WO2005113616A2 - Melange amidon-polyester obtenu par extrusion reactive - Google Patents

Melange amidon-polyester obtenu par extrusion reactive Download PDF

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Publication number
WO2005113616A2
WO2005113616A2 PCT/US2005/015377 US2005015377W WO2005113616A2 WO 2005113616 A2 WO2005113616 A2 WO 2005113616A2 US 2005015377 W US2005015377 W US 2005015377W WO 2005113616 A2 WO2005113616 A2 WO 2005113616A2
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WO
WIPO (PCT)
Prior art keywords
polyester
blend
containing polymer
hydroxyl containing
starch
Prior art date
Application number
PCT/US2005/015377
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English (en)
Other versions
WO2005113616A3 (fr
Inventor
Syed S. H. Rizvi
Sathya Kalambur
Original Assignee
Cornell Research Foundation, Inc.
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 Cornell Research Foundation, Inc. filed Critical Cornell Research Foundation, Inc.
Publication of WO2005113616A2 publication Critical patent/WO2005113616A2/fr
Publication of WO2005113616A3 publication Critical patent/WO2005113616A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C08L3/10—Oxidised starch
    • 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
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • the invention is directed to starch or other hydroxyl containing polymer blend with polyester, of improved mechanical properties.
  • One embodiment herein is directed at a hydroxyl containing polymer-polyester blend comprising plasticized oxidized hydroxyl containing polymer crosslinked with polyester, the blend having maximum tensile strength greater than elongation at break greater than 50% of that of the polyester.
  • Another embodiment herein is directed at a method for preparing blend of hydroxyl containing polymer and polyester, of maximum tensile strength greater than 25%) of that of the polyester, Young's modulus greater than 25%> of that of the polyester and elongation at break greater than 50% of that of the polyester comprising the steps of (a) forming an admixture of hydroxyl containing polymer and polyester in a hydroxyl containing polymer-polyester weight ratio ranging from 1 :10 to 10:1, plasticizer in a hydroxyl containing polymer weight ratio ranging from 1 : 10 to 1:1 and H 2 0 2 in an amount effective to oxidize the hydroxyl containing polymer, and (b) feeding the admixture into an extruder and extruding therein or therethrough to cause oxidation of the hydroxyl containing polymer to form oxidized hydroxyl containing polymer and cause crosslinking between oxidized hydroxyl containing polymer and polyester of the admixture.
  • the maximum tensile strength data in MPa set forth herein is determined by ASTM Test D638-96.
  • the Young's modulus data in MPa set forth herein is determined by ASTM Test D638-96.
  • the ultimate elongation data (%), i.e., elongation at break data (%) set forth herein, is determined by ASTM Test D638-96.
  • FIG. 1A is a graph of wt % organoclay versus Youngs Modulus and shows results of Working Example I.
  • FIG. 1 B is a graph of wt % organoclay versus elongation at break and shows results of Working Example I.
  • FIG. 1C is a graph of wt % organoclay versus maximum tensile strength and shows results of Working Example I.
  • the hydroxyl-containing polymer is preferably starch (e.g., wheat starch, high amylose corn starch, waxy maize starch and their blends).
  • the starch can also be obtained, for example, from rice, potato, peas and/or tapioca.
  • Native wheat and corn starches which are preferred for use herein, contain about 75% amylopectin fraction and 25% amylose fraction where the amylose fraction has a degree of polymerization (DP) ranging from lxlO 2 to 4x10 5 and the amylopectin fraction has a DP ranging from lxlO 4 to 4x10 7 , with branches after every 19-25 linear units.
  • DP degree of polymerization
  • the hydroxyl containing polymer can also be, for example, cellulosic polymer (M n ranging from 160,000 to 500,000,000 g/mol as determined by gel permeation chromatography or intrinsic viscosity measurements) or polyvinyl alcohol (M n ranging from 25,000 to 300,000 g/mol as determined by gel permeation chromatography).
  • the oxidation converts the hydroxy of the hydroxyl containing polymer to carboxyl, aldehyde and ketone and fosters crosslinking by abstraction of hydrogen atoms adjacent to carbonyl on both oxidized hydroxyl containing polymer and polyester.
  • the plasticizer is present to facilitate forming hydroxyl containing polymer melts during preparation processing without significant molecular breakdown.
  • the plasticizer is a trihydric alcohol, very preferably glycerol.
  • suitable plasticizers include monohydric, dihydric and polyhydric alcohols. Some examples are ethylene glycol, propylene glycol, erythritol, pentaerythritol, sorbitol and higher molecular weight plasticizers such as polyglycerol. Plasticizers used herein may also act as substrates in the oxidation/crosslinking pathways.
  • the polyester is preferably a biodegradable polyester and when such polyester is used in a blend with oxidized starch or native starch (with or without clay), the blend is biodegradable.
  • Biodegradable polyesters for use herein include, for example, polycaprolactone (e.g., poly (e-caprolactone), denoted PCL, polybutylene succinate, denoted PBS, polytetramethylene adipate-co-terephthalate (PAT), polyhydroxyl butyrate-valerate (PHBV), polylactic acid (PLA) and polyglycolic acid (PGA).
  • the polyester can also be a non4?iodegradable polyester, e.g., polyethylene terephthalate.
  • the polyesters typically have M n ranging from 40,000 to 300,000 g/mol as determined by gel permeation chromatography using polystyrene standards.
  • the blend comprises glycerol plasticized oxidized starch crosslinked with polyester.
  • the blend can optionally contain nanoclay modified to contain organic cation. Suitable nanoclays include montmorillonite, hectorite and saponite modified to contain organic cation.
  • a preferred clay ingredient is montmorillonite modified to contain quaternary ammonium octadecyl cations (C18H 35 NH ). The clay functions to allow reduction in temperature during preparation processing, for obtaining the stated mechanical properties.
  • the blend is preferably formulated from (A) 9 to 91 weight percent hydroxyl containing polymer and (B) from 91 to 9 weight percent polyester, based on (A) plus (B) being 100%; very preferably is formulated from (A) 10 to 95 weight percent plasticized hydroxyl containing polymer and (B) 90 to 5 weight percent polyester, based on (A) and (B) being 100%.
  • the hydroxyl-containing polymer: plasticizer weight ratio can range, for example, from 10:1 to 1 :1 ; 2:1 is used in Working Example I.
  • the blend is additionally formulated to contain from 0.5 to 10%, preferably more than 1%, nanoclay modified to contain organic cation, based on the weight of the blend including the organic cation modified clay.
  • the second embodiment of the invention which is directed to preparing hydroxyl containing polymer-polyester blend of maximum tensile strength greater than 25%> of that of the polyester, Young's modulus greater than 25% of that of the polyester and elongation at break greater than 50% of that of the polyester, comprising the steps of (a) forming an admixture of hydroxyl containing polymer, plasticizer in a hydroxyl containing polymer plasticizer weight ratio ranging from 10:1 to 1 :1, polyester in a hydroxyl containing polymer: polyester weight ratio ranging from 1 : 10 to 10:1 and H 0 in an amount effective to oxidize the hydroxyl containing polymer, and (b) feeding the admixture into an extruder and extruding the admixture therein or therethrough to cause oxidation of the hydroxyl containing polymer to form oxidized hydroxyl containing polymer and cause crosslinking between oxidized hydroxyl containing polymer and polyester of the admixture.
  • the hydroxyl containing polymers, plasticizers and polyesters are those of the first embodiment.
  • the hydroxyl containing polymer is native wheat starch
  • the plasticizer is glycerol
  • the polyester is polycaprolactone (M n of 80,000) or polytetramethylene adipate- co-terephthalate. (high molecular weight, Eastar Bio Ultra)
  • the blends are useful as plastic substitutes.
  • the hydroxy containing polymer: polyester weight ratio ranges from 1: 10 to 10:1
  • the hydroxyl-containing polyme ⁇ plasticizer weight ratio ranges from 10:1 to 1 :1
  • the H 0 can be present in amount ranging from 0.01 ml/gm of hydroxyl containing polymer to 0.36 ml/gm of hydroxyl containing polymer on a 30% H 0 solution in water basis.
  • the admixture for step (a) of the second embodiment can optionally include ferrous ions, e.g., in the form of ferrous sulfate, to catalyze the oxidation, e.g., in an amount of 0.0069-1.5 g/ml of peroxide (30%) solution in water basis); cupric ion, e.g., in the form of cupric sulfate is also optionally included to catalyze oxidation and decrease molecular weight of oxidized starch (by a pathway called the Ruff degradation pathway) but is omitted in applications requiring contact with food materials. When cupric sulfate is included, it is used in an amount of 0.0020-0.0125 g/gram starch.
  • transition metal catalysts like iron, can replace copper.
  • the H 0 2 and the catalysts perform a dual role, generating free hydroxyl radicals (i) for hydroxyl containing polymer oxidation and (ii) for causing crosslinking of oxidized starch and polyester.
  • Nanoclay e.g., montmorillonite, hectorite or saponite, modified to contain an organic cation, e.g., montmorillonite modified to contain C
  • Step (b) can be carried out in a batch extruding step or in a single continuous reactive extrusion process where oxidation and crosslinking successively occur.
  • reactive extrusion is used herein to mean extrusion of plasticized hydroxyl containing polymer and polyester blend in the presence of hydrogen peroxide and catalyst(s) with or without clay.
  • the extrusion temperature generally ranges from 90°C to 150°C but clay is a necessary ingredient to obtain the stated mechanical properties if the extrusion temperature is less than 130°C. There is no significant effect on properties when higher temperatures (130° C or higher) are used with clay.
  • the plasticizer facilitates forming hydroxyl containing polymer, e.g., starch, melts during extrusion without significant molecular breakdown.
  • the plasticizer may also act as a substrate for oxidation/crosslinking pathways during extrusion.
  • the final products obtained which are embraced by the first embodiment of the invention herein are, for example, mixtures of starch, oxidized starch, glycerol, polycaprolactone and crosslinked oxidized starch-polycaprolactone.
  • the invention is further described in Kalambur, S.B.
  • the starch was native wheat starch (MIDSOL 50, Midwest Grain Products, Atchison, Kansas).
  • the organoclay was Nanocor I.30E (montmorillonite) type with sodium cations, modified to replace sodium cations with quaternary ammonium octadecyl cations (C 1 8H35NH ).
  • Ingredients were pre-mixed and fed to a co-rotating twin-screw microextruder (DACA Instruments, Goleta, California). The residence time was kept at 3 minutes. Melt was extruded out of the die of the microextruder in the form of cylindrical strands.
  • the temperature throughout the extruder was maintained at 120°C. Screw speed was maintained at 125-130 rpm.
  • the extruder barrel was blanketed with nitrogen during extrusion. Two batches of each formulation were extruded to ensure reproducibility.
  • the extruded strands were injection molded in a micro-injector (DACA Instruments, Goleta, California) at 80-1 10 psi and 120°C in the form of dog-bone pieces of area of 1.5 x 4 mm 2 .
  • the mold was maintained at ambient temperature. The conditions were such as to obtain peroxide oxidation to almost 100% conversion because of high temperature (120° C) during the reactive extrusion process.
  • Relative crystallinity that is the heading of the right hand column of Table 4 is a measure of change in PCL crystallinity of PCL in starch-PCL blend compared to 100% PCL (relative crystallinity of 1.0)
  • crystallization temperature in blends subjected to reactive extrusion increased as the amount of organoclay increased from 1 to 9% but were lower than that of blend without organoclay not subjected to reactive extrusion and also compared to 100% PCL.
  • percent crystallinity increased with increasing organoclay content for the compositions obtained by reactive extrusion. The differences, however, were small.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention concerne un mélange de polymère contenant de l'hydroxyle, de l'amidon par exemple, et de polyester, du polycaprolactone par exemple. Ce mélange contient un polymère contenant de l'hydroxyle oxydé et plastifié, réticulé avec du polyester, et il présente des propriétés d'allongement à la rupture supérieures à 50 % de celles du polyester. Ledit mélange est obtenu par le mélange d'un polymère contenant de hydroxyle, de polyester, d'un plastifiant et de H2O2, puis par extrusion réactive de ce mélange. L'introduction de nanoargile modifiée au moyen d'un cation organique permet d'utiliser une température d'extrusion inférieure pour obtenir le même allongement à la rupture.
PCT/US2005/015377 2004-05-04 2005-05-04 Melange amidon-polyester obtenu par extrusion reactive WO2005113616A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US56764604P 2004-05-04 2004-05-04
US60/567,646 2004-05-04

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WO2005113616A2 true WO2005113616A2 (fr) 2005-12-01
WO2005113616A3 WO2005113616A3 (fr) 2006-03-16

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7998888B2 (en) 2008-03-28 2011-08-16 Kimberly-Clark Worldwide, Inc. Thermoplastic starch for use in melt-extruded substrates
US8147965B2 (en) 2008-05-14 2012-04-03 Kimberly-Clark Worldwide, Inc. Water-sensitive film containing thermoplastic polyurethane
US8188185B2 (en) 2008-06-30 2012-05-29 Kimberly-Clark Worldwide, Inc. Biodegradable packaging film
US8227658B2 (en) 2007-12-14 2012-07-24 Kimberly-Clark Worldwide, Inc Film formed from a blend of biodegradable aliphatic-aromatic copolyesters
US8283006B2 (en) 2008-12-18 2012-10-09 Kimberly-Clark Worldwide, Inc. Injection molding material containing starch and plant protein
US8329601B2 (en) 2008-12-18 2012-12-11 Kimberly-Clark Worldwide, Inc. Biodegradable and renewable film
US8334327B2 (en) 2006-08-31 2012-12-18 Kimberly-Clark Worldwide, Inc. Highly breathable biodegradable films
US8338508B2 (en) 2008-05-14 2012-12-25 Kimberly-Clark Worldwide, Inc. Water-sensitive film containing an olefinic elastomer
US8759279B2 (en) 2008-06-30 2014-06-24 Kimberly-Clark Worldwide, Inc. Fragranced biodegradable film
US8927617B2 (en) 2008-06-30 2015-01-06 Kimberly-Clark Worldwide, Inc. Fragranced water-sensitive film
US10689566B2 (en) 2015-11-23 2020-06-23 Anavo Technologies, Llc Coated particles and methods of making and using the same
US10982013B2 (en) 2014-06-02 2021-04-20 Anavo Technologies, Llc Modified biopolymers and methods of producing and using the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5736586A (en) * 1994-08-08 1998-04-07 Novamont S.P.A. Biodegradable foamed plastic materials
JP2000109665A (ja) * 1998-10-02 2000-04-18 Nippon Shokuhin Kako Co Ltd 有機物質含有生分解性組成物の製造方法
US20020168518A1 (en) * 2001-05-10 2002-11-14 The Procter & Gamble Company Fibers comprising starch and polymers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5736586A (en) * 1994-08-08 1998-04-07 Novamont S.P.A. Biodegradable foamed plastic materials
JP2000109665A (ja) * 1998-10-02 2000-04-18 Nippon Shokuhin Kako Co Ltd 有機物質含有生分解性組成物の製造方法
US20020168518A1 (en) * 2001-05-10 2002-11-14 The Procter & Gamble Company Fibers comprising starch and polymers

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8334327B2 (en) 2006-08-31 2012-12-18 Kimberly-Clark Worldwide, Inc. Highly breathable biodegradable films
US8227658B2 (en) 2007-12-14 2012-07-24 Kimberly-Clark Worldwide, Inc Film formed from a blend of biodegradable aliphatic-aromatic copolyesters
US9150699B2 (en) 2007-12-14 2015-10-06 Kimberly-Clark Worldwide, Inc. Film formed from a blend of biodegradable aliphatic-aromatic copolyesters
US7998888B2 (en) 2008-03-28 2011-08-16 Kimberly-Clark Worldwide, Inc. Thermoplastic starch for use in melt-extruded substrates
US8445110B2 (en) 2008-05-14 2013-05-21 Kimberly-Clark Worldwide, Inc. Water-sensitive film containing thermoplastic polyurethanes
US8147965B2 (en) 2008-05-14 2012-04-03 Kimberly-Clark Worldwide, Inc. Water-sensitive film containing thermoplastic polyurethane
US8338508B2 (en) 2008-05-14 2012-12-25 Kimberly-Clark Worldwide, Inc. Water-sensitive film containing an olefinic elastomer
US8188185B2 (en) 2008-06-30 2012-05-29 Kimberly-Clark Worldwide, Inc. Biodegradable packaging film
US8759279B2 (en) 2008-06-30 2014-06-24 Kimberly-Clark Worldwide, Inc. Fragranced biodegradable film
US8927617B2 (en) 2008-06-30 2015-01-06 Kimberly-Clark Worldwide, Inc. Fragranced water-sensitive film
US9617400B2 (en) 2008-06-30 2017-04-11 Kimberly-Clark Worldwide, Inc. Fragranced water-sensitive film
US8329601B2 (en) 2008-12-18 2012-12-11 Kimberly-Clark Worldwide, Inc. Biodegradable and renewable film
US8283006B2 (en) 2008-12-18 2012-10-09 Kimberly-Clark Worldwide, Inc. Injection molding material containing starch and plant protein
US10982013B2 (en) 2014-06-02 2021-04-20 Anavo Technologies, Llc Modified biopolymers and methods of producing and using the same
US10689566B2 (en) 2015-11-23 2020-06-23 Anavo Technologies, Llc Coated particles and methods of making and using the same

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