CN1066077A - Biodegradable amyloid composition - Google Patents

Abstract

The invention provides a kind of biodegradable composition that obtains by melt, this melt comprises starch, softening agent and at least a homopolymer chain enol and/or chain-ol copolymer, this polymkeric substance is to combine under the condition that fully guarantees the even melt of formation, it is characterized in that at least a concentration that is present in the composition is 10-120 part to per 100 portions of dry starch.The invention still further relates to and make method for compositions and by the goods of described composition manufacturing.

Description

Biodegradable amyloid composition

The present invention relates to the biodegradable polymers composition, said composition is by heating and add the goods that pressure energy formation has basic size stability.The present invention be more particularly directed to biologically degradable starch-containing and at least a composition that is selected from homopolymer chain enol and/or chain-ol copolymer.Said composition is particularly useful for injection moulding, film forming and formation foam package material.

Known already that the native starch that exists in the plant prod can carry out pyroprocessing and generate melt.Produce this melt preferably to the starchy material heating, temperature surpasses the second-order transition temperature of its each component and makes it to stand heat absorption to be reset more than the melt temperature and the formation melt.Starchy material preferably contains the softening agent of specified quantity, and water preferably, melt form to be in the airtight volume of high temperature and under high pressure to carry out.

Basically be under anhydrous condition, fusion starch is possible under the situation that a kind of liquid of glass-transition temperature of starch and melt temperature exists but be higher than at other suitable softening agent such as boiling point.The different uniformity coefficient of measuring in melt forms by various different methods are possible.For example a kind of method is the quantity that is retained in the granular texture in the starch melt with the microscope measurement, starch with damage degree is that melt has uniform properties basically for preferred product, show essentially no (or minimizing) granular texture with about 500 times observation by light microscope, so fused starch presents seldom or free of birefringence, and studies show that by the X-ray and to significantly reduce in melt or do not have a starch crystals degree.

The invention has the advantages that composition can be generated by the starch with quite low damage degree.

EP-A-0375831 and EP-A-0376201(are with the name of National Storch and Chemical Co.) to discuss and environmental treatment plastic refuse associated problem, this discussion is cited reference.These two pieces of patent disclosures low density closed pore starch product, be particularly useful for doing wrapping material, the content at least 45% of amylose starch in the starch wherein, preferably at least 65%.Another EP-A-0376201 has revealed salt has been added in the starch substance that its concentration is 2% of described substance weight, can cause improving the foaming closed pore product of even foam structure.

All reasons with regard to above-mentioned previous starch composites, have been used to make biodegradable wrapping material, owing to generally can't provide the required synthetic materials of a kind of tenable selection to replace it.

The present invention provides this selection especially.

But, Ind.Eng.Chem.Prod.Res.Dev(194; 23, p594-595) narrated the extruding of starch of water-soluble poval increase-volume.Reducing so that contain the melt-flow index that the composition of 1: 1 lower molecular weight (20000) polyvinyl alcohol and low-molecular-weight (30000) W-Gum has along with the increase of starch concentration according to this melt flow index of revealing this extrudate is 0.53.The composition that comprises so low melt-flow index is to be not suitable for injection-molded item, and wherein generally needing melt-flow index is about 7 or higher composition.Therefore, being worth surprised is that the present composition that contains suitable high density starch can be easy to injection moulding.

The melt-flow index of composition is defined as when composition stands the external force of 0.2160 gram, in the weight (gram) of 10 minutes pressures by the thermoplastic in 1 2.0665mm aperture.

In forming the technology of thermoplastics, undoubtedly be that its main ingredient should be a high molecular, preferably the molecular weight of described main ingredient should be similar identical value.

Surprised is that the goods with good physical and dimensional stability can be formed by composition of the present invention, compares with the starch ingredients of composition wherein that to have low-molecular-weight polyvinyl alcohol be to exist with relative high density.

According to biodegradable composition provided by the present invention, be to make by comprising the melt that starch, softening agent and at least one be selected from homopolymer chain enol and/or chain-ol copolymer, these components are to combine being enough to guarantee to form under the condition of even melt, it is characterized in that above-mentioned at least one concentration that exists in the composition is 10 to 120 minutes to per 100 minutes dry starch.

Softening agent is meant certain material is mixed in the material to increase the Young's modulus of its flexibility, processibility or extensibility or reduction melt viscosity, reduction second order transition temperature or reduction product.Term softening agent one speech comprises solvent-type plasticizer, non-solvent type plasticizer and internal plasticizer.Preferred plasticizer is a water.

The present invention also comprises melt that is obtained by described composition and moulded products, particularly foam, film, stratiform and the injection-molded item of being made by described melt.Described even melt generally is thermoplastic, particularly preferably is thermoplastic.

In an embodiment of composition, starch is a kind of high amylose starch mutation, and the content of its amylose starch is up to about 95%(weight), be preferably 70～95%(weight).

But, described starch not necessarily the high amylose starch mutation amount that may contain amylose starch up to about 65%, up to about 45% with up to about 35%.The content of amylose starch is possible between 25 and 35% in the starch.The lower bound of the amylose content in the starch is preferably about 10～15%(weight).

Composition of the present invention preferably can contain have an appointment 10～100 fens described polymkeric substance and/or multipolymer (for per 100 minutes weight dry starch), and in preferred embodiment, it is about 10～85 minutes described polymkeric substance or multipolymer that composition contains per 100 minutes starch.

Composition also can comprise 10～65 fens, particularly 20～40 minutes polymkeric substance or multipolymer (for 100 fens starch).

Homopolymer chain enol is polyvinyl alcohol preferably, and available polyvalent alcohol such as glycerol are carried out pre-plasticising.Polyvinyl alcohol is more suitable is that degree of hydrolysis is that about 45-100%, number-average molecular weight are about 15000～250000, and more preferably number-average molecular weight is 15000-150000.

Particularly preferred composition is to contain the pre-treatment polyvinyl alcohol that exists with melt form, and it can make its fusion by adding to the enough energy of polyvinyl alcohol, and eliminates crystallization in the melt basically and make in advance.This crystalline product of eliminating fully in the melt is preferred especially.This pretreated polyvinyl alcohol is disclosed in EP-A-0415357.

Above-mentioned chain-ol copolymer preferably contains vinyl alcohol units and the unitary synthetic copolymer of aliphatics, it can be by vinyl acetate, be preferably vinyl acetate and be preferably ethene, propylene, iso-butylene and/or vinylbenzene and so on monomer and carry out copolymerization, the hydrolysed ethylene ester group makes subsequently.

Described multipolymer is known, narrates in " Encyclopedia of polymer Science and Technology, Interscience publ, Vol.14,1971 ".

Composition also can comprise compound and the boron-containing compound that is selected from nucleator, filler, stablizer, tinting material and fire retardant.Described composition also can comprise known processing aid, as lubricant, releasing agent and softening agent etc.

Recognize that component concentrations can be come fixed (if desired) according to the master batch preparation method in the composition.Starch can be modified and become to contain ether or ester group.

The present invention also provides a kind of production method for compositions, comprise a kind of starting composition softening agent and at least a starting composition that is selected from homopolymer chain enol and/or chain-ol copolymer that contains starch a) is provided, the concentration that polymkeric substance exists in composition is 10～120 minutes concerning per 100 minutes described starch;

B) during processing or plasticising, the plasticizer loading of regulating composition is about 0.5～about 40%(weight of total amount of composition);

C) composition after will regulating is heated to 100～220 ℃ of temperature, and its time at least enough forms uniform composition melt.

D) should removing excessive moisture before entering the forcing machine die head, to obtain moisture content be between about 5～20%; With

E) extrude the composition of heating.

The present invention also comprises a kind of melt that acquires as stated above.

The invention still further relates to the described method for compositions of under control plasticizer loading, temperature and pressure condition, making such as a kind of thermoplastic melt, wherein said method is a currently known methods, for example the foaming, film forming, compression moulding, injection moulding, blowing, vacuum forming, thermoforming, extrude, coextrusion and in conjunction with etc.

The present invention is by following specification sheets, in conjunction with the following example and accessory claim, make the invention is intended to more clear and definite.

Ordinance of the present invention is listed in the accessory claim.

The present invention relates to a kind of Biodegradable composition, it is to be made by starch-containing, softening agent and at least a melt that is selected from homopolymer chain enol and/or chain-ol copolymer, these components combine together under the condition that enough promotes even melt to generate, and the concentration that exists at least a polymkeric substance in the composition is 10～120 minutes to per 100 minutes dry starch.Described even melt is a preferably polyvinyl alcohol (PVA) of thermoplastic characteristics, homopolymer chain enol, and its number-average molecular weight is equivalent to the polymerization degree at least about 15000(and is at least 340).The number-average molecular weight of PVA is more preferably about 50000～250000, is preferably about 80000～120000.To the composition of foaming, it is about 160000～250000 that the number-average molecular weight of its PVA is preferably, and more preferably 160000～200000.

Polyvinyl alcohol (PVA) is generally prepared by the hydrolysis or the alcoholysis of polyvinyl acetate (PVA).The degree of hydrolysis that is used for polyvinyl alcohol of the present invention is preferably about 75～99.9 moles of %, and preferred degree of hydrolysis is about 80～99.9 moles of %, most preferably is 87～99.9 moles of %.

Described polyvinyl alcohol is known and by Air products and chemicals Inc., 7201 Hamilton Boulevard, Allentown, USA sells, it is 87-89% that name is called Airvol 540s(degree of hydrolysis, the about 106000-110000 of molecular weight); Airvol 205s(degree of hydrolysis is 87-89%, molecular weight is about 110-31000), Elvanol 90-50(degree of hydrolysis is 99.0～99.8%, and molecular weight is about 35-about 80000) and Airvol 107(degree of hydrolysis be 98.0-98.8%, molecular weight is 11000～31000).

EP-A0415357(is with the name of Air products and chemicals Inc) but narration polyethylene extrusion alcohol composition and preparation method thereof.Comprise that according to the method for EP-A0415357 giving the enough energy of polyvinyl alcohol makes its fusion and eliminate degree of crystallinity in the melt basically, and from melt, remove energy with the speed of enough avoiding polyvinyl alcohol to decompose simultaneously.Therefore, the present invention plans to use the disclosed component through pretreated polyvinyl alcohol of EP-A0415357.Therefore, composition of the present invention contains the pre-treatment polyvinyl alcohol with melt form, and this melt is by giving the enough energy of polyvinyl alcohol and make its fusion and eliminating the degree of crystallinity in the melt basically and remove from melt with the speed of enough avoiding polyvinyl alcohol to decompose simultaneously that energy makes.

The pre-treatment polyvinyl alcohol can be by adding polyol plasticiser wherein, and its amount is the 2-30%(weight of polyvinyl alcohol) come plastifying.Preferably the pre-treatment polyvinyl alcohol is by adding polyol plasticiser wherein, and its amount is the 2-20%(weight of polyvinyl alcohol) come plasticising.The pre-treatment polyvinyl alcohol also can comprise sodium acetate and phosphoric acid, and its mol ratio is about 2 to 1.Sodium-acetate exists in the polyvinyl alcohol as a kind of a kind of pair of product by its production method, and under the condition that melt forms, this sodium-acetate plays a part the polyvinyl alcohol decomposition catalyst.Therefore, phosphoric acid can be added in the polyvinyl alcohol component, and the ratio of making the adding of pre-treatment polyvinyl alcohol melt thus is that per 2 molar acetate esters add 1 equimolar acid, for the described sodium-acetate that neutralizes.The essentially no sodium-acetate of polyvinyl alcohol with low ash does not need to add described phosphoric acid.

Pretreated polyvinyl alcohol melt has a maximum melt temperature (by determine with dsc method), than low about 5 ℃ at least of corresponding untreated polyvinyl alcohol, preferably hangs down about 10 ℃ at least, more preferably hangs down about 15 ℃ at least.

The formation of this pre-treatment polyvinyl alcohol melt need be imported at least about the specific energy of 0.27KWh/Kg and give polyvinyl alcohol, the described energy of typical requirement about 0.3 to about 0.6KWh/Kg.In the upper limit of practical end-point energy, input should be about 0.6KWh/Kg, because any required energy of the pure and mild elimination degree of crystallinity of molten polyethylene that exceeds must be removed as " wasted energy ", this wasted energy reduces the benefit that the pre-treatment polyvinyl alcohol forms.Optimum is that polyvinyl alcohol needs intake about 0.35 to about 0.45KWh/Kg, with the pure crystallization of also eliminating basically in the melt of molten polyethylene.

The described PVA(that composition preferably comprises about 10-100 branch says per 100 minutes starch), in particularly preferred embodiment, composition contains the per 100 minutes starch of 10 to about 85 minutes described PVA(of having an appointment).For 100 fens starch, same polymkeric substance or multipolymer content were the 10-65 branch, and particularly the 20-40 branch also is extremely suitable.

Preferred chain-ol copolymer is to contain vinyl alcohol units and unitary these multipolymers of aliphatic chain.It is by vinyl acetate between to for plastic and ethene and/or propylene, preferably carries out copolymerization with ethene, and group makes with the posthydrolysis vinyl acetate-based.This multipolymer can have different water Jie degree.Preferably ethylene/vinyl alcohol polymers (EVOH) and propylene/ethylene alkoxide polymer.Ethylene/vinyl alcohol polymers most preferably.The unitary mol ratio of vinyl alcohol units and alkene is preferably about 40: 60 to about 90: 10, more preferably about 45: 55 to about 70: 30.The ethylene content of most preferred EVOH is 44%.

Exist in starch in the present composition and be a kind of in the native starch that is selected from plant-sourced at least, it is by potato, rice, tapioca (flour), corn, pea, rye, oat, wheat gained, comprise the starch that physically modified starch, radiation starch, the unit price that wherein combines with phosphate group or divalent ion have been removed, not only can part but also can all be removed, with replace arbitrarily by different divalent ions or with unit price or polyvalent ion, not only can part but also the starch that can all replace; Pre-extrusioning starch is through so heating so that the endothermic transition characteristic of stipulating before oxidation and thermal destruction is handled.Use for some, preferred starch be amylose content at about 70-95%, be preferably about 75～85% high amylose starch, percentage ratio is the weight percentage of starch.The lower bound of amylose content is preferably about 10-15%(weight in the starch).Starch ingredients in the composition of the present invention is included in no additional water but has fusion starch under the situation at other softening agent such as glycerine.But preferred plasticizer is a water.Preferably starch forms melt under the situation that water exists, and water may exist in the starting ingredient, makes composition of the present invention by this melt, and its water-content is about 0.5～40%(weight in total starting ingredient weight).

Water-content is counted about 10-20%(weight by the composition weight of following explanation in the composition of the present invention), be preferably 14-18%(weight), especially with 17%(weight) to be advisable, starch can mix with any desired sequence and polymkeric substance or multipolymer and other additive arbitrarily as described below.For example starch can with the additive of all predetermined use, comprise that polymkeric substance or multipolymer mix and form multipolymer, blend can be heated to form even melt then, this melt generally is thermoplastic.

But starch can mix with any additive, and starch, is further processed the sort of mixture as fusion and granulation before the polyvinyl alcohol then adding polymkeric substance or multipolymer.But starch preferably and additive and polymkeric substance or multipolymer such as polyvinyl alcohol be mixed together the formation free flowing powder, can be used for continuous processing, fusion and granulation or directly be extruded into curing composition of the present invention.

Composition can be arbitrarily by starch at least and a kind of being selected from through the homopolymer chain enol of preprocessing and multipolymer in conjunction with forming.Described preprocessing comprises provides particle or pellet, and it is enough being made under the even fusion formation condition of acquisition component.In addition or additional, homopolymer chain enol and copolymerization can be with as polyvalent alcohols, the pre-plasticising as glycerine.The starch that exists in the composition can be in 15-40%(weight) in the presence of the moisture and pre-fusion under above-mentioned given temperature and pressure.Composition can comprise at least a weighting agent, filler, lubricant, releasing agent, softening agent, stablizer, tinting material and the fire retardant of being selected from arbitrarily.

Weighting agent comprises water-soluble and/or water-swelling polymer, and this polymkeric substance comprises known thermoplastic polymer, as gelatin, plant glutin, acroleic acid esterification protein; Water miscible polysaccharide, as alkylcellulose, hydroxy alkyl cellulose and hydroxyalkyl alkylcellulose, as methylcellulose gum, Walocel MT 20.000PV, Natvosol, hydroxypropylcellulose, hydroxyethylmethyl-cellulose, Vltra tears, hydroxy butyl methyl cellulose, cellulose ester and hydroxy alkyl cellulose ester, as ethanoyl phthalic ester Mierocrystalline cellulose (CAP), Vltra tears (HPMCP); Carboxyl alkyl cellulose, carboxyalkyl alkylcellulose, carboxyl alkyl cellulose ester such as carboxymethyl cellulose and their an alkali metal salt; As starch like derivatives by all above-mentioned derivatived cellulose names; Water miscible synthetic polymer such as polyacrylic acid and salt thereof and water-soluble polyacrylate, polymethyl acrylic acid and salt thereof and water-soluble poly methacrylic ester basically basically, water-soluble poly vinyl acetate, poly-phthalic acid vinyl acetate (PVAP), Polyvinylpyrolidone (PVP), polybutene acid basically; Have cationic modified acrylate and methacrylic ester, for example a kind of uncle or season amino group, as diethylamino ethyl base, it can quaternized (if desired); With described mixture of polymers.

Term " water-soluble or water-swelling polymer " be meant when this polymkeric substance at room temperature soak in the liquid water time absorption or absorb for dry polymeric, be at least 30%(weight) water.

Suitable filler comprises as timber deutero-material and magnesium, aluminium, silicon and titanyl compound, exists in the composition packing density up to about 20%(weight), be preferably about 3.0-10%(weight) (in the gross weight of composition).

Lubricant comprises the stearate of aluminium, calcium, magnesium and tin, and free acid and Magnesium Silicate q-agent, silicone and lecithin class material, list and two glyceryl ester (these are to the object of the invention one similar approach effect).Suitable lubricant also comprises unsaturated fatty acids acid amides, C preferably ₁₈-C ₂₄The acid amides of unsaturated acid, for example acid amides and the C of cis-13-docosenoic acid (mustard acid amides) ₁₂-C ₂₄The acid amides of carboxylic acid, for example the acid amides (Shan Yu acid amides of docosoic acid).Particularly preferred lubricant is a stearic acid, it exist in amount in the composition for per 100 minutes starch for up to 10 minutes, be preferably the 1-3 branch, most preferably be 1 fen.

Composition of the present invention also can comprise nucleator (when particularly composition is foam forms).Having granular size is the 0.01-5 micron, and it is selected from silicon-dioxide, titanium dioxide, aluminum oxide, barium oxide, magnesium oxide, sodium-chlor, Potassium Bromide, trimagnesium phosphate, barium sulfate, Tai-Ace S 150, Boron Nitride and Magnesium Silicate q-agent, or its mixture.Preferred described nucleator is selected from silicon-dioxide, titanium dioxide, aluminum oxide, barium oxide, magnesium oxide, sodium-chlor and Magnesium Silicate q-agent or its mixture.

Particularly preferred nucleator is Magnesium Silicate q-agent (little talcum), and for up to 10 fens nucleators, preferably the 1-3 branch most preferably was 2 fens to the amount in composition for per 100 minutes starch.

Softening agent comprises urea and lower molecular weight polyalkylene oxide, for example polyoxyethylene glycol, polypropylene glycol polyethylene-propylene glycol), low-molecular-weight organic softening agent is as glycerine; Tetramethylolmethane; Glyceryl monoacetate, diacetate esters or triacetate; Propylene glycol; Sorbitol Powder; Diethyl sulfide is for Soduxin; Triethyl citrate and tributyl citrate and other play the material of similar effect.

The amount that described softening agent exists in the composition is preferably about 0.5～40%(weight), more preferably about 0.5～5%(weight) (weight with whole components is benchmark, comprises moisture wherein).

The total content of softening agent in the composition (comprise water, exist as softening agent) preferably is no more than about 25%(weight), be most preferably not exceeding about 20%(weight) (in composition total weight).

Stablizer comprises antioxidant such as thiobisphenol, alkylidene bisphenols, secondary arylamine; Anti-photolysis stablizer, as UV absorption agent and quencher, the hydrogen peroxide decomposition agent; Radical remover and biocide.

Tinting material comprises known azoic dyestuff, organic or inorganic pigment, or the tinting material of natural source, mineral dye be preferred, as iron or titanyl compound.The concentration of these oxide compounds in composition is about 0.01～10%(weight), be preferably about 0.05～3%(weight) (in the gross weight of composition).The amount of most preferred tinting material in composition is about 0.03-0.07%(weight to total composition).The amount of ferric oxide is a 0.05%(weight).

Composition also can comprise the fire retardant of fire retardant such as phosphorous, sulphur and halogen, or its mixture.

Suitable phosphonium flame retardant comprises diethyl N, two (2-hydroxyethyl) the aminomethylphosphonic acid esters of N-; The dimethyl methyl phosphonate acid esters; Phosphonic acids, methyl-, dimethyl esters, with the polymkeric substance of the oxide compound of oxyethane and phosphine, the phosphoric acid ester/phosphonate oligomers of fat; Tributyl phosphate; Triphenylphosphate; Tricresyl phosphate hydroxy toluene ester; 2-ethylhexyl diphenyl phosphate and tributoxyethyl phosphate; These fire retardants can be from Akzo Chemicals Inc.of 300 South Riverside Plaza Chicago, Illinois, and USA obtains.

Phosphonium flame retardant preferably comprises that two (hydroxypropyl) sec-butyl phosphine oxygens (can be from Chemi-cal products Group of FMC corporation, 2000 Market street, philadelphia pennsylvania 19103, USA) obtain and from Albright and Wilson Americas Inc. post-office box 26229, Richmond, Virginia, 23260, the following compounds that USA obtains: poly-propenoxylated dibutyl pyrophosphoric acid, phosphonic mixture, methyl-, (5-ethyl-2-methyl isophthalic acid, 3,2-dioxo phosphoric acid-5-yl) methylethyl ester, p-oxide compound and phosphonic acids, methyl-, two [(5-ethyl-2-methyl isophthalic acid, 3,2-titanium dioxide phosphoric acid-5-yl) methyl] ester, p, p '-dioxide sells with trade name Amgard V19; Ammonium polyphosphate; The quadrol polyphosphate; The melamine phosphoric acid ester; Two melamine phosphoric acid ester; Red phosphorus with microcyst.

When adopting ammonium polyphosphate and quadrol polyphosphate to make fire retardant, preferably these fire retardants and ortho-phosphoric acid disodium are made into damping fluid so that few to the equipment used corrosion when processing contains the composition of fire retardant.

Also having phosphonium flame retardant preferably is phosphoric acid Guanidinium salt (can be from Chemie Linz GmbH of St Peter Strasse 25, A-4021, Linz, Australia obtains).

Suitable halogen containing flame-retardant comprises chlorination stone vinegar (from Occidental Chemical Cor-poration, of 360 Rainbow Boulevard South, Box 728, Niagra Falls, New York 14302 obtains); PHT4 and five, eight, decabromodiphynly oxide is (from Great Lakes Chemical corporation, of P.O.Box 2200, West Lafayette, Indiana, 47906, USA obtains) and the bromine chlorinated paraffin, brominated epoxy resin, brominated Polystyrene, three (2-chloropropyl) phosphoric acid ester and four methylol phosphonium chlorides (can be the same from Albright and Wilson(address) obtain).

Halide-containing preferably comprises dibromoneopentyl glycol and tribromoneoamyl alcohol (can be from AmeriBrom Inc of 1250 Broadway New York, New York 10001 U.S. obtain).

Suitable sulfur-bearing fire retardant comprises ammonium sulfate; Ammonium sulfamate; With four (methylol) Liu Suan Phosphonium (all can be from American cyanomid company, of one cyanamid plaza, Wayne, New Jersey, 07470, United States Patent (USP)), sulfuric acid Guanidinium salt, (from chemie Linz(address such as above-mentioned obtaining) also can be used as fire retardant.

The amount of the above-mentioned fire retardant that exists in the starch-containing composition is a 0.1-10%(weight to the starch ingredients of composition), be preferably 1-6%(weight), most preferably be 2-4%(weight).

Other suitable fire retardant comprises trihydrate, aluminium acetylacetonate, the Burow Solution of aluminium; Hydroxyl yellow soda ash aluminium; Hydroxyl carbonic acid magnalium; Weisspiessglanz; Molybdenum oxide; Eight molybdic acid aluminium; Zinc molybdate; Magnesium hydroxide, zinc borate; Five aluminum borates; Boric acid and sodium tetraborate.These fire retardants are generally available, and particularly the Borax compound can (California 90010, USA) for 3075 Wilshire Boulevard, Los Angles from the acquisition of U.S. Borax and Chemical company.

The amount that the fire retardant of these rank rears can exist in the composition is 1-90%(weight to the starch ingredients in the composition), 20～80%(weight preferably), most preferably be weight into 40-75%().

Particularly preferred fire retardant is a phosphoric acid Guanidinium salt, ammonium phosphate and/or quadrol polyphosphate (having or do not exist the ortho-phosphoric acid disodium) and sulfuric acid Guanidinium salt or ammonium sulfate.

Can be added to that another material comprises animal or plant fat in the composition, preferably its hydrogenated form at room temperature is these fat of solid particularly, and the fusing point of this fat is preferably at least 50 ℃, and comprises C ₁₂, C ₁₄, C ₁₆And C ₁₈The triglyceride level of lipid acid.

Fat is added to only contains thermoplastic melt and in the material of filler-free or softening agent, or be added to single or two-glyceryl ester or phosphide melt together in, wherein Yelkin TTS is preferred.Described single and two glyceryl ester preferably obtain by described animal or plant adipose-derived.Described fat, the total concn of single, two-glyceryl ester and phosphide can be up to 5%(weight) (gross weight with composition is a benchmark).

Other compounds that can be added to or exist in the composition comprise boron-containing compound, become composition molding film, sheet material or fiber all the more so especially.Exist the goods of described its production of compound compositions to have the transparency improved, Young's modulus and tear strength.Preferred boron-containing compound is boric acid, metaboric acid, basic metal and alkaline earth salt, borax and derivative thereof, and the amount that may exist in compound described in the composition is 0.002～0.4%(weight to the composition speech), 0.01～0.3%(weight preferably).

The inorganic salt of basic metal or alkaline-earth metal, it is 0.1～5%(weight for total composition that special Licl and Nacl can add the amount that exists in the composition).Exist in salt described in the composition and still can further improve Young's modulus, the transparency and the tear strength of making goods by composition.

Recognize that concentration of component in the composition, particularly tinting material and borax compound can obtain (if desired) by the master batch method.

Above-mentioned composition is that heating generates thermoplastic melt under controlled temperature and pressure condition.When being used for moulding composition of the present invention or melt, these fused melts can be processed by any traditional forming method, the present invention also relates to described method.Therefore, described melt can be with the processing of general thermoplastic material method therefor, for example injection moulding, blowing, extrude, coextrusion, compression moulding, vacuum forming and thermoforming and produce moulded products.These goods comprise that (special candle is used for container, packing case carton, dish, cup, composition contains fire retardant) dish, sheet material and wrapping material (comprising filling kind in bulk), moulded products also comprises pellet and particle, and it can grind and makes powder and be used to make moulded products.Particularly preferred goods are foam forms, injection moulding form, or extrude form.

The working pressure and the temperature range of suitable injection moulding, film forming, foaming and extrusion molding disclose as follows.

The injection moulding of composition

According to method fusion starch of the present invention is that it is heated under sufficient temp, and its time requires enough to form even melt.

Composition is preferably in the airtight volume and heats, and for example in an encloses container, or heats in the limited bulk that sealing function produced by fusion feeding material not.This effect appears in the screw rod of forcing machine and the machine barrel or in the injection-moulding device.

Therefore, described screw rod and machine barrel should be managed to be situated between becomes an airtight volume.The pressure that is produced in this volume is equivalent to the vapour pressure of softening agent under the temperature that is adopted (being generally water), and being to be appreciated that in using described screw rod or machine barrel pressure application or producing may be known thing.

The pressure of better using and/or producing in injection moulding or the pressure range of appearance extruding in be exactly known originally, can be up to about 150 * 10 ⁵N/m ², preferably up to about 75 * 10 ⁵N/m ², most preferably be up to about 50 * 10 ⁵N/m ²

Be preferably 100 ℃ to 220 ℃ in the used temperature of injection moulding composition, more preferably 160 to 200 ℃, most preferably be 160 to 180 ℃, precise temp depends on the type and the character of the starch that adopts.Preferably use potato or W-Gum in order to be easy to processing.

Resulting like this fusion starch composites is carried out granulation, and prepare to mix with the mixture that obtains granular fusion starch material with other component and wait to be fed in the spiro rod machine tube by selected mixing and work program.

The film forming of composition

Composition as above carries out plasticising, and different is to be in the process of injection moulding and extrusion compositions, about 10-20 ℃ of the general Heating temperature height more used than the sort of routine.

The foaming of composition

The foaming present composition becomes the foamy method to comprise:

A) provide a kind of starting composition, said composition comprises starch, softening agent and at least a homopolymer chain enol and/or the chain-ol copolymer of being selected from, and the concentration that exists in polymkeric substance in the composition is the 10-120 branch to per 100 minutes described starch;

B) during processing or plasticising, the plasticizer loading in the composition is adjusted to about 15-40%(weight of total composition weight).

C) the adjusted composition of heating under temperature between 100-220 ℃, should enough form uniform composition melt heat-up time at least.

D) removing excessive moisture before arriving extrusion die is about 10-20% to obtain moisture content; With

E) under the condition of cross section greater than the outlet opening of forcing machine die head of extrudate hypothesis, extrude the composition that heated.

Preferred plasticizer is a water, before extruding, the moisture content of composition is adjusted to the 14-20%(weight of total composition weight), 16-18%(weight more preferably), most preferably be 17%(weight), composition most preferably is under about 180 ℃ of-200 ℃ of temperature and heats in about 160 ℃ of-200 ℃ of temperature, its pressure is equivalent to the water vapor pressure under described temperature at least, and the time was at least 30 seconds.

Composition can molding, adopts known thermoforming process to extrude subsequently.

The present invention can be further clear and definite after illustrating by the following example.

Embodiment 1

With 10 kilograms of potato starches, 2.8 kilogram about 106000-110000 of number-average molecular weight and degree of hydrolysis are the polyvinyl alcohol (Airvoll 540s) of 87-89%, 200 gram Magnesium Silicate q-agents and 100 gram stearic acid mix, then the moisture content of mixture is adjusted to about 28%(weight of wetting starch mixture), the moisture content of blending ingredients can be transferred to about 25-30%(weight), those results similar (identical) of its result and following gained.

The starch of regulating like this is fed into the screw rod corotation is housed changes the inlet part of the twin screw extruder of horizontal garden post machine barrel (Leistritz.Model LSM 34), its outlet die head is installed in the discharge end of forcing machine, the opposite of inlet part.

Then starch composites is heated to 155 ℃, about 70 seconds of time also carried out under control pressure, and control pressure is meant the pressure in the time of must avoiding producing water vapor under described temperature.Therefore, fused starch is extruded from the outlet die head of forcing machine, cooling extruded thing and granulation.

It is about 17% that granulation fusion starch mixture moisture content is defined as, and is fed into the inlet part of single screw extrusion machine then.Spiro rod length and diameter are that the forcing machine of 10-30 also is applicable to processing of the present invention than extrusion ratio in 25 scopes.

The mixture of Xing Chenging ℃ is extruded then in 20-60 time second internal heating to 190 like this, according to extrudate analysis from forcing machine die head aperture, extrudate presents cross section and forms the foam material that is suitable as wrapping material greater than the cross section in described aperture, produce perforate and closed-cell foam, with regard to density, rebound resilience and compressibility, have excellent characteristic really.

Allow extrudate cooling, its bulk density can according to by Hwang and Hayakawa etc. at J.Food sci., the method described in vol 45 p1400-1407 is measured, document specification sheets is cited for referencial use.The rebound resilience of extrudate and compressibility Texture analyser, in the prior art known to the those of skill in the art, according to EP-A89111295.5(publication number 0375831) in disclosed program measure, disclosure is quoted as proof for referencial use equally in this by the present invention.

The foamy bulk density, rebound resilience and compressibility are listed in table 1.

Embodiment 2-5

Repeat example 1, but with the different polyvinyl alcohol of measuring.The amount that the composition of example 2-5 contains polyvinyl alcohol is respectively 20,25 with respect to the dry measure of starch ingredients, 30 and 35%(weight).The bulk density of the composition of Xing Chenging, rebound resilience and compressibility are listed in the table 1 like this.

Embodiment 6-9

Repeat example 1, different is that potato starch substitutes with W-Gum, the concentration of polyvinyl alcohol is with respect to 10% of dry starch weight, 20%, 25% or 30%(weight), foamy rebound resilience, compressibility and the bulk density of Sheng Chaning is similar to potato starch like this, is listed in the table 1, and the foamy characteristic that contains 20% polyvinyl alcohol is good especially.

Table 1

Routine number	Polyvinyl alcohol (dividing/100 fens starch)	Bulk density (kilogram/rice 2）	Rebound resilience (%)	Compressibility (gram/rice 3）
					2 3 1 4 5	20 25 28 30 35	19 15.4 8.5 13.7 24.6	35 45 61 54 73	21 16 14 9 5

Embodiment 10

10 kilograms of starch, 4.5 the kilogram number-average molecular weight is that about 106000-110000 and degree of hydrolysis are the polyvinyl alcohol (Airvoll 540s) of 87-89%, 200 gram Magnesium Silicate q-agents and 100 gram stearic acid mix, then the moisture content of blended component is transferred to the 22%(weight of wetting starch mixture), starch through adjusting like this is fed into the inlet part that is provided with at the twin screw extruder of horizontal garden post machine barrel inner screw rotation, the outlet die head is installed in the discharge end of forcing machine, the opposite of inlet part.Starch composites is needing under the described temperature to avoid to form at need under the minimum pressure of water vapor and had been heated to 155 ℃ of temperature-times about 1 minute then.Therefore, fusion starch is extruded from the outlet die head of forcing machine, cooling extruded thing and granulation.

It is about 17% that granulation starch mixture moisture content is defined as, and the inlet part of single screw extrusion machine is gone in charging then.Spiro rod length and diameter ratio are 25.Then starch mixture was heated to 180-200 ℃ at 0.3 to 1 minute, extrudes with sheet-form again, make moulded products by the known technology thermoforming subsequently, as dish, cup and dish etc.

Embodiment 11

The present embodiment narration is by the tension specimen that blend adopts injection moulding to make of extruding of polyvinyl alcohol (through the form of pre-treatment or granulation melt) and starch.

50 fens high molecular, the be situated between polyvinyl alcohol (Airvol 540) of (87-89 mole %) of portion water, its polymerization degree is about 2200, and ash oontent is about 0.19% to import in the high-tenacity Littleford 180L mixing machine, and mixing machine starts with 900RPM.

When the temperature of polyvinyl alcohol reaches 65 ℃, in mixing machine, add 12.5 fens glycerine with steady rate slowly.After glycerine adds, again 0.17 minute 85% phosphoric acid and 0.25 fen glyceryl monooleate are added in the mixture as processing aid.

Water coolant is added in the mixing machine chuck, and control keeps the temperature of product to be lower than 100 ℃ all the time in whole process.After monoleate adds, proceed to mix till making the polyvinyl alcohol mixture that easily flows with low speed again.Then mixture is put into Littleford 400L cooling mixing machine and made product temperature drop to 40 ℃.So the mixture that produces be runny, do not have caking or do not have degradation material.

The polyvinyl alcohol material of Xing Chenging is packed in the constant volume feeder and is fed into 46mm back and forth (for the known type of skilled present technique personnel) in the forcing machine of rotation like this.The design requirements of screw rod can reach that high degree of mechanical can be imported and the product-free degraded.Forcing machine is a vented extruder, and the vacuum tightness (10 o'clock Hg) that the venting port of position at diameter 7 places partly adopts 254 Bristols is to remove in the polymkeric substance any residual moisture and to be transformed into formed acetic acid in the Sodium phosphate dibasic by sodium-acetate.The melt temperature of the polymkeric substance in the workspace of forcing machine remains on the upper end by the polymer melt curve of dsc (DSC) expression.At 183 ℃, measure melt temperature down for 197 ℃ and 199 ℃.Typical operational condition is:

Screw speed 300RPM

140 ℃ of extruder temperatures

Barrel zone temperature

150 ℃ in first district

150 ℃ in second district

21.7 kilograms/hour of throughput rates

201 ℃ of maximum melt temperatures

Screw rod power 6.5kw

0.30 kilowatt/hour of specific energy input

Product leaves forcing machine and is cooled to be lower than its second-order transition temperature at once to prevent the crystallization of product degraded and polymkeric substance, because it can cause the formation of gel in thermoforming operating process subsequently.The line material adopts general method to be cut into particle and it is collected.

The essentially no crystallization of particle of producing, and gel-free, the smooth straw yellow that is.

A) restrain the potato starch that contains 15.1% water to 9500 and put into super mixer, under agitation add the polyvinyl alcohol particle that 2875 grams as above produce (with respect to the weight of starch ingredients 30%), 80.75 gram hydrogenated fat (lubricant releasing agent, sell with Boeson VP by Boehringer Ingelheim) and 40.37 gram melt-flow promotor (Lecithin is sold with Metarinp by Lucas Meyer).The water-content of final mixture is 14.43%.

B) 10.000 grams are changeed in the twin screw extruder (Type C ontinua 37) by the hopper Wer-ner l pfleiderer corotation of packing into by the mixture of (a) preparation.

The temperature profile that machine barrel is four sections is respectively 20 ℃/180 ℃/180 ℃/80 ℃.Blend extrude with mixture output be 8 kilograms/time (screw speed is 200rpm) carry out.In the ingress with flow velocity be 2 kilograms/time add entry so that during extruding the water-content of material reach 31.5%.At the forcing machine final stage, adopt 80 millibars of decompressions, make portion water become water vapor and remove.

The particulate water-content is 17.5%, and it is measured after at room temperature reaching balance.

C) particle (water-content is 17.5%) of the mixture of the pre-blend that obtains as (b) is gone in the injection moulding machine (Arburg 329-210-750) by a hopper feed, produces tension specimen.The temperature profile of machine barrel is 90 ℃/165 ℃/165 ℃.

Injection volume is 8 grams, and 450 seconds residence time, injection pressure is 2082 crust, back-pressure 80 crust, screw speed 180rpm.

To place relative humidity be that 50% weather cabinet 5 days is as the arbitrary standards condition to the tension specimen of Sheng Chaning (it is a standard design, Din No.53455) like this.

(d) on the Ewick tension test instrument tension specimen after the conditioning is being carried out the stress/strain testing of characteristic then.

Use extending speed is 10 millimeters/minute measure sample at room temperature, the sample that obtains like this with compare by the sample of not making through pretreated polyvinyl alcohol, demonstrate and improved dimensional stability and improved physicals.

Embodiment 12

(a) restrain the potato starch that contains 15% moisture to 8000 and place high-speed mixer, under agitation add 3200 the gram pretreated polyvinyl alcohol particle (with respect to starch ingredients weight 40%), 68 gram hydrogenated fats (follow the lubrication prescription releasing agent, sell with Boeson VP) and the molten stream of 34 grams promotor (Lecithin is sold with Metarin P by Lucos Meyer) by Boehringer Ingelheim.The water-content of final mixture is 15.6%.

(b) 10.000 gram mixtures by (a) preparation are fed into Werner ﹠amp; In the grain bucket of the twin screw extruder that the pflelderer corotation changes (model C onlinua 37).

The temperature profile that machine barrel is four sections is respectively 20 ℃/50 ℃/100 ℃/50 ℃.Extruding operation and be in mixture output is (spiro rod rate is 200rpm) time to carry out in 8 kilograms/time.Ingress adopt flow velocity be 1 kilogram/time add entry so that during extruding the water-content of material reach 25%.Back segment at forcing machine adopts 22 millibars of decompressions to make a part of water become water vapor and removes.

So the particulate water-content of producing is 14.8%, it be at room temperature reached measure after the balance and.The particulate water-content under stirring state, is transferred to 17% by spray water in general mixing machine.

(c) the premixed compound particles that obtains as (b) enters injection moulding machine (Arburg 329-210-750) by a hopper, in order to produce tension specimen.The temperature profile of machine barrel is 90 ℃/185 ℃/185 ℃/185 ℃.

Shot weight is 7.9 grams, and the residence time is 450 seconds, and injection pressure is 2200 crust, and back-pressure is 80 crust, and spiro rod rate is 180rpm.

It is that to make sample equilibrate to water-content as the arbitrary standards condition in 5 days be about 14% for 50% weather cabinet that the tension specimen of producing is like this placed relative humidity.

(d) on the Ewick tension test instrument tension specimen after the conditioning is being carried out stress/strain test (as described in Example 7) then.The sample that obtains is like this compared with the sample of not making through pretreated polyvinyl alcohol, demonstrates to have improved dimensional stability and improved rational energy.

Embodiment 13

Present embodiment narration is extruded blend injection moulding candle cup by polyvinyl alcohol and starch.

Starch (the Hylon VII of preparation W-Gum or high amylose starch, obtain from Nationol starch and chemical corporotion, the address is Finderne Avenuep.o.Box 6500 Bridgewater, New Jersey 08807, the U.S.), Boeson vp(sells by Boehringer Ingelheim) and the mixture of Yelkin TTS (by Lucas Meyer with Metarin p sale), wherein the ratio of three components was respectively 100: 2: 1.

13.6 kilograms this mixtures are fed into the inlet part that the twin screw extruder (Leistritz Model LSM 34) that the screw rod corotation changes is housed in the post machine barrel of horizontal garden, the outlet die head is installed in the discharge end of forcing machine, the opposite of inlet part.

Adding 440 gram glycerine, 5.2 kilograms of number-average molecular weights in this mixture is that the plastifying polyvinyl alcohol of 88-99% and enough water are can be mixed into the mixture of suitable batching for about 15000-45000 and degree of hydrolysis.Institute's amount of water depends on the character of starch to a great extent, can be determined by those of skill in the art.

Then starch composites is heated to about 175 ℃ temperature, the time is about 30-120 second and carries out under control pressure, and control pressure is meant the pressure in the time of must avoiding producing water vapor under described temperature.Soluble in water ammonium sulfate, it was added to the starch composites of heating and pressurization before the outlet die head of forcing machine is extruded at composition.

The weight that adds ammonium sulfate makes in the refrigerative extrudate ultimate density with respect to the 3.5%(weight of starch ingredients amount).From the fused starch that the outlet die head of forcing machine is extruded, cooling extruded thing and granulation.The pellet (water-content is preferably about 11%) that adds the premixed mixture of gained goes into to be equipped with in the injection moulding machine (Arburg 320) that is suitable for producing the candle cup die head by hopper feed.

Under the situation of W-Gum, melt temperature is 165 ℃, and injection volume is 9 grams, and the residence time is 240 seconds, and injection pressure is 1100 crust, and spiro rod rate is 190rpm, and the mould temperature is 17 ℃.

So the candle cup of producing has good physical, basic size stability, and is made by the composition that meets following condition, and it is enough to the requirement that stops burning and satisfy DIN 75200 flames retardance standard.

Embodiment 14-16

Repeat example 13, different is to change the composition of making candle cup.Suitable compositions is listed in the table below in 2.Injection pressure, the residence time etc., not being both at polyvinyl alcohol did not have to improve a little under the pre-plastifying situation injection pressure (to about 1200 crust) basically as example 13.

Embodiment 17

Repeat example 13, not being both used fire retardant is many Guanidinium of quadrol acid esters, and the amount that exists in composition is a 4%(weight with respect to its starch ingredients).In routine 13-17, fire retardant is that the final step in the composition batching adds before injection moulding.The residence time of composition in forcing machine remains to minimum degree (comprising fire retardant now).

In addition, that part of of forcing machine contact flame-proof starch composition should be improved especially to be fit to reduce the infection of inhibitor to forcing machine.

The candle cup of producing by routine 13-17 has good physicals, basic size stability, and they are by the enough fire retardancy of having of composition manufacturing, satisfy DIN 75200 flame-retardant standards.

Table 2

Routine number	Starch type	PVOH	Glycerine	Fire retardant	Processing aid
						14 15 16	100 fens Hylon VII of 100 fens corns of 100 fens corns	60 minutes, (with about 20%, the glycerine of (weight) carries out internally plasticized) 48 fens 30 fens Airvol of Mowiol 10-98	5 minutes 12 minutes	5 fens ammonium sulfate of 3.5 fens ammonium sulfate of 2 fens ammonium polyphosphates	1 fen Yelkin TTS of 2 fens Boeson 2 fens Boeson of 1 fen Yelkin TTS of 3 fens stearic acid

Embodiment 18

Preparation contains the composition of polyvinyl alcohol, glycerine, W-Gum, Boeson, Yelkin TTS and water, and its each component ratio in composition is 96: 24: 100: 1: 0.5: 12.The number-average molecular weight of polyvinyl alcohol is about 106000-110000, and water Jie degree is about 88%(Airvoll 540s).

Composition is fed into the inlet part that the twin screw extruder (Leistritz Model LSM 34) that the screw rod corotation changes is housed in the post machine barrel of horizontal garden, the outlet die head is installed in the discharge end of forcing machine, the opposite of inlet part.

Under the control pressure in the time of under described temperature, can avoiding starch composites to produce water vapor then, use the mechanical energy (person skilled in the art is known in the prior art) that provides by powerful screw mechanism to be heated to 171-185 ℃, be about 60-120 second heat-up time.

Plastification composite is till forming even melt in forcing machine, and after this, the water-content of composition dropped to about 10% before extruder barrel outlet composition.Use general follow-up equipment, melt forming is become the film of all thickness between the 0.2-0.5mm.Resulting film (itself is applicable to packaging application) can be used for preparing the sandwich-like product that comprises described film and metal (being preferably aluminium) paper tinsel.0.4mm thickness thin film be preferred especially.

Embodiment 19

According to the foregoing description, by containing W-Gum, 1%(weight) stearic acid, the 2%(weight of (with respect to starch weight)) Chematoic 5M and optional 0.05%(weight) the composition of ferric oxide (back both also for starch) make particle.Composition also contains 20%(weight) following polyvinyl alcohol (for starch):

A) water Jie degree is the Airvol 540 of 87-89%

B) water Jie degree is 98.4% Mowiol 56-98;

C) water Jie degree is the Mowiol 66-100 of 99-7%;

D) water Jie degree is 99.3% Airvol 165

The pellet that contains various polyvinyl alcohol stirred 72 hours in 30 ℃ of soft water separately, and filtered sample is measured because the loss of molten its weight of Jie of pellet then.

Following table 3 shows anti-basically molten Jie of the starch composites of the polyvinyl alcohol that contains the Gao Shuijie degree, and these samples that contain the polyvinyl alcohol of relative reduction water Jie degree are easy to molten Jie.The composition of water-proof relatively example 19 is that the utmost point is applicable to that preparation continues to discharge the fertilizer system.

Table 3

Sample	The weight loss of sample (%)	Observe
			a b c d	27.1 0.9 1.3 2.2	Very easily molten Jie's no change no change no change

Consider enforcement of the present invention, should only not be subjected to the limitation of the above example explanation of enumerating, the personnel skilled to present technique all can improve or change as the case may be, only otherwise the regulation that deviates from accessory claim of the present invention all is feasible.

Claims (91)

1, a kind of biodegradable composition that makes by melt, this melt comprises starch, softening agent and at least a homopolymer chain enol and/or the chain-ol copolymer of being selected from, these components are to combine under the condition that can fill the even melt of part assurance formation, and the concentration that it is characterized in that existing at least a polymkeric substance in the composition is the 10-120 branch to per 100 minutes dry starch.

2, according to the composition of claim 1, wherein the content of the interior amylose starch of starch is up to about 95%.

3, according to the composition of aforementioned claim, wherein the content of the interior amylose starch of starch is between about 70 and about 95%.

4, according to the composition of claim 1, wherein the content of the amylose starch of starch is up to about 65%.

5, according to the composition of aforementioned claim, wherein the content of the interior amylose starch of starch is up to about 45%.

6, according to the composition of claim 4, wherein the content of the interior amylose starch of starch is up to about 35%.

7, according to the composition of claim 4, wherein the content of the interior amylose starch of starch is at least about 15-25%.

8, according to the composition of claim 1, wherein composition comprises and divides described polymkeric substance for per 100 minutes starch for about 10-100.

9, according to the composition of claim 1, wherein composition comprises and divides described polymkeric substance for per 100 minutes starch for about 10-85.

10, according to the composition of claim 1, wherein composition comprises the described polymkeric substance that per 100 minutes starch is divided for about 20-40.

11, according to the composition of claim 1, wherein homopolymer chain enol is a polyvinyl alcohol.

12, according to the composition of claim 11, wherein polyvinyl alcohol is to be essentially complete water to be situated between.

13, according to the composition of claim 11, wherein polyvinyl alcohol water Jie degree is about 75-100%.

14, according to the composition of claim 11, wherein polyvinyl alcohol water Jie degree is about 85-99%.

15, according to the composition of claim 11, wherein polyvinyl alcohol water Jie degree is about 87-99.9%.

16, according to the composition of claim 11, wherein the number-average molecular weight of polyvinyl alcohol is 15000-250000.

17, according to the composition of claim 16, wherein the number-average molecular weight of polyvinyl alcohol is 15000-150000.

18, according to the composition of claim 16, wherein the number-average molecular weight of polyvinyl alcohol is 160000-250000.

19, according to the composition of claim 1, wherein water Jie degree of polyvinyl alcohol be at least about 97% and its number-average molecular weight be about 15000-150000.

20, according to the composition of claim 19, wherein water Jie degree of polyvinyl alcohol be at least about 97% and its number-average molecular weight be about 50000-150000.

21, according to the composition of claim 19, wherein water Jie degree of polyvinyl alcohol be at least about 97% and its number-average molecular weight be about 70000-150000.

22, according to the composition of claim 19, wherein water Jie degree of polyvinyl alcohol be at least about 97% and its number-average molecular weight be about 100000-150000.

23, according to the composition of claim 1, wherein homopolymer chain enol or multipolymer are the pretreated polyvinyl alcohol of a kind of process, it is to make its fusion and eliminate crystallization in the melt basically by enough energy being added to polyvinyl alcohol, and removes energy with the speed of enough avoiding its decomposition from the polyvinyl alcohol melt simultaneously and the polyvinyl alcohol melt that forms and making.

24, according to the composition of claim 1, also contain by vinyl acetate and ethene and/or propylene carry out copolymerization subsequently water Jie vinyl acetate group obtain contain vinyl alcohol units and the unitary chain-ol copolymer of aliphatic chain.

25, according to the composition of aforementioned claim, wherein multipolymer comprises ethylene/vinyl alcohol.

26, according to the composition of claim 24, therein ethylene alcohol unit and the unitary mol ratio of alkene are about 40: about 90: 10 of 60-.

27, according to the composition of aforementioned claim, wherein said mol ratio is 45: 55 to about 70: 30.

28, according to the composition of claim 27, the ethylene content of therein ethylene/vinyl alcohol is 44%.

29, according to the composition of claim 23, wherein have a maximum melt temperature through pretreated polyvinyl alcohol, can be by determine with dsc method, this temperature is hanged down about 5 ℃ at least than the melt temperature of corresponding untreated polyvinyl alcohol.

30, according to the composition of claim 29, wherein maximum melt temperature is than low about 10 ℃ at least of undressed polyvinyl alcohol.

31, according to the composition of claim 1, wherein composition also comprises at least a weighting agent, filler, lubricant, releasing agent, softening agent, stablizer, tinting material, fire retardant, basic metal or alkaline earth salt and the boron-containing compound of being selected from.

32, according to the composition of claim 31, the concentration that wherein said filler exists in the described composition is about 0.02～20%(weight) (weight with composition is benchmark).

33, according to the composition of claim 32, the concentration that wherein said filler exists in the described composition is counted about 3-10%(weight with the weight of composition).

34, according to the composition of claim 31, the concentration that wherein said softening agent exists in the described composition is counted about 0.5～15%(weight with the weight of composition).

35, according to the composition of claim 34, the concentration that wherein said softening agent exists in the described composition is counted about 0.5～5%(weight with the weight of composition).

36, according to the composition of claim 35, the softening agent of wherein said composition and the summation of water-content are no more than about 25%(weight in the weight of composition).

37, according to the composition of aforesaid claim, the softening agent of wherein said composition and the summation of water-content are no more than about 20%(weight in the weight of composition).

38, according to the composition of claim 31, the concentration that wherein said tinting material exists in the described composition is counted about 0.01-10%(weight with the weight of composition).

39, according to the composition of claim 31, wherein said lubricant is selected from list or two glyceryl ester, Yelkin TTS and stearic acid.

40, according to the composition of claim 39, wherein lubricant is a stearic acid.

41, according to the composition of aforementioned claim, wherein lubricant exists in concentration in the composition up to 10 minutes of per 100 minutes starch.

42, according to the composition of aforementioned claim, wherein to have concentration be the 1-3 branch of per 100 minutes starch to lubricant.

43, according to the composition of claim 39, wherein to exist in the concentration in the composition be 1 minute of per 100 minutes starch to lubricant.

44, according to the composition of claim 1, wherein composition comprises nucleator, its size of particles is about 0.01-5 micron, it is selected from silicon-dioxide, titanium oxide, aluminum oxide, barium oxide, magnesium oxide, sodium-chlor, Potassium Bromide, trimagnesium phosphate, barium sulfate, Tai-Ace S 150, Boron Nitride and Magnesium Silicate q-agent, or its mixture.

45, according to the composition of aforementioned claim, wherein nucleator is Magnesium Silicate q-agent (little talcum).

46, according to the composition of claim 44, wherein composition comprises 10 fens reagent up to per 100 minutes starch.

47, according to the composition of claim 46, wherein the composition 1-3 that comprises per 100 minutes starch divides described reagent.

48, according to the composition of claim 47, wherein composition comprises 2 fens described reagent of per 100 minutes starch.

49, according to the composition of claim 39, wherein fire retardant is selected from phosphoric acid Guanidinium salt: diethyl-N, two (2-hydroxyethyl) the aminomethylphosphonic acid esters of N-; The dimethyl methyl phosphonate acid esters; Phosphonic acids, methyl-, dimethyl esters is with the polymkeric substance of the oxide compound of oxyethane and phosphine; Phosphoric acid ester/the phosphonate oligomers of fat; Tributyl phosphate; Triphenylphosphate; Tricresyl phosphate hydroxy toluene ester; 2-ethylhexyl diphenyl phosphate and tributoxyethyl phosphate; Two (hydroxypropyl) sec-butyl phosphine oxide; Many propenoxylated dibutyl pyrophosphoric acid; Phosphonic acids, methyl-, (5-ethyl-2-methyl isophthalic acid, 3,2-dioxo phosphine-5-yl) methylethyl ester, p-oxide compound and phosphonic acids, methyl-, two [(5-ethyl-2-methyl isophthalic acid, 3,2-dioxo phosphine-5 base) methyl] ester, p, the mixture of p '-dioxide (selling) with trade name Amgard V19; Ammonium polyphosphate; The quadrol polyphosphate; The melamine phosphoric acid ester; Two melamine phosphoric acid ester; Red phosphorus with microcapsule.

50, according to the composition of claim 49, wherein fire retardant is ammonium polyphosphate or quadrol polyphosphate or its mixture.

51, according to the composition of claim 50, wherein ammonium polyphosphate or quadrol polyphosphate and disodium pyrophosphate are made into damping fluid.

52, according to the composition of claim 39, wherein fire retardant is selected from sulfuric acid Guanidinium salt, ammonium sulfate, Ammonium sulfamate and four (methylol) Liu Suan Phosphonium.

53, according to the composition of claim 39, wherein fire retardant exists in amount in the composition with respect to about 0.1-10%(weight of the weight of the starch ingredients of composition).

54, according to the composition of claim 52, wherein fire retardant exists in amount in the composition with respect to about 1-6%(weight of the weight of the starch ingredients of composition).

55, according to the composition of claim 54, wherein fire retardant exists in amount in the composition with respect to about 2-4%(weight of the weight of the starch ingredients of composition).

56, according to the composition of claim 31, wherein boron-containing compound is selected from boric acid, metaboric acid, basic metal and alkaline earth salt, borax and derivative thereof.

57, according to the composition of claim 56, wherein said compound exists in 0.002～0.4%(weight that amount in the composition is equivalent to composition weight).

58, according to the composition of claim 57, wherein said compound exists in amount in the composition with respect to the 0.01-0.3%(weight of composition weight).

59, according to the composition of claim 31, wherein the amount of the inorganic salt of basic metal or alkaline-earth metal existence is with respect to the 0.1-5%(weight of the weight of composition), and be selected from LiCl and NaCl.

60, according to the composition of claim 1, at least a native starch that is selected from plant-sourced of starch wherein, this starch is by potato, rice, rye, tapioca (flour), corn, pea, oat, wheat gained, comprise physically modified starch, radiation starch, the starch that has been removed of unit price that combines with phosphate group and divalent ion wherein, can partly or entirely remove, and replace arbitrarily by different divalent ions or with unit price or polyvalent ion, not only can part but also the starch that can all replace; Pre-extrusioning starch and warp so heat so that stood the starch of special endothermic transition before oxidation and thermal destruction.

61, according to the composition of any one aforementioned claim, it is to be selected from a kind of of melt, foam, film, particle, pellet and powder type.

62, according to the composition of claim 61, it is form of foam.

63, according to the composition of claim 62, wherein the bulk density of composition is about 8.5～30 kilograms/meter ³In the scope.

64, according to the composition of claim 62, wherein the rebound resilience of composition is in about 46～63% scopes.

65, according to the composition of claim 62, wherein the compressibility of composition is in about 6-15% scope.

66, according to the composition of claim 61, it is melt form.

67, according to the composition of claim 61, when being used to make moulded products, goods comprise bottle, film, pipe, rod, laminar film, capsule, bag, particle, powder, pellet, foam, container, packing case carton, dish, cup, dish, sheet material, wrapping material and foam package material-(comprising in bulk).

68, according to the composition of claim 1, by be selected from foaming, film forming, pressing mold, injection moulding, blowing, vacuum forming, thermoforming, extrude, coextrusion and the method that is used in combination thereof come moulding.

69, according to the composition of claim 1, come moulding by foaming method.

70, according to the composition of claim 1, come moulding by film.

71, according to the composition of claim 1, by injection moulding.

72, according to the composition of claim 1, by extruding or co-extrusion modling.

73, according to the composition of claim 1, come moulding by being selected from compression moulding, blowing, vacuum forming, thermoforming and bonded method thereof.

74, the method for compositions of production claim 1, it is characterized in that a) providing and contain starch, softening agent and at least a starting composition that is selected from homopolymer chain enol and/or chain-ol copolymer, the concentration that its polymkeric substance exists in the composition is 10～120 minutes to per 100 minutes described starch;

B) during processing or plasticising, the plasticizer loading of composition is transferred to about 0.5-40%(weight into total composition);

C) in an airtight volume, at temperature 100-220 ℃, pressure is equivalent under the water vapor pressure adjusted composition be heated when described temperature at least, at least enough forms the melt of composition heat-up time;

D) removing any excessive moisture before entering the forcing machine die head is about 5-20% to obtain moisture content; With

E) extrude the composition of heating.

75, the method for aforementioned claim, wherein softening agent is a water.

76, the method for aforementioned claim, wherein the content of softening agent is transferred to about 15～40%(weight of total composition amount in step b)), the composition water-content that obtains in step d) is about 10-20%, extrudes the composition of heating under the condition of extruding the aperture of extrudate mode cross section greater than the forcing machine die head.

77,2 method according to Claim 8, the wherein said at least a polyvinyl alcohol that comprises.

78, according to the method for aforementioned claim, wherein homopolymer chain enol and/or multipolymer are a kind of pretreated polyvinyl alcohol, it is to make its fusion and eliminate crystallization in the melt basically by enough energy being added to polyvinyl alcohol, and removes energy with the speed of enough avoiding making its decomposition from the polyvinyl alcohol melt simultaneously and the melt that forms makes.

79, according to the method for aforementioned claim, wherein composition also includes sodium-acetate and phosphoric acid, and its mol ratio is about 1 to 2.

80, according to the method for claim 78, wherein pretreated polyvinyl alcohol has a maximum melt temperature (by determine with dsc method), and this temperature is than low about 5 ℃ at least of corresponding untreated polyvinyl alcohol.

81, according to the method for claim 78, the predetermined energy of the 0.27Kwh/ kilogram of wherein having an appointment at least during pre-processing adds to polyvinyl alcohol and makes its fusion and eliminate degree of crystallinity in the melt basically.

82, according to the method for aforementioned claim, wherein predetermined energy is about 0.3～0.6Kwh/ kilogram.

83, according to the method for claim 75, wherein before extruding, the water-content of composition is adjusted to the 10-20%(weight of total composition), and composition heated under the 100-200 ℃ of temperature and under the pressure of the water vapor pressure when being equivalent to described temperature at least, be 0.5-2 minute its heat-up time.

84, according to the method for claim 75, wherein before extruding, the water-content of composition is adjusted to the 15-18%(weight of total composition), and composition heated under the pressure of the water vapor pressure corresponding in described temperature time the under the 150-200 ℃ of temperature and at least, be 0.5-1 minute its heat-up time.

85, according to the method for claim 76, wherein before extruding, the water-content of composition is adjusted to the 17%(weight of total composition), and composition heated under 180～200 ℃ of temperature and under the pressure of the water vapor pressure when being equivalent to described temperature at least, be 0.5-1 minute its heat-up time.

86,2 method according to Claim 8 wherein is heated to the fusion of starch substance and the temperature more than the second-order transition temperature to composition.

87, according to the method for claim 75, wherein starting composition is welcome by starch at least with a kind ofly be selected from homopolymer chain enol and multipolymer mixes and forms, and this polymkeric substance is mixed in advance combination under the condition that enough forms melt.

88, according to the method for aforementioned claim, wherein starting composition fusion and have the moisture of promising composition weight 15～40%.

89, according to the method for aforementioned claim, wherein starting composition fusion under 100～200 ℃ of temperature.

90, the forming method of the composition of claim 1, it is selected from foaming, film forming, compression moulding, injection moulding, blowing, vacuum forming, thermoforming, extrudes, coextrusion and in conjunction with etc.

91, the forming method of the composition of claim 66, it is selected from foaming, film forming, compression moulding, injection moulding, blowing, vacuum forming, thermoforming, extrude, coextrusion and in conjunction with etc.