt, with reference to the weight of the starch component, of an additive selected from the group consisting of boric acid, borax, metaboric acid, aluminium hydroxide and alkali-metal salts.

24. A composition according to claim 23, wherein the starch component has an amylopectin content higher than 70% by wt.

26. Articles, including films, sheets, fibres and filaments when obtained by the use of a polymeric composition according to any one of claims 1 or 8.

27. A composition according to claim 11, wherein components A and B are present in a weight ratio of from 1:

4 to 4;

1.

9. A composition according to claim B, wherein component B comprises a polymer selected from the group consisting of polyvinylalcohol, ethylene-acrylic acid, ethylene-vinylacetate, ethylene-vinylalcohol, modified ethylene-vinylalcohol, modified polyvinylalcohol and mixtures thereof.

10. A composition according to claim 9, wherein component B comprises poly-ethylene-vinylalcohol obtained by hydrolysis of the corresponding poly-ethylene-vinylacetate, having an ethylene content lower than 44% by weight and hydrolysis degree of the acetate groups of from 50 to 100%.

25. A thermoplastic polymeric composition including starch component, a synthetic thermoplastic polymer component and a plasticizer, wherein the synthetic thermoplastic component comprises blends of both (1) a polymer selected from the group consisting of ethylene-vinylalcohol copolymer and polyvinylalcohol and (2) an aliphatic polyester, and the plasticizer is selected from the group consisting of:

(a) polyols formed by from 1 to 20 repeating hydroxylated units each including from 2 to 6 carbon atoms,

(b) ethers, thioethers, inorganic and organic esters, acetals and amino-derivatives of polyols formed by from 1 to 20 repeating hydroxylated units, each including from 2 to 6 carbon atoms,

(c) reaction products of polyols having from 1 to 20 repeating hydroxylated units, each including from 2 to 6 carbon atoms, with chain extenders,

(d) oxidation products of polyols having from 1 to 20 repeating hydroxylated units, each including from 2 to 6 carbon atoms, including at least one aldehydic or carboxylic functional group or a mixture thereof, said starch component and said synthetic polymer component being present in a ratio of from 1;

9 to 9;

1.