WO1997044388A1 - Biodegradable polyester and natural polymer compositions and expanded articles therefrom - Google Patents
Biodegradable polyester and natural polymer compositions and expanded articles therefrom Download PDFInfo
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- WO1997044388A1 WO1997044388A1 PCT/US1997/007410 US9707410W WO9744388A1 WO 1997044388 A1 WO1997044388 A1 WO 1997044388A1 US 9707410 W US9707410 W US 9707410W WO 9744388 A1 WO9744388 A1 WO 9744388A1
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- starch
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/127—Mixtures of organic and inorganic blowing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S521/916—Cellular product having enhanced degradability
Definitions
- the present invention generally relates to expanded articles, and more particularly relates to biodegradable admixtures of hydroxy-functional polyester and natural polymers which may be expanded as resilient, compressible, low density articles that are resistant against moisture, and are useful for applications such as packaging.
- U.S. Patent 4,863,655 inventors Lacourse et al., issued September 5, 1989, describes the disposal problems associated with most presently used packaging materials formed from synthetic polymers.
- expanded polystyrene is a resilient, compressible and low density (about 0.25 lb/ft 3 ) protective packaging filler material and performs its protective function well (e.g. as the ubiquitous "peanuts"), it is not biodegradable.
- U.S. Patent 4,863,655 also describes a biodegradable packaging material as an alternative to expanded polystyrene comprising an expanded amylose starch product. Although biodegradable, the special high amylose component used is quite expensive.
- another difficulty with the solution described by U.S. Patent 4,863,655 is that the expanded amylose starch material is not, by itself, suitable for preparing containers where moisture resistance is a necessary property (e.g. various take ⁇ out food containers) .
- Starch behavior during extrusion and injection molding has been the focus of considerable studies.
- the state of starch in these various physical changes has been described under names such as melted starch, molecularly dispersed or disrupted starch, destructured starch, and so forth.
- a historical review of starch transformation when extruded is described by Shogren et al., "Development of Starch-Based Plastics — A Reexamination of Selected Polymer Systems in Historical Perspective," Starch/ Starke , 45 , pp. 276-280 (1993).
- U.S. Patent 5,185,382 inventors Neumann et al., issued February 9, 1993, describes biodegradable packagings formed from starch and a polyalkylene glycol or derivative.
- a preferred polyalkylene glycol is polyethylene glycol.
- use of these water soluble components mean that expanded products have little resistance to moisture. Further, the bulk density property from many of the formulations tends to be rather high.
- a composition comprises a synthetic polymer and a natural polymer.
- the synthetic polymer includes a water insoluble, biodegradable hydroxy-functional polyester.
- the natural polymer preferably is starch or a modified starch in gelatinized form.
- This composition is usefully subjected to an expansion process whereby an expansion agent (e.g. water) and a nucleating agent cause bubbles, or cells, to form, which results in desired expanded articles.
- an expansion agent e.g. water
- a nucleating agent e.g. water
- the composition is thus usually referred to as a "precursor" composition.
- precursor compositions of this invention are admixtures of two essential components: hydroxy-functional polyester and natural polymer, such as starch, preferably in the form of gelatinized starch.
- inventive precursor compositions and expanded articles show a remarkable compatibility with natural polymers, such as starch and modified starch, and expanded articles therefrom are water resistant.
- inventive foamed articles have shown no substantial disintegration when immersed in water at ambient conditions for at least about 30 minutes.
- the precursor composition is a molten admixture which, is the presence of an expanding agent and a nucleating agent, may be extruded as a resilient, compressible, low density, substantially closed cell matrix.
- This compressible and resilient matrix may be the desired end result article (e.g. packaging "peanuts") or may be further processed to form desired articles, particularly by a thermoforming technique such as molding. Molded articles have exterior surfaces with sufficient resistance to moisture as to be suitable for packaging materials with a liquid component, such as hot (moisture emitting) take-out foods.
- another aspect of the invention is an article comprising a compressible and resilient body.
- the body includes two biodegradable components.
- the first component is preferably starch or a modified starch.
- the second component is a water insoluble, synthetic polymer, preferably a hydroxy-functional polyester, such as a poly(hydroxyester) or a poly(hydroxyester ether).
- the body has an exterior surface where the synthetic polymer predominants and conveys water resistance.
- the interior has the starch component predominating.
- Representative chemical 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.
- the body has the synthetic polymer predominating at an exterior surface, whereas the starch component predominates in the interior.
- the preferred starch component is derived from a gelatinized starch or a gelatinized modified starch.
- modified starch 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.
- One preferred embodiment precursor composition had 10 wt.% of a hydroxy-containing polyester, 89 wt.% gelatinized starch and water (where about 17 wt.% of the total composition was water), and 1 wt.% nucleating agent, which was expanded in a pilot scale twin screw extruder. This resulted in expanded articles with a bulk density of about 0.64 lb/ft 3 (2.5 x IO" 2 g/cm 3 ), a resilience of about 64% and a compressibility of about 0.10 MPa. These expanded articles were tested for moisture resistance. Even after being immersed in water at room temperature and stirred with a magnetic stirring bar at 200 rpm for 30 minutes, the water remained clear, which indicated that no substantial disintegration of the articles had occurred.
- precursor compositions of present invention include two essential components: the first component is a synthetic, water-insoluble biodegradable polymer, preferably an hydroxy-functional polyester; and, the second component is a natural polymer, preferably a starch or modified starch in gelatinized form.
- compositions of the invention may be present in varying amounts, although the natural polymer in the total precursor composition and in resulting expanded articles following extrusion will be present as greater than 50 wt.% of the total, preferably be greater than about 70 wt.% of total, and most preferably be up to about 97 wt.% of total.
- the synthetic polymer will be present in minor amounts, such as from a few weight percent up to about 30 wt.% of the total. Particularly preferred ranges of the synthetic polymer in foamed articles will be about 5-10 wt.%.
- Useful biodegradable, water insoluble, synthetic polymers for use in inventive compositions and expanded articles include hydroxy-functional polyesters, which may be prepared from base-catalyzed nucleophilic addition of suitable acids to epoxies. This 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 suitable 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.
- 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.
- 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.
- 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), and tubers such as potato and canna. While less preferred, flours whose contents are predominately starch, and which may also contain protein, oil and fiber, are operative in the invention.
- starch When starch is said to be “gelatinized” it has melted and lost its crystalline state.
- the starch molecules have taken on a random, disordered configuration and the starch chains have become entangled.
- the two molten polymers naturally polymer and synthetic polymer
- the synthetic polymer has been found to partition so as to predominate along exterior surfaces of the extruded body and to remain as the predominate component along exterior surfaces of further processed (e.g. thermoformed) articles. This is a desirable property since the synthetic polymer is water insoluble and thus conveys resistance to water for articles ultimately formed from the inventive precursor compositions.
- 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).
- Starches are preferred for use as the natural polymers, particularly due to ready availability and low cost.
- Extrudates from the inventive precursor compositions have substantially closed cell structures with good resilience and compressibility. Expansion, or foaming, is achieved from the precursor compositions in molten form.
- Precursor compositions of the invention will typically be processed in a suitable apparatus, such as a single screw extruder or a twin screw extruder as are well known in the food science field.
- Food extruders can be regarded as high temperature, short time reactors, in which granule starch having a moisture content of roughly 10-25% is first compressed into a dense, compact solid and then is converted into a molten, amorous mass by the high pressure, heat, and mechanical sheer forces encountered during processing. Starch extrudates tend to expand upon exiting the extruder die.
- twin screw extruders tend to be more expensive, but permit the addition of water as an expanding agent during the processing.
- the precursor composition fed into a twin screw extruder need not have the starch in a pre-gelatinized form, since starch gelatinization can occur during the extrusion process itself as water is added.
- water can serve both as a gelatinizing agent for the natural polymer as well as an expanding agent for the precursor composition.
- the precursor composition will have the starch already gelatinized.
- a precursor composition in which the starch component is to be gelatinized will typically have water present in a range of about 25 wt.% to 30 wt.% with respect to total composition.
- Water is the usual liquid in which starch is gelatinized and its role in the gelatinization can be viewed as one of plasticizer. While water is preferred, other gelatinizing agents, or plasticizers, can be used, for example, such as urea or glycerol.
- nucleating agents which can improve the uniformity of cells formed during expansion and which tend to make the cells smaller.
- Suitable nucleating agents include, for example, talc, silicon dioxide, amorous silicates, spray-dried silicon, calcium carbonate, and the like.
- plasticizer in addition to the gelatinizing agent as already discussed
- a plasticizer 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.
- the plasticizers When incorporated into composition of the invention, the plasticizers preferably are biodegradable. Examples of biodegradable plasticizers include various esters, such as phthalate esters, and various other biodegradable esters known in the chemical arts.
- Resiliency was determined in the following described experiments using a Stevens LFRA Texture Analyzer employing a cylindrical probe (TA-6, 0.25 inch diameter) run at a probe speed of 0.5 mm/sec and a probe distance of 0.3 mm. Compressibility describes the force necessary to deform a material. Desired compressibility for extruded products are in a range of about 50 to 1000 g/cm 2 (0.05 MPa to 1 MPa) . Compressibility in the following experiments was determined using the apparatus and conditions as described already in measuring resiliency.
- Precursor compositions of the invention were prepared in two steps.
- the first step was wherein granules of starch, pellets of hydroxy-containing polyester, and a trace amount of talc (as nucleating agent) were admixed with water.
- This mixture was agitated, heated, and the starch was gelatinized ("compounding").
- This compounding was performed on a Brabender PL 2000 torque rheometer using a mixing screw.
- the water content was 18-21 wt.% before the compounding.
- Temperatures during the compounding ranged from about 90°C to about 135°C.
- the resultant precursor compositions in which starch was present in gelatinized form were in the initial form of strands, which were then air cooled and pelletized. The pellets were adjusted to about 17 wt.% moisture and then were processed in the second, expansion step.
- This second step was a single screw expansion in which temperatures used in different barrels were in the range of 70°C to about 210°C.
- inventive composition 6 was expanded at 150 rpm with a die temperature of 150°C and barrels 1, 2, and 3 being, respectively, 70°C, 200°C, and 200°C.
- Use, as here, of a single screw extruder tends to lead to higher bulk density for the extrudate.
- the lower capacity of the apparatus require generally higher temperatures in order to avoid pressure build-up during the extrusion. Nevertheless, as shown by the data summarized in Table 1, generally acceptable properties were obtained for the so-processed inventive extrudates.
- Formulations of cornstarch (85-95%), Bis Adipic polyester (5-15%), and talc (0.5-1%) were prepared and moisture adjusted to about 17%. These compositions were processed in a Wenger TX-52 Twin Screw Extruder fitted with a slit die of 0.3 mm x 6 mm. The extrudates of the various compositions were expanded ribbons of about 25-30 mm in width and 10-12 mm in thickness. Sections of the ribbons about 25 cm in length were placed across a mold cavity configured to produce a tray of width 130 mm, length 215 mm, depth 20 mm and a thickness of about 3 mm. The ribbons extended beyond the width and length of the mold cavity. The mold was heated to 100°C and the mold was closed for about 10 seconds. Upon opening the mold, the foam ribbons had become compressed and rigid and had assumed the shape of the mold cavity. The rigidity of the thermoformed ribbons increased with increasing polyester content.
- This example illustrates practice of the invention for producing thermoformed articles.
- a first comparative material was "Eco-Foam” from National Starch and Chemicals (comparative peanut 1).
- a second comparative product was “Clean-Green” from Clean Green (comparative peanut 2).
- a third comparative product was “Enpak” from DuPont (comparative peanut 3).
- the inventive peanut was prepared as described by Example 2. Each of the three comparative and the inventive peanut were placed in a 200 ml flask of water at room temperature and then stirred with a magnetic stir bar at 200 rpm.
- the comparative peanut 1 started to disintegrate after about 1 minute.
- the comparative peanut 2 started to disintegrate after 2 minutes 20 seconds.
- the comparative peanut 3 started to disintegrate after 2 minutes.
- the inventive peanut showed no signs of disintegration after 30 minutes and the water in which it was suspended remained clear. Thus, the inventive peanut was water resistant.
- a foamed "peanut" of the invention is illustrated in an S.E.M. at a magnification of 250.
- the majority of cells in the matrix are closed.
- the cell sizes have a diameter of about 100 ⁇ m to about 150 ⁇ m.
- Foamed articles, or bodies, of the invention have a thin layer of the synthetic polymer predominating on the exterior surface, which conveys water resistance to the articles. This outside layer is observable even on a macroscopic level as conveying a rather smooth surface to the exterior.
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Abstract
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97921484A EP0902808A1 (en) | 1996-05-24 | 1997-05-01 | Biodegradable polyester and natural polymer compositions and expanded articles therefrom |
AU27510/97A AU723451B2 (en) | 1996-05-24 | 1997-05-01 | Biodegradable polyester and natural polymer compositions and expanded articles therefrom |
JP09542406A JP2001502362A (en) | 1996-05-24 | 1997-05-01 | Biodegradable polyester and natural polymer composition and its foamed products |
CA002254058A CA2254058A1 (en) | 1996-05-24 | 1997-05-01 | Biodegradable polyester and natural polymer compositions and expanded articles therefrom |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/653,635 US5665786A (en) | 1996-05-24 | 1996-05-24 | Biodegradable polyester and natural polymer compositions and expanded articles therefrom |
US08/653,635 | 1996-05-24 |
Publications (1)
Publication Number | Publication Date |
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WO1997044388A1 true WO1997044388A1 (en) | 1997-11-27 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US1997/007410 WO1997044388A1 (en) | 1996-05-24 | 1997-05-01 | Biodegradable polyester and natural polymer compositions and expanded articles therefrom |
Country Status (6)
Country | Link |
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US (2) | US5665786A (en) |
EP (1) | EP0902808A1 (en) |
JP (1) | JP2001502362A (en) |
AU (1) | AU723451B2 (en) |
CA (1) | CA2254058A1 (en) |
WO (1) | WO1997044388A1 (en) |
Cited By (4)
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WO1998051728A2 (en) * | 1996-12-31 | 1998-11-19 | The Dow Chemical Company | Hydroxy-functionalized polyester and poly(ester ether) oligomers |
WO1999013003A1 (en) * | 1997-09-08 | 1999-03-18 | Biotechnology Research And Development Corporation | Biodegradable polyester compositions with natural polymers and articles thereof |
EP1074604A2 (en) | 1999-08-03 | 2001-02-07 | Basf Aktiengesellschaft | Biodegradable soil loosening media |
US6573308B1 (en) | 1999-08-11 | 2003-06-03 | Basf Aktiengesellschaft | Biologically degradable foamed material particles |
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US6299969B1 (en) * | 1991-11-25 | 2001-10-09 | National Starch & Chemical Investment Holding Corporation | Expanded starch-based shaped products and the method of preparation thereof |
US5852078A (en) * | 1996-02-28 | 1998-12-22 | The United States Of America As Represented By The Secretary Of Agriculture | Biodegradable polyester compositions with natural polymers and articles thereof |
SG67489A1 (en) * | 1997-04-07 | 1999-09-21 | Mitsui Chemicals Inc | Laminating propylene/1-butene random copolymer composition and composite film using the same |
DE69805085T2 (en) * | 1997-09-05 | 2002-08-14 | Dow Chemical Co | EMULSIONS WITH A LARGE INNER PHASE AND STABLE DISPERSIONS BASED ON HYDROXY-FUNCTIONAL POLYMERS |
US6184261B1 (en) * | 1998-05-07 | 2001-02-06 | Board Of Regents Of University Of Nebraska | Water-resistant degradable foam and method of making the same |
NZ510462A (en) * | 1998-08-21 | 2003-07-25 | Bio Technology Res & Dev Corp | Method of making biodegradable polymer compositions |
US7022836B2 (en) * | 1999-02-01 | 2006-04-04 | National Starch And Chemical Investment Holding Corporation | Methods for producing and transforming cassava protoplasts |
US6376583B1 (en) | 1999-03-12 | 2002-04-23 | The Dow Chemical Company | Process for preparing starch and epoxy-based thermoplastic polymer compositions |
US6191196B1 (en) | 1999-04-12 | 2001-02-20 | The United States Of America As Represented By The Secretary Of Agriculture | Biodegradable polymer compositions, methods for making same and articles therefrom |
US7037959B1 (en) * | 1999-04-12 | 2006-05-02 | The United States Of America As Represented By The Secretary Of The Agriculture | Biodegradable polymer compositions methods for making same and articles therefrom |
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US6310136B1 (en) * | 1999-08-17 | 2001-10-30 | The United States Of America As Represented By The Secretary Of Agriculture | Blends of biodegradable poly(hydroxy ester ether) thermoplastic with renewable proteins |
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US6296795B1 (en) | 2000-05-19 | 2001-10-02 | George S. Buck | Non-woven fibrous batts, shaped articles, fiber binders and related processes |
US6280514B1 (en) * | 2000-06-23 | 2001-08-28 | National Starch And Chemical Investment Holding Corporation | Process for making a foamed polysaccharide aqueous-based adhesive |
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NZ575069A (en) * | 2006-07-28 | 2010-09-30 | Biograde Hong Kong Pty Ltd | Masterbatch and polymer composition |
US8592641B2 (en) * | 2006-12-15 | 2013-11-26 | Kimberly-Clark Worldwide, Inc. | Water-sensitive biodegradable film |
US8329977B2 (en) | 2007-08-22 | 2012-12-11 | Kimberly-Clark Worldwide, Inc. | Biodegradable water-sensitive films |
DE102007050770A1 (en) * | 2007-10-22 | 2009-04-23 | Biotec Biologische Naturverpackungen Gmbh & Co. Kg | Polymeric material and process for its preparation |
GB0911172D0 (en) | 2009-06-29 | 2009-08-12 | Univ Leicester | New polysaccharide-based materials |
US20120009420A1 (en) | 2010-07-07 | 2012-01-12 | Lifoam Industries | Compostable or Biobased Foams |
US8962706B2 (en) | 2010-09-10 | 2015-02-24 | Lifoam Industries, Llc | Process for enabling secondary expansion of expandable beads |
US8907155B2 (en) | 2010-11-19 | 2014-12-09 | Kimberly-Clark Worldwide, Inc. | Biodegradable and flushable multi-layered film |
US9327438B2 (en) | 2011-12-20 | 2016-05-03 | Kimberly-Clark Worldwide, Inc. | Method for forming a thermoplastic composition that contains a plasticized starch polymer |
US9718258B2 (en) | 2011-12-20 | 2017-08-01 | Kimberly-Clark Worldwide, Inc. | Multi-layered film containing a biopolymer |
US10400105B2 (en) | 2015-06-19 | 2019-09-03 | The Research Foundation For The State University Of New York | Extruded starch-lignin foams |
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- 1997-05-01 JP JP09542406A patent/JP2001502362A/en active Pending
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US6025417A (en) * | 1996-02-28 | 2000-02-15 | Biotechnology Research & Development Corp. | Biodegradable polyester compositions with natural polymers and articles thereof |
WO1998051728A2 (en) * | 1996-12-31 | 1998-11-19 | The Dow Chemical Company | Hydroxy-functionalized polyester and poly(ester ether) oligomers |
WO1998051728A3 (en) * | 1996-12-31 | 1999-04-01 | Dow Chemical Co | Hydroxy-functionalized polyester and poly(ester ether) oligomers |
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EP1074604A2 (en) | 1999-08-03 | 2001-02-07 | Basf Aktiengesellschaft | Biodegradable soil loosening media |
US6573308B1 (en) | 1999-08-11 | 2003-06-03 | Basf Aktiengesellschaft | Biologically degradable foamed material particles |
Also Published As
Publication number | Publication date |
---|---|
EP0902808A1 (en) | 1999-03-24 |
AU723451B2 (en) | 2000-08-24 |
US5665786A (en) | 1997-09-09 |
US5854345A (en) | 1998-12-29 |
JP2001502362A (en) | 2001-02-20 |
CA2254058A1 (en) | 1997-11-27 |
AU2751097A (en) | 1997-12-09 |
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