[go: up one dir, main page]

WO1997031979A1 - Compositions de polyesters biodegradables avec polymeres naturels et articles fabriques a partir de ces compositions - Google Patents

Compositions de polyesters biodegradables avec polymeres naturels et articles fabriques a partir de ces compositions Download PDF

Info

Publication number
WO1997031979A1
WO1997031979A1 PCT/US1997/003310 US9703310W WO9731979A1 WO 1997031979 A1 WO1997031979 A1 WO 1997031979A1 US 9703310 W US9703310 W US 9703310W WO 9731979 A1 WO9731979 A1 WO 9731979A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
starch
granules
natural polymer
weight
Prior art date
Application number
PCT/US1997/003310
Other languages
English (en)
Inventor
Julious L. Willett
William N. Doane
Wayne Xu
Original Assignee
Biotechnology Research And Development Corporation
The United States Of America As Represented By The Secretary Of Agriculture
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
Priority to AU20645/97A priority Critical patent/AU2064597A/en
Priority claimed from US08/804,376 external-priority patent/US5852078A/en
Application filed by Biotechnology Research And Development Corporation, The United States Of America As Represented By The Secretary Of Agriculture filed Critical Biotechnology Research And Development Corporation
Publication of WO1997031979A1 publication Critical patent/WO1997031979A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/14—Hemicellulose; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • 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
    • 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
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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

Definitions

  • the present invention generally relates to compositions useful for forming articles by means such as thermoplastic processing (e.g., molding, extrusion and casting), and more particularly relates to hydroxy- functional polyester containing compositions.
  • Articles with good mechanical properties such as tensile strength and/or tensile elongation, can be made with such polyesters in combination with natural polymers.
  • Such articles are biodegradable and have a reduced cost of manufacture due to the inclusion of a low cost natural polymer, such as starch.
  • the present invention has several embodiments that solve the problems discussed above.
  • a formed article comprises a continuous synthetic polymer phase and a discontinuous natural polymer phase.
  • the synthetic polymer phase includes a hydroxy-functional polyester that is surprisingly compatible with the natural polymer phase.
  • Articles of this embodiment can be formulated so as to have a tensile strength above about 20 MPa (sufficiently strong for example, so as to form disposable utensils) or to have a tensile elongation above about 200% (sufficient stretchability, for example, so as to form thin wrapping films).
  • a composition is provided with 45 wt.% starch granules (derived from corn) having an elongation of about 500%, while another is a composition composed of about 50 wt.% starch granules (derived from corn) which has a tensile strength of about 50 MPa.
  • the hydroxy-functional polyesters with which inventive compositions and articles may be formed by inclusion of natural polymer granules show a remarkable compatibility with natural polymers. This is illustrated by tests showing that inclusion of small amounts of granular starch into several hydroxy- functional polyesters actually increases the tensile strength of the hydroxy-functional polyester. Another example of the remarkable compatibility of the hydroxy- functional polyesters and granular starch is shown in instances where inclusion of plasticizer actually leads to moderately improved tensile strength although presence of plasticizer in other polymer compositions typically softens such compositions.
  • compositions of the invention are useful for formed articles, particularly by thermoforming techniques such as molding, extrusion and casting, and preferably comprise a hydroxy-functional polyester, such as a poly(hydroxyester) or a poly(hydroxyester ether), admixed with starch or modified starch granules derived from a grain, a root, a legume, or mixtures thereof.
  • modified is meant that the starch can be derivatized or modified by typical processes known in the art (e.g. esterification, etherification, oxidation, acid hydrolysis, cross-linking and enzyme conversion).
  • a modified starch may be a starch ester, a starch ether, or a crosslinked starch.
  • the granules preferably have less than about
  • 15 wt.% water and preferably have a particle size of less than about 50 ⁇ m.
  • compositions of the invention can optionally include various additional materials, such as for example plasticizers, processing aids, and filler materials, such as for example cellulose, vegetable fibers, calcium carbonate, talc, etc.
  • additional materials such as for example plasticizers, processing aids, and filler materials, such as for example cellulose, vegetable fibers, calcium carbonate, talc, etc.
  • Figure 1 is a scanning electron micrograph of one inventive embodiment at a magnification of 1000;
  • Figure 2 is another scanning electron microgram of another inventive embodiment, but again at a magnification of 1000, and was made following an elongation test;
  • Figures 3A and 3B are electron micrographs of a composition at two different stages of mixing:
  • Figure 3A is a micrograph of an inventive composition (designated 53) after it has been compounded once and thus only partially mixed;
  • Figure 3B is a micrograph of this inventive composition (now designated 53') after it has been compounded twice and is an example of a thoroughly mixed composition;
  • Figure 4 is an electron micrograph of an inventive composition designated 77"; and, Figure 5 is an electron micrograph of an inventive composition designated 78".
  • compositions made from a mixture of synthetic and natural polymers comprise essentially two critical components: the first component is an hydroxy- functional polyester, and the second component is a natural polymer.
  • the first component is an hydroxy- functional polyester
  • the second component is a natural polymer.
  • Forming a continuous polymer matrix (sometimes also described as a continuous polymer phase)
  • the hydroxy-functional polyester provides much of the structural framework of the resulting composition.
  • these granules are dispersed throughout the continuous polymer matrix formed by the hydroxy-functional polyester.
  • These natural polymer granules remain discrete units within the polyester polymer matrix, and thus the natural polymer granules are sometimes referred to as being in a discontinuous phase.
  • the natural polymer is preferably in the form of granules derived from starch or a derivatized (modified) starch, but can also be granules of other natural polymers (e.g. guar gum, cellulose, and the like).
  • Granules should have a particle size of less than about 100 ⁇ m, and preferably have a particle size of up to 50 ⁇ m and a water content of less than about 15 wt.%, more preferably less than about 10 or 11 wt.%. These two essential components are admixed in varying amounts.
  • the natural polymer may be present in a trace amount or may comprise up to 75% of the resulting composition by weight.
  • Preferred compositions contain between about 15% to about 75 % natural polymer by weight.
  • compositions contain between about 40% to about 75% natural polymer by weight.
  • higher amounts of natural polymer are preferred.
  • more energy is normally required to disperse adequately the granules throughout the continuous polymer matrix.
  • compositions of the present invention might be multiply compounded, or compounded using a more efficient processing apparatus (e.g. a twin screw extruder as is known to the art) .
  • a more efficient processing apparatus e.g. a twin screw extruder as is known to the art
  • other strategies for more efficient mixing as known to the art may be used such as the addition of dispersal agents.
  • compositions have been found effective in significantly improving properties of the resulting compositions by thoroughly dispersing the granules so as each substantially to be in contact with (surrounded by) the polymer matrix.
  • compositions have been made containing between about 45% and about 75% by weight of the natural polymer and having tensile strengths above about 20 MPa and generally above about 30 MPa.
  • a composition containing 50% starch by weight had a tensile strength of about 50 MPa.
  • Useful hydroxy-functional polyesters for this invention may be prepared from base-catalyzed nucleo- philic addition of suitable acids to epoxies, which reaction generates both an ester linkage and a pendent hydroxyl group. Transesterification and cross linking reactions are eliminated through use of quaternary ammonium halide salts as initiators for the reaction of diacids with diglycidyl ethers, providing convenient preparation of high molecular weight, thermoplastic, hydroxy-functional polyesters in ether solvents at temperatures from 80°C-160°C.
  • the preparation and structures for such hydroxy-functional polyesters suit- able in practicing this invention may be as described by U.S.
  • Patent 5,171,820 inventors Mang and White, issued December 15, 1992, which is hereby incorporated in its entirety by reference.
  • Data provided by the Dow Chemical Company indicates the biodegradable nature of these polymers through the ability of various soil bacteria (such as Pseudomonas putida ) to use the synthetic polymers as a substrate for cell culture growth.
  • Representative structures for suitable hydroxy-functional polyesters in practicing this invention are preferably represented by Formula A (where n provides a sufficient molecular weight, such as for example a m.w. of about 50,000-100,000). Higher molecular weights are preferred due to higher strength.
  • each of R 1 and R 2 is individually a divalent organic moiety which is predominately hydrocarbon
  • each R 3 is individually hydrogen or lower alkyl
  • y is a fraction from 0 to 0.5
  • x is a fraction from about 0.05 to about 0.4.
  • Y is hydrogen or glycidyl and Y' is glycidyl arylene ether, glycidyl alkyene ester, glycidyl alkylene ether or glycidyl arylene ester.
  • suitable polyesters have repeating units represented by Formula B (where each of R 1 , R 2 , R 3 , x, and y are as defined above).
  • polyesters are prepared from diglycidyl esters of an aliphatic diacid such as adipic due to the ready availability and reasonable price for adipic acid as a source of reactant.
  • Other particularly preferred polyesters may be prepared from dihydric phenols, such as hydroquinone.
  • n preferably is as earlier described.
  • starch is a low-cost and abundant natural polymer composed of amylose and amylopectin.
  • Amylose is essentially a linear polymer having a molecular weight in the range of 100,000-500,000, whereas amylopectin is a highly branched polymer having a molecular weight of up to several million.
  • Unmodified, natural starches are obtained in granular form and may be derived from cereals or grains (such as corn, wheat, rice and sorghum), roots (such as cassava), legumes (such as peas). Such starch granules typically have a particle size less than about 50 ⁇ m, which is the preferred particle size.
  • flours whose contents are predominately starch, and which may also contain protein, oil and fiber, are operative in the invention. Where such other natural polymers are used, they should be processed so as to be in granular form and preferably will have a relatively uniform particle size of about 50 ⁇ m or less.
  • Starch granules for use in this invention will normally have a water content of less than about 15 wt.%, more preferably less than about 10-11 wt.%. As will be exemplified, granules may be pre-dried to less than about 1% moisture before compounding. Although preferred, pre-drying is not believed necessary.
  • Derivatized starches are also suitable for use in this invention.
  • modified starches is meant to include starches which have been chemically treated so as to form starch esters, starch ethers, and crosslinked starches.
  • modified starches is meant that the starch can be derivatized or modified by typical processes known in the art (e.g. esterification, etherification, oxidation, acid hydrolysis, cross- linking and enzyme conversion).
  • modified starches include esters, such as the acetate ester of dicarboxylic acids/anhydrides.
  • alkenyl-succinic acids and hydrides, ethers (such as the hydroxyethyl and hydroxypropyl starches), starches oxidized with hypochlorite, starches reacted with cross-linking agents such as phosphorus oxychloride, epichlorhydrin, hydrophobic cationic epoxides, and phosphate derivatives prepared by reaction with sodium or potassium orthophosphate or tripolyphosphate and combinations thereof.
  • cross-linking agents such as phosphorus oxychloride, epichlorhydrin, hydrophobic cationic epoxides, and phosphate derivatives prepared by reaction with sodium or potassium orthophosphate or tripolyphosphate and combinations thereof.
  • starch esters may be prepared using a wide variety of anhydrides, organic acids, acid chlorides, or other esterification reagents.
  • anhydrides are acetic, propionic, butyric, and so forth.
  • the degree of esterification can vary as desired, such as from one to three per glucosidic unit of the starch, or as appropriate given the number of hydroxyl groups in the monomeric unit of the natural polymer, if selected to be other than starch.
  • Similar or different esterified natural polymers, with varying degrees of esterification can be blended together for practicing the invention.
  • esterified starches are stable to attack by amylases, in the environment the esterified starches are attached by microorganisms secreting esterases which hydrolyze the ester linkage.
  • Starch esters tend to be hydrophobic in contrast to starch raw materials (that is, derived by usual techniques from natural sources such as corn) .
  • hydrophobic starch ester rather than a hydrophilic starch in formulating compositions of the invention.
  • Starches are preferred for use as the natural polymers, particularly due to ready availability and low cost, but other suitable natural polymers (in or prepared to be in granular form of a suitable particle size) are hydroxyl containing polymers such as cellulose, hemicellulose, chitin, guar gum, locust bean gum, pectin, xanthan, algin, agar, and dextran. Some of these can play the role of filler, also. Excellent results have been obtained with both granulated guar gum and cellulose powder, as will be exemplified hereinafter.
  • Optional Components are hydroxyl containing polymers such as cellulose, hemicellulose, chitin, guar gum, locust bean gum, pectin, xanthan, algin, agar, and dextran.
  • Plasticizers can be added to inventive compositions to achieve greater material processability and product flexibility, although plasticizers typically soften the compositions in which they are included. This is not always true, however, of compositions of the invention, as will be discussed hereinafter.
  • Molded articles and films prepared from blends including plasticizers preferably use plasticizers that are biodegradable.
  • biodegradable plasticizers include various esters, such as phthalate esters, and various other biodegradable esters known in the chemical arts.
  • Inorganic and organic fillers can be added, such as talc, calcium carbonate, diatomaceous earth, and so forth.
  • Biodegradable organic fillers such as cellulose and other fibers and the like are well known.
  • compositions of the invention can be processed by various methods such as extrusion, injection molding, and film forming methods.
  • extrusion casting can give translucent, flexible films.
  • Inventive embodiments were prepared from premixed batches of starch or derivatized starch and polyester and optionally containing plasticizer or other additives.
  • the starches were pre-dried to less than 1% moisture before compounding. Compounding was then accomplished on a Brabender PL2000 torque rheometer using a mixing screw with a fluted dispersive mixing section and a notched distributive section. Strands from the die were air cooled and pelletized.
  • tensile bars (ASTM D638 Type V) either with a Cincinnati Millicron Model ACT-75B or a Rabit Hy-4 ram-type machine with a single cavity mold.
  • tensile bars were compression molded in a Carver Press or were stamped from compression molded blanks formed in a Carver Press.
  • Tensile bars were conditioned at 50% RH and 23°C for one day before testing in order to provide equivalent conditions in comparing one run to another. Selected compositions were also tested after immersion in water for one day. Tensile tests were performed on an Instron Model 4201 testing system.
  • inventive compositions may be made as formed articles.
  • Compositions of the invention are suitable for thermoplastic processing, such as molding, extrusion and casting, in applications where solid articles are desired as well as where thin, stretchable films are desired.
  • processability places an upper limit on the starch content (e.g. about 70 wt.% or 80 wt.%).
  • Embodiments of the invention were prepared as described by Example 1. Four were selected or having a tensile strength above about 20 MPa, as is set out by the data of Table 1.
  • the natural polymer used for all four compositions was corn derived starch granules.
  • the inventive composition 1 is remarkable in its tensile strength property when one considers that the tensile strength of 100% BIS CHD polymer is 60-61 MPa. This means the inventive composition with 15 wt.% starch has a tensile strength that is increased with respect to the polyester itself. This is another illustration of the remarkable compatibility between natural polymers, such as the granular starch component, and the hydroxy-functional polyester for compositions of the invention.
  • inventive compositions 3 and 4 had only about Vb the tensile strength in comparison to a composition with all polyester, nevertheless even the highly starch filled composition had a tensile strength adequate for forming a number of useful articles, such as for example disposable utensils.
  • Example 1 Further embodiments of the invention were prepared as described by Example 1. Nine were selected for having a tensile strength at about 20 MPa or greater. These are set out by the data of Table 2.
  • the granules used as natural polymers for the Table 2 compositions were corn derived starch.
  • compositions 11-14 included ESTAFLEX plasticizer (acetyltributylcitrate), compositions 15-16 included PARAPLEX plasticizer (epoxidized soybean oil), compositions 7-9 included either PEG 3350 or PEGC 20M plasticizer (polyethylene glycols).
  • the data of Table 2 illustrate the uses of various optional components, such as different plasticizers, in compositions of the invention.
  • inventive composition 3 from Table 1 A comparison of inventive composition 3 from Table 1 with inventive composition 15 of Table 2 illustrates that the use of particular plasticizers can even moderately improve tensile strengths.
  • This is another example of the remarkable compatibility of the two essential components of the invention because plasticizer is normally used to improve processing, but normally softens the composition.
  • inventive compositions 16 and 7-9 of Table 2 and inventive compositions 3 and 4 of Table 1 have tensile strength values in the range of about 18-23 MPa.
  • inventive compositions have better tensile strength than the biodegradable compositions reported by Ramsey, supra , but by contrast to the Ramsey compositions the inventive compositions included between about 45-60 wt.% starch granules (whereas the Ramsey compositions included only about 25 wt.% granular starch) .
  • inventive compositions with yet another hydroxy-functional polyester While inventive composition 28 (with 15 wt.% starch) has good tensile strength, it is considerably less than that found with inventive composition 1 where the hydroxy-functional ester was BIS CHD. However, with increased amounts of starch granules (in the range of 30 wt.% to 45 wt.% starch) the tensile strength improved.
  • Fig. 1 illustrates inventive composition 31. As illustrated, the discontinuous starch granules are well adhered in the continuous polyester phase. By contrast, non-inventive compositions of starch and with various polyesters were found readily to fall apart and when viewed with analogously magnified micrographs to have visible holes where the non-adhered starch granules had fallen out.
  • inventive compositions 23-25 gave outstanding elongation properties. For comparison, for example, the elongation to break (percent) for 100% high density polyethylene is 759. Thus, inventive compositions 23-25 compare quite favorably in elongation to 100% high density polyethylene, yet include up to 45 wt.% in starch granules.
  • Fig. 2 illustrates inventive composition 19.
  • hydroxy-functional polyester was BIS Adipic.
  • b Plasticizer was a modified polyethylene glycol.
  • compositions were prepared with other starches or derivatized starches.
  • diepoxide corn a reaction product of bisphenol A diglycidyl ether (10%) and corn starch
  • hydroxyethyl corn and corn flour were each formulated with BIS Adipic polyesters in amounts of about 40%-50% flour or derivatized starch.
  • BIS Adipic polyesters in amounts of about 40%-50% flour or derivatized starch.
  • Table 3 compositions (using BIS adipic) have to date been found to be preferred to all the flours and derivatized starches tested.
  • compositions were prepared, but instead of starch, flour or derivatized starch, the natural polymers used were either guar gum or cellulose. Both were in granule form with particle sizes well below 100 ⁇ m.
  • the method of preparation for the compositions was the same as described in Example 1. Table 7 summarizes the results.
  • compositions are prepared using the steps previously outlined in Example 1.
  • the starches were pre-dried to less than 1% moisture and then compounded with a Brabender PL2000 torque rheometer using a mixing screw with a fluted dispersive mixing section and a notched distributive section. Strands from the die were air cooled and pelletized. The compounded pellets were passed a second time through the Brabender PL2000 torque rheometer and the extruded strands were again air cooled and pelletized.
  • the pellets would then be passed through the Brabender PL2000.
  • the resulting strands would then be air cooled and pelletized. This may be repeated until the compounding step no longer substantially improves the properties (such as tensile strength or tensile elongation) of the resulting compositions.
  • the starch was derived from corn b ESTAFLEX (acetyltributylcitrate) was used as the plasticizer.
  • Figs. 3A and 3B dramatically illustrate the difference in electron micrographs when the composition is thoroughly mixed.
  • Fig. 3A is a scanning electron micrograph of inventive composition 53 after a single compounding step. Because this composition was processed in essentially the same way as previous inventive compositions 1-44, not surprising, Fig. 3A is similar to the micrographs illustrated by Figs. 1 and 2. It has been discovered that if the scanning electron micrograph displays granules that are substantially uncovered by the continuous polymer matrix like those shown by Figs. 1-3A, then the resulting composition is only partially mixed.
  • Fig. 3B is a scanning electron micrograph of composition 53 after the mixture has been compounded twice.
  • this micrograph discrete granules are not readily visible. Although the granules remain discrete units within the admixture, the composition is so thoroughly mixed that the granules are each substantially surrounded by the continuous polymer matrix. Without being bound by theory, it is believed that the resulting strength of the composition increases as the granules become better mixed within the continuous polymer matrix.
  • compositions are preferably mixed until each granule is substantially surrounded by the continuous polymer matrix. Table 9 illustrates twice compounded embodiments with starch from various sources.
  • Embodiments of the invention were essentially prepared as described by Example 11. However, in this example, the moisture content of the starch was adjusted to various levels before the first compounding. The starch was derived from corn. Results are shown in Table 10.
  • Figs. 4 and 5 are scanning electron micrographs of inventive compositions 77" and 78". Despite having been compounded only once, because a more efficient processing apparatus was used, the resulting compositions are still thoroughly mixed.
  • Pellets of inventive compositions 77" and 78" were processed on a Brabender PL2000 torque rheometer fitted with a 4 inch adjustable ribbon die which was adjusted to an opening of 0.015 inches.
  • the resulting extruded ribbons of the inventive compositions were air cooled and cut into lengths of about 12 inches.
  • Two sections of each inventive composition, each measuring about 3-4 inches by 12 inches were thermoformed into trays measuring about 5 inches by 9 inches. For a tray this size, two sections which overlapped at the center of the mold were required.
  • the thermoforming process was at 50°C and 75°C for inventive compositions 77" and 78" respectively. Thermoformed trays from each inventive composition were functional and sturdy.

Landscapes

  • 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

Cette invention se rapporte à des compositions qui contiennent un polyester hydroxy-fonctionnel et un polymère naturel. Des articles peuvent être fabriqués à partir d'une telle composition, de façon à posséder des résistances à la rupture par traction suffisamment importantes pour qu'on puisse former des ustensiles jetables, ou de façon à présenter une élasticité suffisante pour que l'on puisse former de minces films d'emballage. Etant donné que les compositions de cette invention contiennent une quantité importante de polymère naturel du type amidon, les articles qui en résultent sont davantage biodégradables et par conséquent plus respectueux de l'environnement que les plastiques du commerce, tels que le polyéthylène ou le polystyrène. Des polymères naturels particulièrement préférés sont les amidons granulaires dérivés de n'importe quelle combinaison de grains ou céréales, de racines et de légumes.
PCT/US1997/003310 1996-02-28 1997-02-26 Compositions de polyesters biodegradables avec polymeres naturels et articles fabriques a partir de ces compositions WO1997031979A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU20645/97A AU2064597A (en) 1996-02-28 1997-02-20 Biodegradable polyester compositions with natural polymers and articles thereo

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US61382496A 1996-02-28 1996-02-28
US1352696P 1996-02-28 1996-02-28
US60/013,526 1996-02-28
US08/613,824 1996-02-28
US76165696A 1996-12-06 1996-12-06
US08/761,656 1996-12-06
US08/804,376 US5852078A (en) 1996-02-28 1997-02-21 Biodegradable polyester compositions with natural polymers and articles thereof
US08/804,376 1997-02-21

Publications (1)

Publication Number Publication Date
WO1997031979A1 true WO1997031979A1 (fr) 1997-09-04

Family

ID=27486307

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/003310 WO1997031979A1 (fr) 1996-02-28 1997-02-26 Compositions de polyesters biodegradables avec polymeres naturels et articles fabriques a partir de ces compositions

Country Status (2)

Country Link
AU (1) AU2064597A (fr)
WO (1) WO1997031979A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999013003A1 (fr) * 1997-09-08 1999-03-18 Biotechnology Research And Development Corporation Compositions de polyester biodegradables renfermant des polymeres naturels et articles a base de ces compositions
EP1247840A4 (fr) * 1999-12-08 2003-08-13 Nat Inst Of Advanced Ind Scien Compositions a base de resine biodegradable
US8889945B2 (en) 2010-12-08 2014-11-18 Kimberly-Clark Worldwide, Inc. Elastic film containing a renewable starch polymer

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3149085A (en) * 1958-10-20 1964-09-15 West Virginia Pulp & Paper Co Method of making synthetic resin from lignin and an epoxide and resulting product
US3850862A (en) * 1972-07-28 1974-11-26 Union Carbide Corp Blends of a biodegradable thermoplastic dialkanoyl polymer and a naturally occurring biodegradable product
JPH05320326A (ja) * 1992-05-18 1993-12-03 Agency Of Ind Science & Technol 生分解性脂肪族ポリエステル重合体及びその製造法
FR2735483A1 (fr) * 1995-06-13 1996-12-20 Potency Sarl Materiau composite totalement biodegradable et procede de fabrication de ce materiau

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3149085A (en) * 1958-10-20 1964-09-15 West Virginia Pulp & Paper Co Method of making synthetic resin from lignin and an epoxide and resulting product
US3850862A (en) * 1972-07-28 1974-11-26 Union Carbide Corp Blends of a biodegradable thermoplastic dialkanoyl polymer and a naturally occurring biodegradable product
JPH05320326A (ja) * 1992-05-18 1993-12-03 Agency Of Ind Science & Technol 生分解性脂肪族ポリエステル重合体及びその製造法
FR2735483A1 (fr) * 1995-06-13 1996-12-20 Potency Sarl Materiau composite totalement biodegradable et procede de fabrication de ce materiau

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 9402, 16 March 1994 Derwent World Patents Index; AN 94-012391, XP002032727 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6025417A (en) * 1996-02-28 2000-02-15 Biotechnology Research & Development Corp. Biodegradable polyester compositions with natural polymers and articles thereof
WO1999013003A1 (fr) * 1997-09-08 1999-03-18 Biotechnology Research And Development Corporation Compositions de polyester biodegradables renfermant des polymeres naturels et articles a base de ces compositions
EP1247840A4 (fr) * 1999-12-08 2003-08-13 Nat Inst Of Advanced Ind Scien Compositions a base de resine biodegradable
US6669771B2 (en) 1999-12-08 2003-12-30 National Institute Of Advanced Industrial Science And Technology Biodegradable resin compositions
US8889945B2 (en) 2010-12-08 2014-11-18 Kimberly-Clark Worldwide, Inc. Elastic film containing a renewable starch polymer

Also Published As

Publication number Publication date
AU2064597A (en) 1997-09-16

Similar Documents

Publication Publication Date Title
US6025417A (en) Biodegradable polyester compositions with natural polymers and articles thereof
CN112876745B (zh) 一种抗菌可生物降解餐具及其制备方法
US5854345A (en) Biodegradable polyester and natural polymer compositions and expanded articles therefrom
US5852078A (en) Biodegradable polyester compositions with natural polymers and articles thereof
US6191196B1 (en) Biodegradable polymer compositions, methods for making same and articles therefrom
CA2113521C (fr) Compositions biodegradables traitables a la chaleur et articles en contenant
CN112940474B (zh) 一种抗菌耐刺破可生物降解包装袋及其制备方法
KR101477049B1 (ko) 생분해성 플라스틱의 제조에 유용한 생분해성 중합체 조성물 및 그러한 조성물을 제조하는 방법
US20060148936A1 (en) Biodegradable polymer compositions, methods for making same and articles therefrom
US5691403A (en) Biodegradable compositions
US6632862B2 (en) Biodegradable polymer compositions, methods for making same, and articles therefrom
CN112251012A (zh) 一种可溶盐辅助增塑直链淀粉制备降解塑料母料的方法
WO1997031979A1 (fr) Compositions de polyesters biodegradables avec polymeres naturels et articles fabriques a partir de ces compositions
KR100257036B1 (ko) 반응성이 우수한 열가소성 전분의 제조방법, 이를 함유하는 수지조성물 및 복합재료
US6630543B1 (en) Method of making biodegradable polymer compositions
JP3372648B2 (ja) 生分解性を有する熱可塑性セルロース誘導体組成物の成形物の製造方法
WO2001072890A1 (fr) Compositions polymeres biodegradables, procedes de fabrication et articles ainsi obtenus
KR0146849B1 (ko) 생분해성 수지 조성물

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM

CFP Corrected version of a pamphlet front page
CR1 Correction of entry in section i

Free format text: PAT. BUL. 38/97 UNDER INID NUMBER (30) "PRIORITY DATA", REPLACE "NOT FURNISHED" BY "08/804376"

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 97531200

Format of ref document f/p: F

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA