Biodegradable aliphatic-aromatic polyesters

• US 8,476,378 B2
• Filed: 05/08/2012
• Issued: 07/02/2013
• Est. Priority Date: 03/18/2005
• Status: Active Grant

• Current Assignee: Novamont S.p.a.
• Original Assignee: Novamont S.p.a.
• Inventors: Bastioli, Catia, Milizia, Tiziana, Floridi, Giovanni, Lallaro, Andrea Scaffidi, Cella, Giandomenico, Tosin, Maurizio
• Primary Examiner(s): Tischler, Frances
• Application Number:
  US13/466,555
• Publication Number:
  US 20120219740A1
• Time in Patent Office: 420 Days
• Field of Search: 528/271, 528/272, 528/300, 528/302, 528/303, 528/304, 528/305, 528/306, 528/308, 528/308.1, 528/308.3, 528/371, 428/35.2, 428/35.7, 428/36.4, 428/77, 428/221, 428/357, 428/409, 428/411.1, 428/480, 525/418, 525/419, 525/437, 525/35, 524/35, 524/47, 524/27
• US Class Current: 525/437
• CPC Class Codes: C08G 63/16 Dicarboxylic acids and dihydroxy compounds
• CPC Class Codes: C08L 1/00 Compositions of cellulose, modified cellulose or cellulose derivatives
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 3/02 Starch; Degradation products thereof, e.g. dextrin
• CPC Class Codes: C08L 67/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds C08L67/06 takes precedence
• CPC Class Codes: C08L 67/04 Polyesters derived from hydroxycarboxylic acids, e.g. lactones C08L67/06 takes precedence
• CPC Class Codes: Y10T 428/1331 Single layer [continuous layer]
• CPC Class Codes: Y10T 428/1334 Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
• CPC Class Codes: Y10T 428/1352 Polymer or resin containing [i.e., natural or synthetic]
• CPC Class Codes: Y10T 428/249921 Web or sheet containing structurally defined element or component
• CPC Class Codes: Y10T 428/29 Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31786 Of polyester [e.g., alkyd, etc.]

Abstract

Biodegradable aliphatic/aromatic copolyester comprising 50 to 60 mol % of an aromatic dicarboxylic acid and 40 to 50 mol % of an aliphatic acid, at least 90% of which is a long-chain dicarboxylic acid (LCDA) of natural origin selected from azelaic acid, sebacic acid, brassylic acid or mixtures thereof; and a diol component.

Claims

1. Polymeric composition comprising

A) a biodegradable aliphatic/aromatic copolyester (AAPE) comprising:

a) an acid component comprising repeating units of;

50 to 60% of an aromatic polyfunctional acid;

40 to 50% of an aliphatic acid, at least 90% of which is a long-chain dicarboxylic acid (LCDA) of natural origin selected from azelaic acid, sebacic acid, brassylic acid or mixtures thereof;

b) at least one diol component;

said aliphatic long-chain dicarboxylic acid (LCDA) and said diol component (b) having a number of carbon atoms according to the following formula;

(CLCDA*YLCDA)/2+CB·

YB>

7.5

where;

CLCDA is the number of carbon atoms of the LCDA and can be 9, 10 or 13;

YLCDA is the molar fraction of each LCDA on the total number of moles of LCDA;

Cb is the number of carbon atoms of each diol component;

Yb is the molar fraction of each diol on the total number of moles of the diol component (b)

said AAPE having;

a biodegradability after 90 days higher than 70%, with respect to pure cellulose according to the Standard ISO 14855 Amendment 1;

a density of equal to or less than 1.2 glee;

a number average molecular weight Mn of 40,000-140,000;

an inherent viscosity of 0.8-1.5; and

B) at least one other polymer selected from other polyesters of the aliphatic/aromatic type or biodegradable polymers of natural origin or of synthetic origin.

2. Polymeric composition according to claim 1, wherein the diol of the aliphatic/aromatic copolyester (A) is selected from the group consisting of:

1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,4-cyclohexanedimethanol, propylene glycol, neo-pentyl glycol, 2-methyl-1,3-propanediol, dianhydrosorbitol, dianhydromannitol, dianhydroiditol cyclohexanediol, and cyclohexanemethanediol.

3. Polymeric composition according to claim 2, wherein said diol has from 2 to 10 carbon atoms.

4. Polymeric composition according to claim 3, wherein said diol has from 2 to 4 carbon atoms.

5. Polymeric composition according to claim 1, wherein the aromatic polyfunctional acid of the aliphatic/aromatic copolyester (A) is selected from the group consisting of the phthalic acids.

6. Polymeric composition according to claim 1, wherein said biodegradable aliphatic/aromatic copolyester (A) further comprises one or more polyfunctional molecules in amounts of between 0.02-3.0 mol % with respect to the amount of dicarboxylic acids.

7. Polymeric composition according to claim 1, wherein the aliphatic acid of the biodegradable aliphatic/aromatic copolyester (A) further comprises at least one hydroxyl acid in an amount of up to 10 mol % with respect to the total molar content of the aliphatic acid.

8. Polymeric composition according to claim 1, wherein the aliphatic long-chain dicarboxylic acid (LCDA) and the diol component (b) of the biodegradable aliphatic/aromatic copolyester (A) have a number of carbon atoms according to the following formula:

(CLCDA*YLCDA)/2+CB·

YB>

8.

9. Polymeric composition according to claim 1 wherein said at least one other polymer (B) is a polymer of synthetic origin selected from the group consisting of polylactic acid, poly-ε

-caprolactone, polyhydroxybutyrates, such as polyhydroxybutyrate-valerate, polyhydroxybutyrate propanoate, polyhydroxybutyrate-hexanoate, polyhydroxybutyrate-decanoate, polyhydroxybutyrate-dodecanoate, polyhydroxybutyrate-hexadecanoate, polyhydroxybutyrate-octadecanoate, and polyalkylene succinates.

10. Polymeric composition according to claim 1, wherein said at least one other polymer (B) is a polymer of natural origin selected from the group consisting of starch, cellulose, chitosan, alginates or natural rubbers.

11. Polymeric composition according to claim 10, wherein said starch or cellulose is modified.

12. Polymeric composition according to claim 11, wherein the modified starch or celluloses are starch or cellulose esters with a degree of substitution of between 0.2 and 2.5, hydroxypropylated starches, and modified starches with fatty chains.

13. Polymeric composition according to claim 10, wherein the starch is present in a destructurized or gelatinized form or in the form of fillers.

14. Polymeric composition according to claim 1, wherein the starch is present in the form of a dispersed phase with an average dimension lower than 1 micron.

15. Polymeric composition according to claim 1, in which the polymer of synthetic origin is polylactic acid and the polymer of natural origin is starch.

16. Polymeric composition according to claim 1, comprising chain extenders, in a quantity comprised between 0.05-2.5 wt. %.

17. A method for the production of at least one member selected from the group consisting of:

films, whether one-directional or two-directional films, and multilayer films with other polymeric materials;

films for use in the agricultural sector as mulching films;

cling films (extensible films) for foodstuffs, for bales in the agricultural sector and for wrapping of refuse;

shrink film;

bags and sheathes for gathering organic matter

packaging for foodstuffs both single-layer and multilayer;

coatings obtained with the extrusion-coating technique;

multilayer laminates with layers of paper, plastic materials, aluminium, or metallized films;

foamed or foamable beads for the production of pieces formed by sintering;

foamed and semi-foamed products;

foamed sheets, thermoformed sheets and containers obtained therefrom for the packaging of foodstuffs;

containers in general for fruit and vegetables;

composites with gelatinized, destructurized and/or complexed starch, natural starch, flours, other fillers of natural, vegetal or inorganic origin; and

fibres, fabrics and non-woven fabrics for the sector of health, sanitary products, and hygiene;

which comprises shaping a polymeric composition according to claim 1.

18. Polymeric composition according to claim 2 wherein said at least one other polymer (B) is a polymer of synthetic origin selected from the group consisting of polylactic acid, poly-ε

-caprolactone, polyhydroxybutyrates, such as polyhydroxybutyrate-valerate, polyhydroxybutyrate propanoate, polyhydroxybutyrate-hexanoate, polyhydroxybutyrate-decanoate, polyhydroxybutyrate-dodecanoate, polyhydroxybutyrate-hexadecanoate, polyhydroxybutyrate-octadecanoate, and polyalkylene succinates.

19. Polymeric composition according to claim 3 wherein said at least one other polymer (B) is a polymer of synthetic origin selected from the group consisting of polylactic acid, poly-ε

-caprolactone, polyhydroxybutyrates, such as polyhydroxybutyrate-valerate, polyhydroxybutyrate propanoate, polyhydroxybutyrate-hexanoate, polyhydroxybutyrate-decanoate, polyhydroxybutyrate-dodecanoate, polyhydroxybutyrate-hexadecanoate, polyhydroxybutyrate-octadecanoate, and polyalkylene succinates.

20. Polymeric composition according to claim 4 wherein said at least one other polymer (B) is a polymer of synthetic origin selected from the group consisting of polylactic acid, poly-ε

-caprolactone, polyhydroxybutyrates, such as polyhydroxybutyrate-valerate, polyhydroxybutyrate propanoate, polyhydroxybutyrate-hexanoate, polyhydroxybutyrate-decanoate, polyhydroxybutyrate-dodecanoate, polyhydroxybutyrate-hexadecanoate, polyhydroxybutyrate-octadecanoate, and polyalkylene succinates.