CA2480539A1 - Amorphous-crystalline block copolymers - Google Patents

Amorphous-crystalline block copolymers Download PDF

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Publication number
CA2480539A1
CA2480539A1 CA002480539A CA2480539A CA2480539A1 CA 2480539 A1 CA2480539 A1 CA 2480539A1 CA 002480539 A CA002480539 A CA 002480539A CA 2480539 A CA2480539 A CA 2480539A CA 2480539 A1 CA2480539 A1 CA 2480539A1
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CA
Canada
Prior art keywords
acid
block copolymer
containers
copolymer according
previous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CA002480539A
Other languages
French (fr)
Other versions
CA2480539C (en
Inventor
Catia Bastioli
Giandomenico Cella
Tiziana Milizia
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novamont SpA
Original Assignee
Novamont S.P.A.
Catia Bastioli
Giandomenico Cella
Tiziana Milizia
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Novamont S.P.A., Catia Bastioli, Giandomenico Cella, Tiziana Milizia filed Critical Novamont S.P.A.
Publication of CA2480539A1 publication Critical patent/CA2480539A1/en
Application granted granted Critical
Publication of CA2480539C publication Critical patent/CA2480539C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/126—Copolymers block
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
    • Y10T428/1341—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber

Abstract

Biodegradable block copolyesters obtained from crystalline blocks and amorphous blocks, wherein the repeating units of both blocks are of the dicarboxylic acid/diol type. Said copolyesters are characterized by a melting temperature, equal to or less than 15% lower than the starting crystalline polymer temperature, and by increased tenacity that makes them particularly useful in the production of different types of objects.

Claims (21)

1. A biodegradable thermoplastic block copolymer made of crystalline blocks and amorphous blocks obtained from at least a crystalline polymer and at least an amorphous polymer, both of them of the dicarboxylic acid/diol type and characterized by a melting Point T mA, referred to the crystalline part, which is equal to or less than 15% lower than the melting Temperature of the crystalline polymer, and by a melting Point T mB referred to the amorphous part, to which a .DELTA.H lower than 10 J/g is associated.
2. The biodegradable thermoplastic block copolymer according to claim l, wherein the crystalline polymer of the diacid/diol type, that originates the crystalline part of the copolymer, is characterized by .DELTA.H >= 50 J/g, T m >=
60°C and Mn >= 25,000, and the amorphous polymer of the diacid/diol type, that originates the amorphous part of the copolymer, is characterized by .DELTA.H <= 30 J/g and a T g lower than 0°C, preferably lower than -10°C.
3. The biodegradable thermoplastic block copolymer according to claims l and 2, wherein the amount of amorphous polymer is within the range of 1 to 70% based on the total amount of amorphous + crystalline polymer, preferably from 5 to 65% and more preferably from 10 to 60%.
4. The biodegradable block copolymer according to any previous claim, wherein the dicarboxylic acid is selected from the group comprising oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid and brassylic acid and mixtures thereof.
5. The biodegradable block copolymer according to any previous claim, wherein said diol is selected from the group comprising 1,2-ethandiol, 1,2-propandiol, 1,3-propandiol, 1,4-butandiol, 1,6-hexandiol, 1,7-heptandiol, 1,8-octandiol, 1,9-nonandiol, 1,10-decandiol, 1,11-undecandiol, 1,12-dodecandiol, 1,4-cyclohexandimethanol, neopentylglycol, 2-methyl-1,3-propandiol, dianhydrosorbitol, dianhydromannitol, dianhydroiditol, cyclohexandiol, cyclohexanmethandiol and mixtures thereof.
6. The biodegradable block copolymer according to any previous claim, comprising an unsaturated comonomer of either natural or synthetic origin in an amount within the range of 0.5 to 45% based on the sum of the amounts of dicarboxylic acid/diol.
7. The biodegradable block copolymer according to claim 6, wherein the synthetic origin unsaturated comonomer is selected from the group comprising malonic acid, fumaric acid, vinyl acetate, acrylic acid, methacrylic acid, hydroxyalkylacrylate and hydroxyalkylinethacrylate, and the natural origin unsaturated comonomer is selected from the group comprising itaconic acid, monounsaturated hydroxyacid, such as ricinoleic acid and lesquerolic acid, and mono-, or polyunsaturated monocarboxylic acid, such as oleic acid, erucic acid, linoleic acid, linolenic acid.
8. The biodegradable block copolymer according to any previous claim, comprising at least a hydroxy acid in an amount within the range of from 0 to 30% moles based on the moles of the aliphatic dicarboxylic acid, said hydroxy acid being selected from the group comprising glycolic acid, hydroxybutyric acid, hydroxycaproic acid, hydroxyvaleric acid, 7-hydroxyheptanoic acid, 8-hydroxycaproic acid, 9-hydroxynonanoic acid and lactic acid and mixtures thereof.
9. The biodegradable block copolymer according to any previous claim, comprising up to 50% moles, based on the total moles of dicarboxylic acid /diol, of an aromatic polyfunctional compound, such as a phthalic acid, in particular therephthalic acid, bisphenol A, and hydroquinone.
10. The biodegradable block copolymer according to any previous claim, comprising one or more polyfunctional molecules, in an amount within the range of 0.1 to 3%
moles based on the dicarboxylic acid, said molecules being selected from the group comprising glycerol, pentaerythritol, trimethylolpropane, neopentyl glycol, citric acid, densipolic acid, auripolic acid, epoxydized soybean oil and castor oil.
11. The biodegradable block copolymer according to any previous claim used in blends, also obtained by reactive extrusion, either with copolymers of the same type or with other biodegradable polyesters or with polymers other than polyesters.
12. The biodegradable block copolymer according to any previous claim used in blends with polymers of natural origin such as starch, cellulose, chitosan, natural rubber, modified starches and celluloses, starch in destructurized and gelatinized form.
13. The block copolymer according to any previous claim used for the production of:
- films, either mono- or bidirectional, and multi-layer films with other polymeric materials;
- films for use in agriculture, such as mulching films;
- bags and liners for organic waste collection;
- mono- or multi-layer food packaging, such as for instance containers for milk, yogurt, meat, drinks, etc;
- coatings obtained by the extrusion coating technique;
- multi-layer laminates with layers from paper, plastics, aluminum, metalized films;
- expanded and semi-expanded products, including expanded blocks obtained from pre-expanded particles;
- expanded sheets, thermoformed sheets and containers obtained therefrom for food packaging;
- containers in general for fruits and vegetables;
- composites with gelatinized, destructurized and/or complexed starch or natural starch as a filler;
- fibers, fabrics and nonwoven fabrics for the sanitary and hygiene sector.
14. Shaped articles obtainable from the biodegradable block copolymer of any of claims from 1 to 12.
15. Shaped articles according to claim 14, wherein said articles are selected from monodirectional films, bidirectional films, multi-layer films with other polymeric materials, mulching films, coatings obtained by extrusion coating technique.
16. Shaped articles according to claim 14, wherein said articles are selected from bags or liners for organic waste collection.
17. Shaped articles according to claim 14, wherein said articles are mono or multilayer food containers selected from milk containers, yogurt containers, meat containers, drinks containers, fruit containers, vegetables containers.
18. Shaped articles according to claim 14, wherein said articles are multilayer laminates comprising a layer of material selected from paper, plastics, aluminum, metallized film.
19. Shaped articles according to claim 14, wherein said articles are selected from semi-expaned products, expanded products, expanded blocks from pre-expanded particles, expanded sheets, thermoformed sheets, containers for food packaging made of expanded sheets or thermoformed sheets.
20. Shaped articles according to claim 14, wherein said articles are selected from composites with gelatinized, destructurized and/or complexed starch or natural starch as filler.
21. Shaped articles according to claim 14, wherein said articles are selected from fibers, fabrics or nonwoven for the sanitary or hygiene sector.
CA2480539A 2002-04-22 2003-04-22 Amorphous-crystalline block copolymers Expired - Fee Related CA2480539C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ITMI2002A000864 2002-04-22
IT2002MI000864A ITMI20020864A1 (en) 2002-04-22 2002-04-22 AMORPHO-CRYSTALLINE BLOCK COPOLYMERS
PCT/EP2003/004070 WO2003089491A1 (en) 2002-04-22 2003-04-22 Amorphous-crystalline block copolymers

Publications (2)

Publication Number Publication Date
CA2480539A1 true CA2480539A1 (en) 2003-10-30
CA2480539C CA2480539C (en) 2011-10-04

Family

ID=11449759

Family Applications (1)

Application Number Title Priority Date Filing Date
CA2480539A Expired - Fee Related CA2480539C (en) 2002-04-22 2003-04-22 Amorphous-crystalline block copolymers

Country Status (12)

Country Link
US (1) US7169860B2 (en)
EP (1) EP1497352B1 (en)
JP (1) JP2005523355A (en)
CN (1) CN1322021C (en)
AT (1) ATE300567T1 (en)
AU (1) AU2003240455A1 (en)
CA (1) CA2480539C (en)
DE (1) DE60301144T2 (en)
ES (1) ES2246477T3 (en)
IT (1) ITMI20020864A1 (en)
TW (1) TWI259190B (en)
WO (1) WO2003089491A1 (en)

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Also Published As

Publication number Publication date
TWI259190B (en) 2006-08-01
DE60301144D1 (en) 2005-09-01
DE60301144T2 (en) 2006-04-20
EP1497352B1 (en) 2005-07-27
CN1646595A (en) 2005-07-27
CN1322021C (en) 2007-06-20
JP2005523355A (en) 2005-08-04
US20050107572A1 (en) 2005-05-19
CA2480539C (en) 2011-10-04
ATE300567T1 (en) 2005-08-15
US7169860B2 (en) 2007-01-30
TW200307703A (en) 2003-12-16
ITMI20020864A1 (en) 2003-10-22
AU2003240455A1 (en) 2003-11-03
ES2246477T3 (en) 2006-02-16
WO2003089491A1 (en) 2003-10-30
EP1497352A1 (en) 2005-01-19
ITMI20020864A0 (en) 2002-04-22

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