WO2006066041A1 - Biopolymere et ses procedes de fabrication - Google Patents

Biopolymere et ses procedes de fabrication Download PDF

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Publication number
WO2006066041A1
WO2006066041A1 PCT/US2005/045502 US2005045502W WO2006066041A1 WO 2006066041 A1 WO2006066041 A1 WO 2006066041A1 US 2005045502 W US2005045502 W US 2005045502W WO 2006066041 A1 WO2006066041 A1 WO 2006066041A1
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WIPO (PCT)
Prior art keywords
distiller
dried
composition
biopolymer
fermentation solid
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PCT/US2005/045502
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English (en)
Inventor
Michael J. Riebel
Original Assignee
Agri-Polymerix, Llc
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Publication of WO2006066041A1 publication Critical patent/WO2006066041A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the present invention relates to a composition, which can be referred to as a biopolymer, including fermentation solid and thermoactive material.
  • the present invention also includes methods of making the biopolymer, which can include compounding fermentation solid and thermoactive material.
  • the present biopolymer can be formed into an article of manufacture.
  • plastics may be formed into lumber replacements, as described in United States Patent No. 5,539,027; components of window and door assemblies, as described in
  • thermoactive materials there remains a need for an inexpensive, biologically derived material that can reduce the cost and consumption of thermoactive materials and/or that can perform better than a filler for a variety of products.
  • the present invention relates to a composition, which can be referred to as a biopolymer, including fermentation solid and thermoactive material.
  • the present invention also includes methods of making the biopolymer, which can include compounding fermentation solid and thermoactive material.
  • the present biopolymer can be formed into an article of manufacture.
  • the present invention relates to a composition including fermentation solid and thermoactive material.
  • the composition can include wide ranges of amounts of these ingredients.
  • the composition can include about 5 to about 95 wt-% fermentation solid and about 1 to about 95 wt-% thermoactive material.
  • the fermentation solid can include, in an embodiment, distiller's dried grain or distiller's dried grain with solubles, which can be derived from fermentation of plant material such as grain (e.g., corn).
  • the thermoactive material can include, for example, at least one of thermoplastic, thermoset material, and resin and adhesive polymer.
  • the present composition can be employed in any of a variety of articles.
  • the article can include the composition including fermentation solid and thermoactive material.
  • the present invention relates to a method of making a composition including fermentation solid and thermoactive material.
  • the method includes compounding ingredients of the composition including but not limited to fermentation solid and thermoactive material.
  • Compounding can include thermal kinetic compounding.
  • the composition can be made as a foamed composition.
  • Producing a foamed composition can include extruding material comprising fermentation solid and thermoactive material; the foamed material need not include blowing or foaming agent.
  • the present composition can be employed in a method of making an article. This method can include forming the article from a composition including fermentation solid and thermoactive material.
  • biopolymer refers to a material including a thermoactive material and a fermentation solid.
  • fertilization solid refers to solid material recovered from a fermentation process, such as alcohol (e.g., ethanol) production.
  • alcohol e.g., ethanol
  • fermented protein solid refers to fermentation solid recovered from fermenting a material including protein.
  • the fermented protein solid also includes protein.
  • DDG distiller's dried grain
  • grain e.g., corn
  • DDG can include residual amounts of solubles, for example, about 2 wt-%.
  • Distiller's dried grain includes compositions known as brewer's grain and spent solids.
  • DDGS distalmost fine grain with solubles
  • wet cake or “wet distiller's grain” refers to the coarse, wet residue remaining after the starch in grain (e.g., corn) has been fermented with selected yeasts and enzymes to produce products including ethanol and carbon dioxide.
  • solvent washed wet cake refers to wet cake that has been washed with a solvent such as, water, alcohol, or hexane.
  • gluten meal refers to a by-product of the wet milling of plant material (e.g., corn, wheat, or potato) for starch.
  • Corn gluten meal can also be a by-product of the conversion of the starch in whole or various fractions of dry milled corn to corn syrups.
  • Gluten meal includes prolamin protein and gluten (a mixture of water- insoluble proteins that occurs in most cereal grains) and also smaller amounts of fat and fiber.
  • plant material refers to all or part of any plant
  • Suitable plant material includes grains such as maize (corn, e.g., whole ground corn), sorghum (milo), barley, wheat, rye, rice, millet, oats, soybeans, and other cereal or leguminous grain crops; and starchy root crops, tubers, or roots such as sweet potato and cassava.
  • the plant material can be a mixture of such materials and byproducts of such materials, e.g., corn fiber, corn cobs, stover, or other cellulose and hemicellulose containing materials such as wood or plant residues.
  • Preferred plant materials include corn, either standard corn or waxy corn.
  • Preferred plant materials can be fermented to produced fermentation solid.
  • prolamin refers to any of a group of globular proteins which are found in plants, such as cereals. Prolamin proteins are generally soluble in 70-80 per cent alcohol but insoluble in water and absolute alcohol. These proteins contain high levels of glutamic acid and proline. Suitable prolamin proteins include gliadin (wheat and rye), zein (corn), and kafirin (sorghum and millet). Suitable gliadin proteins include a-, ⁇ -, J-, and ⁇ -gliadins.
  • the term "zein” refers to a prolamin protein found in corn, with a molecular weight of about 40,000 (e.g., 38,000), and not containing tryptophan and lysine.
  • glass transition point or “T g” refers to the temperature at which a particle of a material (such as a fermentation solid or thermoactive material) reaches a "softening point” so that it has a viscoelastic nature and can be more readily compacted. Below T g a material is in its "glass state” and has a form that can not be as readily deformed under simple pressure.
  • melting point or “T m” refers to the temperature at which a material (such as a fermentation solid or thermoactive material) melts and begins to flow. Suitable methods for measuring these temperatures include differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DTMA), and thermal mechanical analysis (TMA).
  • DSC differential scanning calorimetry
  • DTMA dynamic mechanical thermal analysis
  • TMA thermal mechanical analysis
  • weight percent (wt-%), percent by weight, % by weight, and the like are synonyms that refer to the concentration of a substance as the weight of that substance divided by the weight of the composition and multiplied by 100. Unless otherwise specified, the quantity of an ingredient refers to the quantity of active ingredient.
  • the term "about" modifying any amount refers to the variation in that amount encountered in real world conditions of producing materials such as polymers or composite materials, e.g., in the lab, pilot plant, or production facility.
  • an amount of an ingredient employed in a mixture when modified by about includes the variation and degree of care typically employed in measuring in a plant or lab producing a material or polymer.
  • the amount of a component of a product when modified by about includes the variation between batches in a plant or lab and the variation inherent in the analytical method. Whether or not modified by about, the amounts include equivalents to those amounts. Any quantity stated herein and modified by "about” can also be employed in the present invention as the amount not modified by about.
  • the present invention relates to a biopolymer that includes one or more fermentation solids and one or more thermoactive materials.
  • the present biopolymer can exhibit properties typical of plastic materials, properties advantageous compared to conventional plastic materials, and/or properties advantageous compared to aggregates including plastic and, for example, wood or cellulosic materials.
  • the present biopolymer can be formed into useful articles using any of a variety of conventional methods for forming items from plastic.
  • the present biopolymer can take any of a variety of forms.
  • the present biopolymer includes fermentation solid integrated with the thermoactive material.
  • a biopolymer including fermentation solid integrated into the thermoactive material is referred to herein as an "integrated biopolymer".
  • An integrated biopolymer can include covalent bonding between the thermoactive material and the fermentation solid.
  • the integrated biopolymer forms a uniform mass in which the fermentation solid has been blended into the thermoactive material.
  • the present biopolymer includes visible particles of remaining fermentation solid.
  • a biopolymer including visible particles of remaining fermentation solid is referred to herein as a "composite biopolymer”.
  • a composite biopolymer can have the appearance of granite, a matrix of thermoactive material with a first appearance surrounding particles of fermentation solid with a second appearance.
  • a significant fraction of the fermentation solid can be blended into and/or bond with the thermoactive material.
  • a composite biopolymer with the appearance of granite can form a single substance from which the particles of fermentation solid can not be removed.
  • the present biopolymer includes a significant portion of fermentation solid present as discrete particles surrounded by or embedded in the thermoactive material.
  • a biopolymer including discrete particles of fermentation solid surrounded by or embedded in the thermoactive material is referred to herein as an "aggregate biopolymer".
  • the significant portion of fermentation solid present as discrete particles can be considered an extender or a filler. Nonetheless, a minor portion of the fermentation solid can be blended into and/or bond with the thermoactive material.
  • the compounded fermentation solid and thermoactive material i.e., the soft or raw biopolymer
  • the soft or raw biopolymer before hardening, takes the form of a dough, which can be largely homogeneous.
  • "largely homogeneous" dough refers to a material with a consistency similar to baking dough (e.g., bread or cookie dough) with a major proportion of the fermentation solid blended into the thermoactive material and no longer appearing as distinct particles.
  • the soft or raw biopolymer includes no detectable particles of fermentation solid, e.g., it is a homogeneous dough.
  • the soft or raw biopolymer can include up to 95 wt-% (e.g., 90 wt-%) fermentation solid and take the form of a largely homogeneous or homogeneous dough. In an embodiment, the soft or raw biopolymer can include about 50 to about 70 wt-% fermentation solid and take the form of a largely homogeneous or homogeneous dough.
  • the raw or soft biopolymer includes visible amounts of fermentation solid.
  • visible amounts of fermentation solid refers to particles that are clearly visible to the naked eye and that provide a granite-like appearance to the cured biopolymer.
  • Such visible fermentation solid can be colored for decorative effect in the cured biopolymer.
  • the granite-like appearance can be produced by employing larger particles of fermentation solid than used to produce a homogeneous or largely homogeneous dough.
  • the biopolymer can include fermentation solid at about 0.01 to about 95 wt-%, about 1 to about 95 wt-%, about 5 to about 95 wt-%, about 5 to about 80 wt-%, about 5 to about 70 wt-%, about 5 to about 20 wt-%, about 50 to about 95 wt-%, about 50 to about 80 wt-%, about 50 to about 70 wt-%, about 50 to about 60 wt-%, about 60 to about 80 wt-%, or about 60 to about 70 wt- %.
  • the biopolymer can include fermentation solid at about 5 wt-%, about 10 wt-%, about 20 wt-%, about 50 wt-%, about 60 wt-%, about 70 wt-%, or about 75 wt-%.
  • the present biopolymer can include any of these amounts or ranges not modified by about.
  • the biopolymer can include thermoactive material at about 0.01 to about 95 wt-%, about 1 to about 95 wt-%, about 5 to about 30 wt-%, about 5 to about 40 wt-%, about 5 to about 50 wt-%, about 5 to about 85 wt-%, about 5 to about 95 wt-%, about 10 to about 30 wt-%, about 10 to about 40 wt-%, about 10 to about 50 wt-%, or about 10 to about 95 wt-%.
  • the biopolymer can include thermoactive material at about 95 wt-%, about 75 wt-%, about 50 wt-%, about 45 wt-%, about 40 wt-%, about 35 wt-%, about 30 wt-%, about 25 wt-%, about 20 wt-%, about 15 wt-%, about 10 wt-%, or about 5 wt.
  • the present biopolymer can include any of these amounts or ranges not modified by about.
  • the biopolymer can include fermentation solid at about 5 to about 95 wt-% and thermoactive material at about 5 to about 95 wt-%, can include fermentation solid at about 50 to about 70 wt-% and thermoactive material at about 30 to about 70 wt-%, can include fermentation solid at about 50 to about 70 wt-% and thermoactive material at about 20 to about 70 wt-%, can include fermentation solid at about 50 to about 60 wt-% and thermoactive material at about 30 to about 50 wt-%, or can include fermentation solid at about 60 to about 70 wt-% and thermoactive material at about 20 to about 40 wt-%.
  • the biopolymer can include about 5 wt-% fermentation solid and about 70 to about 95 wt-% thermoactive material, about 10 wt-% fermentation solid and about 70 to about 90 wt-% thermoactive material, about 50 wt-% fermentation solid and about
  • thermoactive material 30 to about 50 wt-% thermoactive material, about 55 wt-% fermentation solid and about 30 to about 45 wt-% thermoactive material, about 60 wt-% fermentation solid and about 20 to about 40 wt-% thermoactive material, about 65 wt-% fermentation solid and about 20 to about 40 wt-% thermoactive material, about 70 wt-% fermentation solid and about 10 to about 30 wt-% thermoactive material, about 90 wt-% fermentation solid and about 5 to about 10 wt-% thermoactive material.
  • the present biopolymer can include any of these amounts or ranges not modified by about.
  • the present biopolymer can have higher thermal conductivity than conventional thermoplastics.
  • the present biopolymer can cool or heat faster than the thermoactive material without fermentation solid.
  • the present biopolymer can cool as rapidly as the apparatus forming it can operate.
  • it is believed that such increased thermal conductivity can be due to the nature of the fermentation solid.
  • the increased thermal conductivity may be due to integration of the fermentation solid into the thermoactive material.
  • increased thermal conductivity employing fermented protein solid may be due to the interaction of the protein with the thermoactive material.
  • the present biopolymer has a granite-like appearance.
  • Biopolymer with a granite-like appearance can include larger particles of fermentation solid than an integrated biopolymer.
  • fermentation solid of a size of about 2 to about 10 mesh can be employed to form biopolymer with a granite-like appearance.
  • a biopolymer including such larger fermentation solid as flow characteristics suitable or even advantageous for compounding and forming.
  • a biopolymer including such a larger fermentation solid takes the form of a composite biopolymer.
  • the present biopolymer can include any of a variety of fermentation solids.
  • Fermentation solid can be recovered from any of a variety of fermentation processes, such as alcohol (e.g., ethanol) production.
  • a fermentation solid can be recovered from, for example, fermentation of plant material.
  • the fermentation solid can be recovered from fermentation of plant material containing starch, such as grain (e.g., cereal grain or legume), starchy root crop, tuber, or root.
  • the fermentation solid e.g., fermented protein solid
  • the fermentation solid can be recovered from fermentation of plant material containing starch and protein, such as grain (e.g., cereal grain or legume), starchy root crop, tuber, or root.
  • the fermentation solid is recovered from fermentation of grain.
  • the fermentation solid known as "distiller's dried grain" can be recovered from fermentation processes that convert grain to ethanol.
  • Fermentation consumes carbohydrate, such as starch, in the plant material and can provide a material with starch levels that have been reduced compared to the plant material.
  • fermentation solid includes a reduced wt-% starch compared to the plant material used in the fermentation.
  • the fermentation solid includes less than or equal to about 10 wt-% carbohydrate, less than or equal to about 5 wt-% carbohydrate, or less than or equal to about 2 wt-% carbohydrate. Fermentation solid with more than 10 wt-% carbohydrate can be employed in the present biopolymer.
  • fermentation solids Numerous fermentation solids have been characterized, primarily as animal feed.
  • the fermentation solids that have been characterized include those known as distiller's dried grain (DDG), distiller's dried grain with solubles (DDGS), wet cake (WC), solvent washed wet cake (WWC), fractionated distiller's dried grain (FDDG), and gluten meal.
  • DDG distiller's dried grain
  • DDGS distiller's dried grain with solubles
  • WWC solvent washed wet cake
  • FDDG fractionated distiller's dried grain
  • gluten meal gluten meal.
  • Fermentation solid can include, for example, protein, fiber, and, optionally, fat. Fermentation solid can also include residual starch.
  • the fermentation solid distiller's dried grain with solubles recovered from dry mill fermentation of corn can include 30 wt-% or more protein.
  • the fermentation solid distiller's dried grain with solubles recovered from conventional dry mill fermentation of corn can include about 30 to about 35 wt-% protein, about 10 to about 15 wt-% fat, about 5 to about 10 wt-% fiber, and about 5 to about 10 wt-% ash.
  • the fermentation solid distiller's dried grain with solubles recovered from conventional dry mill fermentation of corn can include about 5 wt-% starch, about 35 wt-% protein, about 15 wt-% fat, about 25 wt- % fiber, and about 5 wt-% ash.
  • the fermentation solid includes or is a DDGS including about 30-38 wt-% protein, about 1 1-19 wt-% fat, and about 25-37 wt-% fiber.
  • the fermentation solid includes or is a DDGS including about 10 wt-% starch, about 35 wt-% protein, about 15 wt-% fat, about 30 wt-% fiber, and about 5 wt-% ash.
  • DDGS can be produced by raw starch fermentation of corn.
  • the present fermentation solid can include any of these amounts or ranges not modified by about.
  • Distiller's dried grains or other distiller's dried plant materials can be derived from any of a variety of agricultural products.
  • "distiller's dried” followed by the name of a plant or type of plant refers to a fermentation solid derived from fermentation of that plant or type of plant.
  • distiller's dried grain refers to a fermentation solid derived from fermentation of grain.
  • distiller's dried corn refers to a fermentation solid derived from fermentation of corn.
  • Distiller's dried sorghum refers to a fermentation solid derived from fermentation of sorghum (milo).
  • Distiller's dried wheat refers to a fermentation solid derived from fermentation of wheat.
  • a distiller's dried plant material need not be exclusively derived from the named plant material. Rather, the named plant material is the predominant plant material or the only plant material in the fermentation solid.
  • the present biopolymer can include any of a variety of fermentation solids including, for example, distiller's dried grain, distiller's dried starchy root crop, distiller's dried tuber, distiller's dried root. Suitable distiller's dried grains include distiller's dried cereal grain and distiller's dried legume.
  • Suitable distiller's dried grains include distiller's dried maize (distiller's dried corn, e.g., distiller's dried whole ground corn or distiller's dried fractionated corn), distiller's dried sorghum (milo), distiller's dried barley, distiller's dried wheat, distiller's dried rye, distiller's dried rice, distiller's dried millet, distiller's dried oats, distiller's dried soybean.
  • Suitable distiller's dried roots include distiller's dried sweet potato and distiller's dried cassava.
  • Suitable distiller's dried tubers include distiller's dried potato.
  • the plant material can include the entirety of a plant or a portion of a plant.
  • the plant or portion of a plant can be fractionated.
  • a fermentation solid derived from fractionated plant material is referred to herein as distiller's dried fractionated plant material, e.g., distiller's dried fractionated grain.
  • the present biopolymer can include any of a variety of fractionated fermentation solids.
  • the present biopolymer can include distiller's dried fractionated corn.
  • the present biopolymer can include distiller's dried corn germ and/or distiller's dried corn endosperm.
  • Distiller's dried grains or other distiller's dried plant materials can be derived from any of a variety of fermentation processes. As the phrase suggests, distiller's dried plant materials have been dried. Drying can be accomplished at elevated temperatures in a fermentation plant or apparatus. Drying can include exposing the wet distiller's plant material with air, which can be a temperatures of 1 ,000 to 1,500 0 F. Although mixed with hot air, the distiller's plant material does not reach temperatures as hot as the hot air. The distiller's plant material can be tumbled or circulated with the air. Thus, for example, after being exposed to air at temperatures of 1 ,000 to 1 ,500 0 F, the distiller's dried plant material can reach a temperature (e.g., at the exit of the drying apparatus) of only about 200 0 F.
  • a temperature e.g., at the exit of the drying apparatus
  • the present fermentation solid e.g., fermented protein isolate
  • a temperature e.g., at the exit from the dryer
  • the present fermentation solid reached a temperature (e.g., at the exit from the dryer) of no higher than about 500 0 F, about 400 "F, about 300 0 F, about 250 0 F, about 200 0 F, or about 180 0 F.
  • the present fermentation solid e.g., fermented protein isolate
  • the present fermentation solid e.g., fermented protein isolate
  • a temperature e.g., at the exit from the dryer
  • the present fermentation solid reached a temperature (e.g., at the exit from the dryer) of no higher than about 300 0 F. In an embodiment, the present fermentation solid (e.g., fermented protein isolate) reached a temperature (e.g., at the exit from the dryer) of no higher than about 250 "F. In an embodiment, the present fermentation solid (e.g., fermented protein isolate) reached a temperature (e.g., at the exit from the dryer) of no higher than about 200 °F. In an embodiment, the present fermentation solid (e.g., fermented protein isolate) reached a temperature (e.g., at the exit from the dryer) of no higher than about 180 0 F. The present fermentation solid can include any of these temperatures not modified by about.
  • distal's dried refers to a fermentation solid that reached a temperature (e.g., at the exit from the dryer) at or below that temperature.
  • distiller's dried grain-200 refers to distiller's dried grain that reached a temperature (e.g., at the exit from the dryer) at or below 200 0 F.
  • the plant material can also be ground. Grinding can subject plant material to elevated temperatures.
  • distal's dried followed by a number with the suffix "gd” refers to a fermentation solid that was ground and dried reaching a temperature (e.g., at the exit from the dryer) at or below that temperature.
  • distiller's dried grain-200gd refers to distiller's dried grain ground and dried and that reached a temperature (e.g., at the exit from the dryer) at or below 200 0 F.
  • a fermentation solid that has been prepared by employing low temperature grinding and/or drying is referred to herein as "gently treated fermentation solid”.
  • a fermented protein solid that has been prepared by employing low temperature grinding and/or drying is referred to herein as
  • Fermentation solid suitable for the present biopolymer can be have a wide range of moisture content.
  • the moisture content can be less than or equal to about 15 wt-%, for example about 1 to about 15 wt-%.
  • the moisture content can be about 5 to about 15 wt-%.
  • the moisture content can be about 5 to about 10 (e.g., 12) wt-%.
  • the moisture content can be about 5 (e.g., 6) wt-%.
  • the present biopolymer can include or can be made from a fermentation solid with any of broad range of sizes.
  • the fermentation solid employed in the biopolymer has a particle size of about 2 mesh to less than about 1 micron (e.g., to about 0.1 or about 0.01 micron), about 2 to about 10 mesh, about 12 to about 500 mesh, about 60 mesh to less than about 1 micron, about 60 mesh to about 1 micron, about 60 to about 500 mesh.
  • Biopolymers including fermentation solid with particle size less than about 1 micron e.g., to about 0.1 or about 0.01 micron
  • the fermentation solid employed in the biopolymer can be or has been treated before compounding by coloring, grinding and screening (e.g., to a uniform range of sizes), drying, or any of a variety of procedures known for treating agricultural material before mixing with thermoactive material.
  • the biopolymer can include fermentation solid at about 0.01 to about 95 wt-%, about 1 to about 95 wt-%, about 5 to about 95 wt-%, about 5 to about 80 wt-%, about 5 to about 70 wt-%, about 50 to about 95 wt-%, about 50 to about 80 wt-%, about 50 to about 70 wt-%, about 50 to about 60 wt-%, about 60 to about 80 wt-%, or about 60 to about 70 wt-%.
  • the biopolymer can include fermentation solid at about 5 wt-%, about 10 wt-%, about 50 wt-%, about 60 wt-%, about 70 wt-%, or about 75 wt-%.
  • the present biopolymer can include any of these amounts or ranges not modified by about.
  • Fermentation solid suitable for the present biopolymer include those derived from dry milling processes known as "raw starch” processes.
  • Raw starch processes producing suitable fermentation solid include those described in U.S. Patent Application No. 10/798,226 and U.S. Provisional Patent Application No. 60/552,108, each filed March 10, 2004, and each entitled “METHOD FOR PRODUCING ETHANOL USING RAW STARCH”.
  • the present fermentation solid e.g., fermented protein solid
  • the present fermentation solid can be advantageously suited for forming biopolymers.
  • the present fermentation solid e.g., fermented protein solid
  • the present fermentation solid e.g., fermented protein solid
  • an embodiment of an integral biopolymer can include covalent bonding between the fermentation solid (e.g., fermented protein solid) and the thermoactive material.
  • the present fermentation solid e.g., fermented protein solid
  • the present fermentation solid imparts desirable thermal conductivity (e.g., advantageously rapid heating and cooling) to the biopolymer.
  • the present fermentation solid e.g., fermented protein solid, such as DDG or DDGS
  • the fermentation solid can be compounded at a temperature at which it exhibits viscoelastic properties, e.g. between T g and T m .
  • the fermentation solid can be compounded at a temperature at which it has melted or can melt, e.g., at or above T m .
  • the biopolymer includes a thermoactive material with a melting point less than about T 1 , for the fermentation solid.
  • the biopolymer includes a thermoactive material with a melting point less than about T n , for the fermentation solid.
  • the fermentation solid can have T m approximately equal to that of the polymer.
  • the T 111 of the fermentation solid can be related to its content of oil or syrup (e.g., solubles) from the plant material or other additives.
  • the T m of the fermentation solid e.g., fermented protein solid, such as DDG or DDGS
  • the T m of the fermentation solid can be selected by controlling the amount of oil or syrup (e.g., solubles) in the material. For example, it is believed that higher oil or syrup (e.g., solubles) content decreases T m and T g and lower oil or syrup (e.g., solubles) content increases T m .
  • the T 111 of fermentation solid can be related to its content of plasticizer (e.g., water, liquid polymer, liquid thermal plastic, fatty acid, or the like).
  • plasticizer e.g., water, liquid polymer, liquid thermal plastic, fatty acid, or the like.
  • the T 111 of the fermentation solid fermentation solid e.g., fermented protein solid, such as DDG or DDGS
  • the T 111 of the fermentation solid fermentation solid can be selected by controlling the amount of plasticizer in the material. For example, it is believed that higher plasticizer content decreases T m and T g and lower plasticizer content increases T m .
  • thermoactive material can be also above the melting point of the thermoactive material and suitable for compounding with the thermoactive material.
  • T g and T m of the fermentation solid allow compounding with polymers with a relatively high melting point, such as polyethylene terephthalate (PET), polycarbonate, and other engineered plastics.
  • the present fermentation solid e.g., fermented protein solid, such as DDG or DDGS
  • the present fermentation solid can include an advantageously processed plant material. Fermenting the plant material can remove a substantial portion of the starch and carbohydrate. It is believed that fermentation can hydrolyze protein. It is believed that hydrolyzing the protein can provide functional groups that can form covalent interactions with the thermoactive material, which can result in advantageous characteristics for the resulting biopolymer. Further, it is believed that, in certain embodiments, fermentation can render the protein less water soluble.
  • the present biopolymer can include fermentation solid (e.g., fermented protein solid, such as DDG or DDGS) including advantageously high levels of the prolamin protein found in cereal grain.
  • These prolamin proteins include zein (e.g., corn zein) and kafirin (e.g., sorghum kafirin).
  • the fermentation solid includes or is prolamin protein, such as zein (e.g., corn zein) and/or kafirin (e.g., sorghum kafirin).
  • the fermentation solid can include prolamin protein isolated or enriched from DDG or DDGS.
  • the fermentation solid can be or include prolamin protein, such as zein (e.g., corn zein) and/or kafirin (e.g., sorghum kafirin), isolated from distiller's dried plant material.
  • prolamin protein such as zein (e.g., corn zein) and/or kafirin (e.g., sorghum kafirin), isolated from distiller's dried plant material.
  • prolamin protein is referred to herein as "isolated prolamin protein”, e.g., "isolated zein” or “isolated kafirin”.
  • the present biopolymer can include fermentation solid recovered from a fermentation process in which the material has been in the presence of relatively high alcohol concentrations.
  • the present fermentation solid be recovered from a fermentation process in which the concentration of alcohol in the beer well reaches or exceeds about 60 wt-%.
  • the present fermentation solid be recovered from a fermentation process in which the concentration of alcohol in the fermenter reaches or exceeds about 19, about 20, or about 21 vol-%.
  • the present biopolymer can include a fermentation solid including diminished levels of fermentable materials, such as starch.
  • a fermentation solid can be produced by fermenting fractionated plant material. For example, removing the bran and/or germ fractions prior to fermentation can concentrate prolamin protein (e.g., zein) in the plant material and resulting fermentation solid.
  • prolamin protein e.g., zein
  • Corn endosperm includes zein. Although not limiting to the present invention, it is believed that fermentation of corn endosperm can result in increased levels of zein in the fermentation solid.
  • the present biopolymer can have advantageous flow characteristics compared to simple thermal plastics.
  • the melt flow index represents the ability of a plastic material to flow. The higher the melt flow index the easier the material flows at a specified temperature. Melt flow index can be measured by a standard test known as MFR or MFI.
  • the test includes a specific force, produced by an accurate weight, extruding a heated plastic material through a circular die of a fixed size, at a specified temperature.
  • the amount of thermoactive material extruded in 10 minutes is called the MFR.
  • This test is defined by standard plastics testing method ASTM D 3364.
  • the present biopolymer can achieve the melt index of a homogeneous thermoactive material but at a lower temperature.
  • a plastic with a melt index of 10 at 230 0 C This plastic can be employed as the thermoactive material in the present biopolymer at a level of only about 30 wt-% thermoactive material and about 70 wt-% of fermentation solid (e.g., fermented protein solid, such as DDG or DDGS).
  • the resulting biopolymer will have a melt index of about 10 at only about 160 "C, which is a much lower temperature than 230 0 C.
  • the resulting biopolymer will have a melt flow index significantly lower than 10 at 230 0 C.
  • Such advantageous flow characteristics can allow processing present biopolymer at lower temperatures. Processing at lower temperatures can save energy and provide for faster cooling.
  • filled plastics such as wood/plastic, fiber filled plastics, mineral filled plastics and other inert fillers typically decrease the melt index of the thermoactive material, which results in less flow or greater force required to induce flow.
  • these conventional filled plastics are harder to process compared to the pure plastic and can require higher temperatures to process and maintain melt flow index.
  • the biopolymer can include any of a wide variety of thermoactive materials.
  • the biopolymer can include any thermoactive material in which the fermentation solid can be embedded.
  • the thermoactive material can be selected for its ability to form a homogeneous or largely homogeneous dough including the fermentation solid.
  • the thermoactive material can be selected for its ability to covalently bond with the fermentation solid.
  • the thermoactive material can be selected for its ability to flow when mixed or compounded with fermentation solid.
  • the thermoactive material can set after being formed. Numerous such thermoactive materials are commercially available.
  • thermoactive materials include thermoplastic, thermoset material, a resin and adhesive polymer, or the like.
  • thermoplastic refers to a plastic that can once hardened be melted and reset.
  • thermoset material refers to a material (e.g., plastic) that once hardened cannot readily be melted and reset.
  • resin and adhesive polymer refers to more reactive or more highly polar polymers than thermoplastic and thermoset materials.
  • Suitable thermoplastics include polyamide, polyolef ⁇ n (e.g., polyethylene, polypropylene, poly(ethylene-copropylene), poly(ethylene-coalphaolefin), polybutene, polyvinyl chloride, acrylate, acetate, and the like), polystyrenes (e.g., polystyrene homopolymcrs, polystyrene copolymers, polystyrene terpolymers, and styrene acrylonitrilc (SAN) polymers), polysulfone, halogenated polymers (e.g., polyvinyl chloride, polyvinylidene chloride, polycarbonate, or the like, copolymers and mixtures of these materials, and the like.
  • polyamide e.g., polyethylene, polypropylene, poly(ethylene-copropylene), poly(ethylene-coalphaolefin), polybutene, polyvinyl chloride, acrylate
  • Suitable vinyl polymers include those produced by homopolymerization, copolymerization, terpolymerization, and like methods.
  • Suitable homopolymers include polyolefins such as polyethylene, polypropylene, poly-1-butene, etc., polyvinylchloride, polyacrylate, substituted polyacrylate, polymethacrylate, polymethylmethacrylate, copolymers and mixtures of these materials, and the like.
  • Suitable copolymers of alpha-olefins include ethylene-propylene copolymers, ethylene-hexylene copolymers, ethylene- methacrylate copolymers, ethylene-methacrylate copolymers, copolymers and mixtures of these materials, and the like.
  • suitable thermoplastics include polypropylene (PP), polyethylene (PE), and polyvinyl chloride (PVC), copolymers and mixtures of these materials, and the like.
  • suitable thermoplastics include polyethylene, polypropylene, polyvinyl chloride (PVC), low density polyethylene (LDPE), copoly-ethylene-vinyl acetate, copolymers and mixtures of these materials, and the like.
  • thermoset materials include epoxy materials, melamine materials, copolymers and mixtures of these materials, and the like.
  • suitable thermoset materials include epoxy materials and melamine materials.
  • suitable thermoset materials include epichlorohydrin, bisphenol ⁇ , diglycidyl ether of 1 ,4-butanediol, diglycidyl ether of neopentyl glycol, diglycidyl ether of cyclohexanedimethanol, aliphatic; aromatic amine hardening agents, such as triethylenetetraamine, ethylenediamine, N- cocoalkyltrimethylenediamine, isophoronediamine, diethyltoluenediamine, tris(dimethylaminomethylphe- nol); carboxylic acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, polyazelaic polyanhydride and phthalic an
  • Suitable resin and adhesive polymer materials include resins such as condensation polymeric materials, vinyl polymeric materials, and alloys thereof.
  • Suitable resin and adhesive polymer materials include polyesters (e.g., polyethylene terephthalate, polybutylene terephthalate, and the like), methyl diisocyanate (urethane or MDI), organic isocyanide, aromatic isocyanide, phenolic polymers, urea based polymers, copolymers and mixtures of these materials, and the like.
  • Suitable resin materials include acrylonitrilc-butadiene-styrene ( ⁇ BS), polyacetyl resins, polyacrylic resins, fluorocarbon resins, nylon, phenoxy resins, polybutylene resins, polyarylether such as polyphenylether, polyphenylsulfide materials, polycarbonate materials, chlorinated polyether resins, polyethersulfone resins, polyphenylcne oxide resins, polysulfone resins, polyimide resins, thermoplastic urethane elastomers, copolymers and mixtures of these materials, and the like.
  • ⁇ BS acrylonitrilc-butadiene-styrene
  • polyacetyl resins such as polyphenylether, polyphenylsulfide materials, polycarbonate materials, chlorinated polyether resins, polyethersulfone resins, polyphenylcne oxide resins, polysulfone resins, polyimide resin
  • suitable resin and adhesive polymer materials include polyester, methyl diisocyanate (urethane or MDI), phenolic polymers, urea based polymers, and the like.
  • the thermoactive material is or includes acrylonitrile-butadiene-styrene (ABS).
  • Suitable thermoactive materials include polymers derived from renewable resources, such as polymers including polylactic acid (PLA) and a class of polymers known as polyhydroxyalkanoates (PHA).
  • PHA polymers include polyhydroxybutyrates (PHB), polyhydroxyvalerates (PHV), and polyhydroxybutyrate-hydroxyvalerate copolymers (PHBV), polycaprolactone (PCL) (i.e. TONE), polyesteramides (i.e. BAK), a modified polyethylene terephthalate (PET) (i.e. BIOMAX), and "aliphatic-aromatic" copolymers (i.e. ECOFLEX and EASTAR BIO), mixtures of these materials and the like.
  • PHA polymers include polyhydroxybutyrates (PHB), polyhydroxyvalerates (PHV), and polyhydroxybutyrate-hydroxyvalerate copolymers (PHBV), polycaprolactone (PCL) (i.e. TONE), polyesteramides (i.e. BAK),
  • thermoactive materials include thermoplastic elastomers, such as thermoplastic polyurethanes, vulcanized thermoplastic polyolefins, thermoplastic vulcanizate, polyolefin elastomers, and the like.
  • Suitable thermoplastic polyurethane can be or include an aromatic polyester-based thermoplastic polyurethane.
  • Such thermoplastic polyurethanes are commercially available under the tradenames TEX1N ® (e.g., TEXIN ® 185) or DESMOP AN ® from Bayer.
  • thermoplastic elastomers are known and commercially available from any of a variety of sources.
  • Suitable thermoplastic elastomers include thermoplastic vulcanizate sold under the tradename SARLINK and the thermoplastic vulcanizate sold under the tradename SANTOPREN E TM.
  • Suitable thermoactive materials include terephthalate polymers, such as poly(trimethylene terephthalate) and polybutylene terephthalate (PBT). These thermoactive materials can include, for example, monomelic units derived from dimethyl terephthalate (DMT) and/or terephthalic acid (TPA) and also 1 ,3- propanediol or 1,4-butanediol.
  • Suitable thermoactive materials include other diol derived polymers, for example, polyesters such as poly(butylene adipate) diols, which can be formulated into urethane elastomers.
  • the biopolymer can include thermoactive material at about 0.01 to about 95 wt-%, about 1 to about 95 wt-%, about 5 to about 30 wt-%, about 5 to about 40 wt-%, about 5 to about 50 wt-%, about 5 to about 85 wt-%, about 5 to about 95 wt-%, about 10 to about 30 wt-%, about 10 to about 40 wt-%, about 10 to about 50 wt-%, or about 10 to about 95 wt-%.
  • the biopolymer can include thermoactive material at about 95 wt-%, about 75 wt-%, about 50 wt-%, about 45 wt-%, about 40 wt-%, about 35 wt-%, about 30 wt-%, about 25 wt-%, about 20 wt-%, about 15 wt-%, about 10 wt-%, or about 5 wt.
  • the present biopolymer can include any of these amounts or ranges not modified by about.
  • the present biopolymer includes a thermoactive material supplied as a liquid (e.g., MDI).
  • the liquid thermoactive material can provide advantageous characteristics to the biopolymer.
  • MDI, organic isocyanide, aromatic isocyanide, phenol, melamine, and urea based polymers, and the like can be considered high moisture content polymers, which can be advantageous for extrusion.
  • Such thermoactive materials can be employed to create a foamed extrusion for lower weight applications.
  • the present biopolymer can also include one or more additives.
  • Suitable additives include one or more of dye, pigment, other colorant, hydrolyzing agent, plasticizer, filler, extender, preservative, antioxidants, nucleating agent, antistatic agent, biocide, fungicide, fire retardant, flame retardant, heat stabilizer, light stabilizer, conductive material, water, oil, lubricant, impact modifier, coupling agent, crosslinking agent, blowing or foaming agent, reclaimed or recycled plastic, urea, and the like, or mixtures thereof.
  • Suitable additives include plasticizer, light stabilizer, coupling agent, urea, and the like, or mixtures thereof.
  • Suitable additives include a polyol ester compound esterif ⁇ ed with a fatty acid, such as those described in U.S. Patent No. 6,903,149.
  • additives can tailor properties of the present biopolymer for end applications.
  • the present biopolymer can optionally include about 1 to about 20 wt-% additive.
  • Hvdrolyzing Agent Hydrolyzing fermentation solid can be accomplished with a highly alkaline aqueous solution containing an alkaline dispersion agent, such as a strong inorganic or organic base.
  • the base can be a strong inorganic base, such as: KOH, NaOH, CaOH, NH 4 OH, hydrated lime or combination thereof.
  • Hydrolyzing can be accomplished by mechanical methods of heat and pressure. Hydrolysis can be accomplished by lowering the pH of the admixture. Chemical compounds such as maleic acid or maleated polypropylene can be added to the fermentation solid. Maleated polypropylenes such as G-3003 and G-3015 manufactured by Eastman chemicals are examples of hydrolysis and/or coupling materials.
  • the fermentation solid and thermoactive material can crosslink via the hydrolysis process and the molding process conditions (high temperature and high pressure).
  • the present biopolymer can optionally include about 0.01 to about 20 wt-% hydrolyzing agent.
  • plasticizers can modify the performance of the biopolymer, for example, by making it more flexible and/or changing flow characteristics.
  • the present biopolymer can include plasticizer in amounts employed in conventional plastics.
  • Suitable plasticizers include natural or synthetic compounds such as at least one of polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, triethylene glycol, diethylene glycol, dipropylene glycol, propylene glycol, ethylene glycol, glycerol, glycerol monoacetate, diglycerol, glycerol diacetate or triacetate, 1,4-butanediol, diacetin sorbitol, sorbitan, mannitol, maltitol, polyvinyl alcohol, sodium cellulose glycolate, urea, cellulose methyl ether, sodium alginate, oleic acid, lactic acid, citric acid, sodium diethylsuccinate, triethyl
  • Crosslinking agents have been found to decrease the creep observed with plastic composite products and/or can modify water resistance. Crosslinking agents also have the ability to increase the mechanical and physical performance of the present biopolymer.
  • crosslinking refers to linking the thermoactive material and the fermentation solid. Crosslinking can be distinguished from coupling agents which form bonds between plastic materials. Suitable crosslinking agents include one or more of metallic salts (e.g., NaCl or rock salt) and salt hydrates (which may improve mechanical properties), formaldehyhde, urea formaldehyde, phenol and phenolic resins, melamine, methyl diisocyanide (MDI), other adhesive or resin systems, mixtures of combinations thereof, and the like.
  • the present biopolymer can optionally include about 1 to about 20 wt-% crosslinking agent.
  • the present biopolymer can include a lubricant.
  • a lubricant can alter the fluxing (melting) point in a compounding, extrusion, or injection molding process to achieve desired processing characteristics and physical properties.
  • Lubricants can be categorized as external, internal, and external/internal. These categories are based on the effect of the lubricant on the melt in a plasticizing screw or thermal kinetic compounding device as follows. External lubricants can provide good release from metal surfaces and lubricate between individual particles or surface of the particles and a metal part of the processing equipment. Internal lubricants can provide lubrication within the composition, for example, between resin particles, and can reduce the melt viscosity. Internal/external lubricants can provide both external and internal lubrication.
  • Suitable external lubricants include non-polar molecules or alkanes, such as at least one of paraffin wax, mineral oil, polyethylene, mixtures or combinations thereof, and the like. Such lubricants can help the present biopolymer (for example, those including PVC) slip over the hot melt surfaces of dies, barrel, and screws without sticking and contribute to the gloss on the end product surface. In addition an external lubricant can maintain the shear point and reduce overheating of the biopolymer.
  • Suitable internal lubricants include polar molecules, such as at least one of fatty acids, fatty acid esters, metal esters of fatty acids, mixtures or combinations thereof, and the like.
  • Internal lubricants can be compatible with thermoactive materials such as olefins, PVC, and other thermally active materials and the fermentation solid. These lubricants can lower melt viscosity, reduce internal friction and related heat due to internal friction, and promote fusion. Certain lubricants can also be natural plasticizers.
  • Suitable natural plasticizcr lubricants include at least one of oleic acid, linoleic acid, polyethylene glycol, glycerol, stcric acid, palmitic acid, lactic acid, sorbitol, wax, epoxified oil (e.g., soybean), heat embodied oil, mixtures or combinations thereof, and the like.
  • the present biopolymer can optionally include about 1 to about 10 wt-% lubricant.
  • the present biopolymer includes a processing aid.
  • Suitable processing aids include acrylic polymers and alpha methylstyrene. These processing aids can be employed with a PVC polymer.
  • a processing aid can reduce or increase melt viscosity and reduce uneven die flow. In a thermoactive material material, it promotes ⁇ uxing and acts like an internal lubricant. Increasing levels of processing aids normally allow lower compounding, extrusion, injection molding processing temperatures.
  • the present biopolymer can optionally include about 1 to about 10 wt-% processing aid.
  • the present biopolymer includes an impact modifier.
  • Suitable impact modifiers include acrylic, chlorinated polyethylene (CPE), methacryalate - butadiene-styrene (MBS), and the like. These impact modifiers can be employed with a PVC thermoactive material. In an embodiment, the present biopolymer can optionally include about 1 to about 10 wt-% impact modifier.
  • the present biopolymer need not but can include a filler.
  • Fillers can reduce the cost of the material and can, in certain embodiments, enhance properties such as hardness, stiffness, and impact strength. Filler can improve the characteristic of the biopolymer, for example, by increasing thermal stability, increasing flexibility or bending, and improving rupture strength.
  • the present biopolymer can be in the form of a cohesive substance that can bind inert filler (such as wood, fiber, fiberglass, etc.) with petroleum based thermoactive materials. Fillers such as wood flour do not particularly enhance the qualities of filled plastic or biopolymer. Conventional fillers such as talc and mica provide increased impact resistance to the present biopolymer, but add weight and decrease the life of an extruder. Fiberglass as a filler adds considerable strength to the product, but at a relatively high cost.
  • the present biopolymer can optionally include about 1 to about 50 wt-% filler.
  • Wood flour and some other fillers used in plasties are not thermally stable.
  • Wood flour does not mix or crosslink with plastics and individual particles are surrounded with plastics under heat and pressure conditions. Mineral, fiberglass, and wood flour are called "inert" fillers due to the fact they can not crosslink or bond to the plastic. Also, wood or cellulose based fillers can not handle the heat requirements of most plastic processes (such as extrusion and injection molding).
  • wood flour fillers degrade and retain moisture.
  • the present biopolymer can include a fiber additive.
  • Suitable fibers include any of a variety of natural and synthetic fibers, such as at least one of wood; agricultural fibers including flax, hemp, kenaf, wheat, soybean, switchgrass, or grass; synthetic fibers including fiberglass, Kevlar, carbon fiber, nylon; mixtures or combinations thereof, and the like.
  • the fiber can modify the performance of the biopolymer. For example, longer fibers can be added to biopolymer structural members to impart higher flexural and rupture modulus.
  • the present biopolymer can include about 1 to about 20 wt-% fiber.
  • the present biopolymer composition need not include or employ a blowing agent.
  • the biopolymer can include or the process employ a blowing agent.
  • Suitable blowing agents include at least one of pentane, carbon dioxide, methyl isobutyl ketone (MIBK), acetone, and the like.
  • the present biopolymer can include urea as an additive.
  • Urea as an additive can advantageously increase thermal conductivity of the present biopolymer and/or provide advantageous flow characteristics as a feature of the present biopolymer. Of course, urea is not required for such advantages. Urea can be added to the present biopolymer during making this material, such as during thermal kinetic compounding.
  • thermoactive material and fermentation solid are compounded.
  • the verb "compound” refers to putting together parts so as to form a whole and/or forming by combining parts (e.g., thermoactive material and fermentation solid).
  • the fermentation solid can be compounded with any of a variety of thermoactive materials, such as thermoset and thermoplastic materials. Any of a variety of additives or other suitable materials can be mixed or compounded with the fermentation solid and thermoactive material to make the present biopolymer.
  • compounding fermentation solid and thermoactive material produces the dough-like material described hereinabove.
  • Compounding can include one or more of heating the fermentation solid and thermoactive material, mixing (e.g., kneading) the fermentation solid and thermoactive material, and crosslinking the fermentation solid and thermoactive material.
  • Compounding can include thermal kinetic compounding, extruding, high shear mixing compounding, or the like.
  • the fermentation solid and thermoactive material are compounded in the presence of hydrolyzing agent.
  • the biopolymer or biopolymer dough can be formed by melting together the fermentation solid and the thermoactive material.
  • thermal kinetic compounding of wood particles and thermoactive material produces a material in which wood particles are easily seen as individual particles suspended in the plastic matrix or as wood particles coated with plastic.
  • the compounded fermentation solid and thermoactive material can be an integrated mass that is homogenous or nearly so.
  • the compounded, raw or soft biopolymer can be used directly or can be formed as pellets, granules, or another convenient form for converting to articles by molding or other processes.
  • Thermal Kinetic Compounding can mix and compound employing high speed thermal kinetic principals.
  • Thermal kinetic compounding includes mixing two or more components with high shear speeds using an impeller.
  • Suitable thermal kinetic compounding apparatus are commercially available, for example, the Gelimat Gl (Draiswerke Company). Such a system can include a computer controlled metering and weight batch system.
  • An embodiment of a thermal kinetic compounding apparatus includes a horizontally positioned mixer and compounding chamber with a central rotating shaft. Several staggered mixing elements are mounted to the shaft at different angles. The specific number and positions of the mixing blades varies with the size of the chamber.
  • a pre-measured batch of thermoactive material and fermentation solid can be fed in to the compounder, for example, via an integrated screw which can be part of the rotor shaft. Alternatively, the thermoactive material and fermentation solid can be fed through a slide door, located on the mixer body.
  • the apparatus can include an automatically operated discharge door at the bottom of the compounding chamber.
  • thermoactive material and fermentation solid In the compounding chamber, the thermoactive material and fermentation solid is subject to extremely high turbulence, due to high tip-speed of the mixing element.
  • the thermoactive material and fermentation solid are well mixed and also subjected to temperature increase from impact against the chamber wall, mixing blades, and the material particles themselves. The friction in the moving particles can rapidly increase temperature and remove moisture.
  • thermoactive material and fermentation solid striking the interior of the chamber heats the material.
  • the material can be heated to about 140 "C to about 250 0 C in times as short as about 5 to about 30 seconds.
  • the process cycle can be microprocessor controlled.
  • the microprocessor can monitor parameters such as energy, input, temperature, and/or time.
  • the apparatus can open the discharge door and discharge of the compounded thermoactive material and fermentation solid (the biopolymer).
  • the discharged compounded thermoactive material and fermentation solid is a uniformly blended, fluxed compound, which can immediately be processed.
  • the energy consumed by blending, dispersing, and fluxing can be about 0.04 kilowatt per pound of product, which compares favorably to 0.06-0.12 kilowatt per pound of product produced by standard twin-screw compounding systems.
  • the compounded thermoactive material and fermentation solid, the biopolymer can then be run through a regrinding process to produce uniform granular materials.
  • regrinding can employ a standard knife grinding system using a screen, which can create smaller uniform particles of a similar size and shape.
  • Such granular materials can be used in, for example, extrusion, injection molding, and other plastic processing.
  • TKC processes expose the thermoactive material and fermentation solid to high temperatures and shear stresses for only a short or reduced time.
  • the duration of TKC can be selected to prevent or reduce thermal degradation.
  • thermal kinetic compounding operates on a mixture of as little as 10 wt-% thermoactive material and as much as 90 wt-% fermentation solid. Such high proportions of fermentation solid are difficult to compound with a conventional twin-screw compounding system.
  • product formulations can be changed rather quickly.
  • the chamber of the apparatus can remain clean upon compounding the fermentation solid and thermoactive material.
  • quick startup and shut down procedures are also possible in the thermal kinetic compounding apparatus as compared to standard compounding systems that require long and extensive shutdown and cleanout processes.
  • thermal kinetic compounding can quickly raise the temperature of the material including fermentation solid to the boiling point of water, at which point vaporization of water slows the temperature rise.
  • a fast rise in temperature can occur until it reaches the T 111 point of the admixture of the thermoactive material and the fermentation solid.
  • Residence time in the chamber can be from about 10 to about 30 seconds. The residence time can be selected based on variables such as diffusion constant time of the particles, initial moisture content, and the like.
  • Thermal kinetic compounding of fermentation solid and thermoactive material can employ various processing parameters to produce a desirable biopolymer.
  • thermal kinetic compounding of fermentation solid and thermoactive material produces a soft or raw biopolymer in the form of a dough, which can be largely homogeneous.
  • thermal kinetic compounding can produce a material with a consistency similar to baking dough (e.g., bread or cookie dough) with a major proportion of the fermentation solid blended into the thermoactive material and no longer appearing as distinct particles.
  • thermal kinetic compounding can produce a soft or raw biopolymer with greater than or equal to 70-90 wt-% of the fermentation solid homogenized into the dough.
  • thermal kinetic compounding can produce a soft or raw biopolymer including no detectable particles of fermentation solid.
  • thermal kinetic compounding can melt together the fermentation solid and the thermoactive material.
  • thermal kinetic compounding of wood particles and thermoactive material produces a material in which wood particles are easily seen as individual particles suspended in the plastic matrix or as wood particles coated with plastic.
  • thermal kinetic compounding can compound fermentation solid and thermoactive material to form an integrated mass that is homogenous or nearly so.
  • thermal kinetic compounding can produce raw or soft biopolymer including visible amounts of fermentation solid. Such compounding can employ particles of fermentation solid with a size of about 2 to about 20 mesh. Thermal kinetic compounding can include compounding the quantities or concentrations listed above for the fermentation solid and thermoactive materials in batch sized suitable for the apparatus. In an embodiment, thermal kinetic compounding can effectively compound fermentation solid with small amounts of thermoactive material (e.g., about 5 to about 10 wt-% thermoactive material) and produce a raw or soft biopolymer. Such amounts of the ⁇ noactive material are small compared to those employed for conventional processes of compounding plant materials, such as wood, with thermoactive materials. Compounding by Extruding
  • the present biopolymer can be formed by any of a variety of extruding processes suitable for mixing or compounding fermentation solid and thermoactive material.
  • extruding processes such as twin screw compounding
  • Compounding by extruding can provide a higher internal temperature within the extruder and promote the interaction of thermoplastics with the fermentation solid.
  • Twin screw compounding can employ co- or counter-rotating screws.
  • the extruder can include vents that allow escape of moisture or volatiles from the mixture being compounded. Using a die on the extruder can compound and form the biopolymer.
  • Processing machinery can be configured to remove water or other matter (gases, liquids, or solids) during processing of materials to form the biopolymer.
  • Water may be extracted for example during twin screw extruding processes or during thermokinetic compounding processes.
  • reference hereinafter is made to extraction of water but it is understood that other liquids, gasses, or solids, such as impurities, decomposition products, gaseous by products, and the like, can be extracted as well.
  • water can be extracted mechanically.
  • compression forces can be applied during extrusion processes to press water from the material.
  • compressing the material during extrusion can press water or other liquids or gases out of internal cells that can form in the material.
  • Heat can also be used to extract water and/or dry the material.
  • heat can be applied during the extrusion process or during other mechanical water-extraction processes.
  • the biopolymer can be immediately processed through a microwave or hot air drying system to remove the balance of water to the equilibrium point of the material. This is typically between 3-8 percent moisture content. A higher addition rate of thermoactive material tends to lower the equilibrium point and further increase chemical bonding efficiencies which creates high degrees of water resistance and mechanical strength.
  • Vacuum or suction techniques can also be applied to extract water trom the biopolymer as well as other impurities or gases.
  • heat, vacuum, and mechanical techniques can be employed together to extract water and other matter from the biopolymer.
  • closed cells can be ruptured through application of one or more of heat, compression, and vacuum suction.
  • the present biopolymer can be suitable for forming (e.g., by extruding or molding) into a myriad of forms and end products.
  • the biopolymer can be in any of a variety of forms, such as particles, granules, or pellets.
  • Articles, such as bars, sheet stock, or other formed articles can be produced from the present biopolymer through any of a variety of common, known manufacturing methods including extrusion molding, injection molding, blow molding, compression molding, transfer molding, thermoforming, casting, calendering, low-pressure molding, high-pressure laminating, reaction injection molding, foam molding, or coating.
  • the present biopolymer can be formed into articles by injection molding, extrusion, compression molding, other plastic molding processes, or with a robotically controlled extruder such as a mini-applicator.
  • the present biopolymer including fermentation solid can be employed in, for example, paints, adhesives, coatings, powder coatings, plastics, polymer extenders, or the like.
  • the formed biopolymer can be coated employing any of a variety of coating technologies (e.g., powder coating). Powder coating can be difficult on most conventional plastics including conventional plant materials, such as wood plastic composite or aggregate materials.
  • the present biopolymer can be produced as material that has a granite-like appearance. This granite-like material can be formed by any conventional methods into slabs, boards, panels, and the like for decorative applications in a home or commercial environment. Further, the granite-like biopolymer can be formed into individual articles for which a granite-like appearance is desirable.
  • the present biopolymer can be foamed either from its soft, raw form or upon melting without addition of foaming or blowing agents. Surprisingly, the present biopolymer can foam upon extruding even in the absence of foaming agents to produce a rigid, strong hardened foam. Although not limiting the present invention, it is believed that the present foam can result from foaming of protein in the fermentation solid.
  • the stiff or solid foam can exhibit greater strength (e.g., flexural modulus) compared to conventional foamed plastics at the same density. Conventional plastics decrease in strength when foamed.
  • the present biopolymer foam may include denatured protein interacting with the thermoactive material to create an advantageously strong biopolymer foam.
  • the protein component of the fermentation solid can participate in foaming of the present biopolymer.
  • foaming of cream to make whipped cream or foaming of egg whites to make meringue or angel food cake Conventional foaming of proteinaceous materials employs up to about 50 wt-% of the weight of the material.
  • the present biopolymer can include up to about 50 wt-% or more of protein from the fermentation solid. It is believed that the protein may foam upon application of kinetic energy during forming the present biopolymer. In the presence of thermoactive material, it is believed that this can yield a stiff or solid foam.
  • the present biopolymer (e.g., in the form of pellets) can be converted to a biopolymer foam by injection molding, extrusion, and like methods employed for forming plastics. Although not limiting to the present invention, it is believed that the heat and kinetic energy applied in these processes, such as by a mixing screw, is sufficient to foam the present biopolymer.
  • injection molding the mold can be partially filled to allow the foaming action of the biopolymer to fill the cavity. This can decrease the density of the molded article without using chemical foaming or blowing agents.
  • Extruding can also be employed to foam the present biopolymer. The dies used in extruding can form the foamed biopolymer.
  • the present biopolymer can be extruded to form an article of manufacture employing any of a number of conventional extrusion processes.
  • the present biopolymer can be extruded by dry process extrusion.
  • the present biopolymer can be extruded using any of a variety of conventional die designs.
  • extruding the present biopolymer to form an article can include feeding the biopolymer into a material preparation auger and converting it to a size suitable for extruding. Extruding can employ any of a variety of conventional dies and any of a variety of conventional temperatures.
  • the compounded biopolymer can be ground to form uniform pellets for use in an injection molding process.
  • the present biopolymer can exhibit faster heating and cooling times during injection molding compared to conventional thermoplastics.
  • the present biopolymer maintains the melt index of the plastic and allows flowability characteristics that allows high speed injection molding. For example, biopolymer including fermentation solid and polypropylene was observed to have higher thermal conductivity than pure polypropylene. Higher thermal conductivity provides faster heating and/or cooling, which can which can speed processes such as injection molding.
  • injection molding the present biopolymer can consume less energy than injection molding thermoactive material or filled thermoplastic material.
  • the biopolymer can be treated for appearance during or after forming.
  • the die or other surface used in forming can form a textured surface on the biopolymer article. Extruding can co-extrude an appearance layer over a biopolymer core.
  • the formed biopolymer can be treated with a multi roller printing process to impart the look of real wood or other desired printed textures or colors.
  • the formed biopolymer can be treated with a thermosetting powder.
  • the thermosetting powder can be, for example, clear, semi- transparent, or fully pigmented.
  • the powder can be heat cured, which can form a coating suitable for interior or exterior uses.
  • the powder can also be textured to provide, for example, a natural wood look and texture.
  • Thermoactive Material Including the Biopolymer can be suitable for compounding with any of a variety of thermoactive materials and can provide advantageous characteristics to the resulting modified thermoactive material.
  • a thermoactive material including an added portion of the present biopolymer can be envisioned to include the present biopolymer as an additive.
  • the modified thermoactive material can have advantageously increased thermal conductivity compared to the thermoactive material lacking the biopolymer.
  • the modified thermoactive material can have advantageous flow characteristics compared to the thermoactive material lacking the biopolymer.
  • the modified thermoactive material can have increased thermal stability compared to the thermoactive material lacking the biopolymer.
  • the modified thermoactive material can have increased mechanical strength compared to the thermoactive material lacking the biopolymer.
  • the present biopolymer can be added to the thermoactive material before making an article from the modified material.
  • the present modified thermoactive material can be employed for forming
  • the present modified thermoactive material can be in any of a variety of forms, such as particles, granules, or pellets.
  • Articles, such as bars, sheet stock, or other formed articles can be produced from the present modified thermoactive material through any of a variety of common, known manufacturing methods including extrusion molding, injection molding, blow molding, compression molding, transfer molding, thermoforming, casting, calendering, low-pressure molding, high-pressure laminating, reaction injection molding, foam molding, or coating.
  • the present modified thermoactive material can be formed into articles by injection molding, extrusion, compression molding, other plastic molding processes, or with a robotically controlled extruder such as a mini- applicator.
  • the present modified thermoactive material includes about 1 to about 50 wt-% of the present biopolymer. In an embodiment, the present modified thermoactive material includes about 2.5 to about 50 wt-% of the present biopolymer. In an embodiment, the present modified thermoactive material includes about 10 to about 50 wt-% of the present biopolymer. In an embodiment, the present modified thermoactive material includes about 20 to about 50 wt-% of the present biopolymer. In an embodiment, the present modified thermoactive material includes about 30 to about 50 wt-% of the present biopolymer. In an embodiment, the present modified thermoactive material includes about 1 , about 2.5, about 10, about 20, about 30, or about 50 wt-% of the present biopolymer. The present modified thermoactive material can include any of these ranges or amounts not modified by about.
  • the present biopolymer can be of a size of about 200 mesh for use as an additive.
  • the present modified thermoactive material includes biopolymer including DDG. In an embodiment, the present modified thermoactive material includes biopolymer including distiller's dried corn.
  • the present invention includes a method of making a modified thermoactive material.
  • a method can include combining (e.g., mixing dry materials) about 50 to about 99 wt-% thermoactive material and about 1 to about 50 wt-% of the present biopolymer.
  • a method can include combining (e.g., mixing dry materials) about 50 to about 97.5 wt-% thermoactive material and about 2.5 to about 50 wt-% of the present biopolymer.
  • Such a method can include combining (e.g., mixing dry materials) about 50 to about 90 wt-% thermoactive material and about 10 to about 50 wt-% of the present biopolymer.
  • Such a method can include combining (e.g., mixing dry materials) about 50 to about 80 wt-% thermoactive material and 20 to about 50 wt-% of the present biopolymer.
  • Such a method can include combining (e.g., mixing dry materials) about 50 to about 70 wt- % thermoactive material and about 30 to about 50 wt-% of the present biopolymer.
  • the present method can employ any of these ranges or amounts not modified by about.
  • thermoactive material such as polypropylene with, for example, 10 wt-% of the present biopolymer as an additive exhibited a decrease of about 35 to about 80 % in the length of the cooling cycle.
  • the present biopolymer can be envisioned or considered as a nucleating agent, e.g., a hyper nucleating agent, for the thermoactive material.
  • the present example describes preparation of a biopolymer according to the present invention and that included fermentation solid (e.g., DDG, a particular fermented protein solid), polypropylene, and maleated acid.
  • fermentation solid e.g., DDG, a particular fermented protein solid
  • polypropylene e.g., polypropylene
  • maleated acid e.g., maleated acid
  • these components were taken in a ratio of 60/38/2 and were compounded using a Gelimate Gl thermal kinetic compounder.
  • the other ratios listed in the table were compounded according to the same procedure.
  • Compounding was conducted at 4400 RPM; the material was and ejected from the compounder at a temperature of 190 0 C.
  • the polypropylene was a commercial product called SB 642 and supplied by Basell Coproration.
  • the biopolymer left the compounder as a dough like mass that resembled bread dough (soft or raw biopolymer).
  • Pellets of the present biopolymer were injection molded in a standard "dogbone” mold on an Toshiba Electric Injection molding press at a temperature in all three zones of 320 0 F.
  • the commercial polypropylene alone was also molded by the same procedure.
  • fermentation solid e.g., fermented protein solid
  • thermoactive material from which it was made. This result is illustrated in each of the three measures of strength for each polymer.
  • the present biopolymer exhibited greater tensile strength than the plastic control. This was surprising.
  • Conventional filled plastic materials filled, for example with inert filler
  • conventional filled plastic material typically have less tensile strength than the plastic material from which they are made.
  • a conventional filled plastic material with as much as 50 wt-% or 70 wt-% inert filler would have less tensile strength than the plastic from which it was made.
  • biopolymers with 50 wt-% or 70 wt-% fermentation solid e.g., fermented protein solid
  • each exhibited greater tensile strength than the plastic control.
  • the present biopolymer gained additional tensile strength upon addition of a cross-linking agent.
  • the present biopolymer exhibited greater flexural modulus than the plastic control.
  • biopolymers with 50 wt-% or 70 wt-% fermentation solid each exhibited greater flexural modulus than the plastic control.
  • the present biopolymer gained additional flexural modulus upon addition of a cross-linking agent.
  • the present biopolymer exhibited decreased displacement (less "stretch”) compared to the plastic control.
  • biopolymers with 50 wt-% or 70 wt-% fermentation solid each exhibited decreased displacement compared to the plastic control.
  • decreased stretch can be considered to relate to increased thermal, process, and structural stability.
  • the embodiment of the present biopolymer maintained its lighter color and was very homogenous in appearance. This indicates that the present biopolymer intermeshed or melted together under the extruder condition employed.
  • a fermentation solid specifically, a gently treated DDG (corn) (70 wt-%) was thermokinetically compounded with a thermoplastic elastomer (24 wt-%), specifically a thermoplastic vulcanizate sold under the tradename SANTOPRENETM or sold under the tradename S ⁇ RLINK ® .
  • the biopolymer also included TiO 2 , a lubricant, and citric acid.
  • thermoplastic vulcanizate yielded parts that were sticky and hard to eject from the injection molder.
  • the injection molding machine was programmed to hit the ejector pins three times to fully remove these sticky parts from the mold. Cooling cycle time was about 30 seconds.
  • Injection molded parts were also made from a mixture of 10 wt-% biopolymer and 90 wt-% thermoplastic vulcanizate. The parts were cooler to the touch and ejected easily with one strike from the pins. The cooling cycle time was reduced to 15-20 seconds. Cooler parts, easy ejection, and shorter cooling cycle time was also obtained for parts including 15 wt-%, 20% wt-%, and 25 wt-% biopolymer.
  • Rates of crystallization were determined employing a differential scanning calorimeter (DSC) (Perkin Elmer). The calorimeter was operated in the mode for detecting "isothermal crystallization". A 10 mg sample of biopolymer (or control thermoactive material) was heated to 30 "C above the melting point of the polymer. The melting point had previously been determined using the DSC. The sample was then rapidly cooled at a rate of 50 0 C /min and then held at about 120 U C. The heat flow was measured as a function of time and as the material changed from a liquid to a solid or crystalline state. The biopolymer employed in this study included fermentation solid (specifically gently treated distiller's dried corn) and polyethylene.
  • biopolymer employed in this study included fermentation solid (specifically gently treated distiller's dried corn) and polypropylene.
  • the present biopolymer was blended with polypropylene and studied by dynamic melt rheometry (ARES). The rheometry was conducted on polymer at 182 0 C (360 0 F) and with strain of 15%.
  • the biopolymer employed in this study included fermentation solid (specifically gently treated distiller's dried corn) and thermoplastic vulcanizate. The materials tested included:
  • Materials including the present biopolymer had significantly different rheological properties compared to polypropylene.
  • materials including the present biopolymer had significantly different values of complex viscosity ( ⁇ *) as a function of frequency ( ⁇ ).
  • the complex viscosity increased for material including 10 wt-% and 30 wt-% biopolymer and polypropylene.
  • the complex viscosity seemed to decrease at 70 wt-% biopolymer.
  • the biopolymer and the composition including 70 wt-% biopolymer were shear sensitive.
  • the phrase "adapted and configured” describes a system, apparatus, or other structure that is constructed or configured to perform a particular task or adopt a particular configuration to.
  • the phrase "adapted and configured” can be used interchangeably with other similar phrases such as arranged and configured, constructed and arranged, adapted, constructed, manufactured and arranged, and the like. All publications and patent applications in this specification are indicative of the level of ordinary skill in the art to which this invention pertains.

Abstract

L'invention concerne une composition, que l'on peut appeler biopolymère, qui renferme un solide de fermentation et un matériau thermoactif. L'invention concerne également des procédés de fabrication du biopolymère, qui peuvent consister à associer un solide de fermentation et un matériau thermoactif. Ledit biopolymère peut être transformé en un article manufacturé.
PCT/US2005/045502 2004-12-13 2005-12-13 Biopolymere et ses procedes de fabrication WO2006066041A1 (fr)

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US63580104P 2004-12-13 2004-12-13
US60/635,801 2004-12-13
US15323205A 2005-06-14 2005-06-14
US11/153,232 2005-06-14

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WO2008030969A2 (fr) * 2006-09-07 2008-03-13 Phillips Plastics Corporation Matériaux composites
CN102336989A (zh) * 2011-10-19 2012-02-01 北京欧尼克新型材料有限公司 Pvc木塑发泡木纹型材及其制备方法
CN102453289A (zh) * 2010-10-22 2012-05-16 中国石油化工股份有限公司 耐光老化、成本低、可再生pvc发泡复合材料及其制备方法
CN110054838A (zh) * 2019-04-26 2019-07-26 四川大学 一种纤维素杂化填料增强聚合物复合材料及其制备方法
CN110736033A (zh) * 2019-10-28 2020-01-31 维吉尔泰光电科技(徐州)有限公司 一种led灯用全塑灯壳
WO2021001197A1 (fr) * 2019-07-01 2021-01-07 Deutsche Institute Für Textil- Und Faserforschung Denkendorf Matériau composite comprenant une matrice à base de matières plastiques organiques et son utilisation

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EP0082581A1 (fr) * 1981-12-29 1983-06-29 Unilever N.V. Produit laitier fermenté contenant des bactéries d'acide lactique et procédé pour sa préparation
US6313105B1 (en) * 1997-07-09 2001-11-06 Aventis Research And Technologies Gmbh & Co Kg Thermoplastic mixtures containing dialdehyde starch and natural polymers
US6323265B1 (en) * 1997-07-09 2001-11-27 Aventis Research & Technologies Gmbh & Co Kg Thermoplastic mixture containing 1,4-α-D-polyglucane, method for making the same and use thereof
WO2004113435A1 (fr) * 2003-06-13 2004-12-29 Agri-Polymerix, Llc Structures et elements biopolymeres

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GB1247473A (en) * 1969-02-06 1971-09-22 Raimund Jetzer Improvements in and relating to the production of press board from refuse
EP0082581A1 (fr) * 1981-12-29 1983-06-29 Unilever N.V. Produit laitier fermenté contenant des bactéries d'acide lactique et procédé pour sa préparation
US6313105B1 (en) * 1997-07-09 2001-11-06 Aventis Research And Technologies Gmbh & Co Kg Thermoplastic mixtures containing dialdehyde starch and natural polymers
US6323265B1 (en) * 1997-07-09 2001-11-27 Aventis Research & Technologies Gmbh & Co Kg Thermoplastic mixture containing 1,4-α-D-polyglucane, method for making the same and use thereof
WO2004113435A1 (fr) * 2003-06-13 2004-12-29 Agri-Polymerix, Llc Structures et elements biopolymeres
US20050019545A1 (en) * 2003-06-13 2005-01-27 Agri-Polymerix, Llc Biopolymer structures and components

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008030969A2 (fr) * 2006-09-07 2008-03-13 Phillips Plastics Corporation Matériaux composites
WO2008030969A3 (fr) * 2006-09-07 2008-04-24 Phillips Plastics Corp Matériaux composites
CN102453289A (zh) * 2010-10-22 2012-05-16 中国石油化工股份有限公司 耐光老化、成本低、可再生pvc发泡复合材料及其制备方法
CN102453289B (zh) * 2010-10-22 2013-12-25 中国石油化工股份有限公司 耐光老化、成本低、可再生pvc发泡复合材料及其制备方法
CN102336989A (zh) * 2011-10-19 2012-02-01 北京欧尼克新型材料有限公司 Pvc木塑发泡木纹型材及其制备方法
CN110054838A (zh) * 2019-04-26 2019-07-26 四川大学 一种纤维素杂化填料增强聚合物复合材料及其制备方法
CN110054838B (zh) * 2019-04-26 2021-04-13 四川大学 一种纤维素杂化填料增强聚合物复合材料及其制备方法
WO2021001197A1 (fr) * 2019-07-01 2021-01-07 Deutsche Institute Für Textil- Und Faserforschung Denkendorf Matériau composite comprenant une matrice à base de matières plastiques organiques et son utilisation
CN110736033A (zh) * 2019-10-28 2020-01-31 维吉尔泰光电科技(徐州)有限公司 一种led灯用全塑灯壳

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