CN1039648C - Biodegradable polymeric compositions based on starch and thermoplastic polymers - Google Patents
Biodegradable polymeric compositions based on starch and thermoplastic polymers Download PDFInfo
- Publication number
- CN1039648C CN1039648C CN93104044A CN93104044A CN1039648C CN 1039648 C CN1039648 C CN 1039648C CN 93104044 A CN93104044 A CN 93104044A CN 93104044 A CN93104044 A CN 93104044A CN 1039648 C CN1039648 C CN 1039648C
- Authority
- CN
- China
- Prior art keywords
- component
- composition
- weight
- acid
- synthetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The biodegradable polymeric compositions comprise a starch based component and a polymeric component comprising polymers of hydroxyacids or mixtures thereof with polymers deriving from ethylenically unsaturated monomers, particularly polymers of ethylene-vinylalcohol or polyvinylalcohol.
Description
The present invention relates to starch-containing and polymer composition thermoplastic synthetic resin, said composition is adapted to pass through the biodegradable substantially goods that the technology production of common process thermoplastic material has satisfied physicals and mechanical property.
The thermoplastic compounds of the above-mentioned type is known and can have bought on market, and narration to some extent in following patent application, EP-A-0032802, EP-A-0327505, WO90/10671, EP-A-0400532, EP-A-404723, EP-A-0404727, EP-A-404728, WO 91/02024 and WO 91/02025.
Usually, composition can obtain by blending starch-based component and synthetic thermoplastic component like this, its blending condition is the common heat refining of extruding, promptly (be generally 5-40% weight at water of limiting the quantity of or softening agent, for starch one aqueous systems) exist down, blending obtains composition under the temperature and pressure that destroys the crystallization of starch and obtain thermoplastic melt being enough to.By this sampling technology, obtain the thermoplasticity blend, wherein starch-based component and synthetic thermoplastic component form and to interpenetrate or to the interpenetrative structure of small part.
An object of the present invention is to provide the novel polymeric compositions of the above-mentioned type, with the corresponding performance of known starch-based composition relatively, composition of the present invention has high biodegradation rate and improved mechanicalness and/or water tolerance and to the improved low-permeability of water vapour.
Another object of the present invention is to improve the processibility of known organism degradation polymer, and novel blend is provided thus, and this blend contains such polymkeric substance, is biodegradable and suitable end article, the especially sheet material of more easily being processed into, film and silk.
Above-mentioned purpose is that the polymer composition by the above-mentioned type reaches, and wherein synthesising thermoplastic copolymer's component contains the polymkeric substance of one or more following components: a) have the aliphatic hydroxy acid of 2 to 24 carbon atoms, corresponding lactone or the homopolymer of rac-Lactide; B) have the aliphatic hydroxy acid of 2 to 24 carbon atoms, corresponding lactone or rac-Lactide and be not the monomeric aliphatic hydroxy acid that contains 2 to 24 carbon atoms of first kind of formation, corresponding lactone or the monomeric multipolymer of rac-Lactide, aromatics oxygen acid, aliphatic series or aromatic isocyanate with being selected from; C) in homopolymer and the multipolymer a) or b) with the block or the graft copolymer of one or more following components: i) Mierocrystalline cellulose or modified-cellulose such as rhodia, carboxymethyl cellulose; Ii) amylose starch, amylopectin, natural or treated starch: iii) by glycol (as 1, the 2-ethylidene glycol, propylene glycol, butyleneglycol, the poly suboxygen ethyl glycol, the poly suboxygen propyl glycol, neopentyl glycol, 1, the 4-butyleneglycol, cyclohexanediol, two anhydrous sorbyl alcohols), polyester prepolyer or have the polymkeric substance of glycol end group and polymkeric substance that following component reaction generates:---aromatics or aliphatic difunctionals isocyanic ester,---aromatics or aliphatic difunctionals epoxy compounds,---aliphatic dicarboxylic acid is (as propanedioic acid, succsinic acid, toxilic acid, fumaric acid, methylene-succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid),---the alicyclic dicarboxylic acid is (as cyclohexane dicarboxylic acid, 2,2, the 2-bicyclooctane dicarboxylic acids),---aromatics acid or anhydride (as phthalic acid), iv) urethane, by vulcabond and amino alcohol deutero-polymeric amide-urethane, polymeric amide, by dicarboxylic acid and amino alcohol deutero-polyesteramide, diester deutero-polyester-urea by amino acid and glycol, v) polyhydroxylated polymkeric substance (as polyvinyl alcohol), the ETHYLENE-VINYL ALCOHOL COPOLYMER thing, all or part of hydrolysis, glycan up to dextrin, vi) polyvinylpyrrolidone, polyvinylpyrrolidone-vinyl acetate copolymer, Ju ethyl oxazoline, vii) ionomer such as polyacrylic ester and polymethacrylate; D) by with as isocyanic ester, epoxide, phenylester and the modification of aliphatic carbonate chain extension agent above-mentioned a) and b) in the monomer of definition or the polyester that common monomer obtains; E) by with polyfunctional acid (as 1,2,4-benzenetricarboxylic acid, 1,2,4,5-pyromellitic acid, polymeric polyisocyanate and polyepoxides) partial cross-linked above-mentioned a) and b) in monomer and the polyester that obtains of monomer altogether.
The homopolymer and the multipolymer of the lactone of ε-hydroxy acid, especially 6 hydroxycaproic acid, 6-Hydroxyoctanoic acid, 3,7-dimethyl-6-Hydroxyoctanoic acid and correspondence are preferred.
As the monomer of the aliphatic hydroxide radical acid that contains 2 to 24 carbon atoms, to consider following acid and corresponding rac-Lactide or lactone especially:---alpha hydroxy acid such as lactic acid and corresponding rac-Lactide, oxyacetic acid and corresponding glycollide;---beta-hydroxy acid such as hydroxy-propionic acid, hydroxy new pentane acid and hydroxyl n-nonanoic acid and corresponding lactone;---γ-alcohol acid such as hydroxybutyric acid and corresponding lactone;---δ-alcohol acid such as hydroxypentanoic acid and corresponding lactone;---ε-alcohol acid is as described above those;---contain hydroxycarboxylic acid such as hydroxydecanoic acid that hydroxyl exceeds the 6-position; Natural source product such as juniperic acid (sabinic acid) and juniperic acid (16-hydroxy-palmitic acid); Hydroxy unsaturated acid such as ricinolic acid; By lipid acid such as miristic acid, palmitinic acid and stearic acid 'alpha '-hydroxylation and deutero-acid; Close lipid acid such as oleic acid, ricinolic acid and erucic acid hydroxylation and deutero-acid by insatiable hunger;---alicyclic alcohol acid such as hexanaphthene alcohol acid and 2,2,2-bicyclooctane alcohol acid.
As aliphatic hydroxide radical acid multipolymer with isocyanic ester, 6-caprolactone and 4,4 '-multipolymer of diphenylmethanediisocyanate (MDI), toluene ester two isocyanic acids (TDI), isophorone diisocyanate or hexamethylene diisocyanate is preferred.
As aliphatic hydroxide radical acid and the lactone of correspondence and the multipolymer of aromatic hydroxy acid, the multipolymer of 6-caprolactone and beta phenyllactic acid or peach acid partially is preferred.
A)-e) the general fusing point of used in the present invention crystalline polymer is 40 to 175 ℃; But crystallization and amorphous polymer all can use; It is preferred having homopolymer and the multipolymer of molecular weight more than 40000.
Known aliphatic polyester with low melting point or low glass transition temp is to be difficult to process with the common technology case as film blowing and blowing that is used for thermoplastic material, particularly about having low-melting poly-epsilon-caprolactone and its multipolymer, the film that is generated feels when extruding and is clamminess thus, and melt strength is low when being higher than 130 ℃; And because the low crystallization rate of this polymkeric substance, the finished product generate the back long crystallisation process take place, and As time goes on can bring undesirable performance variation.Have been found that starch and polymkeric substance mixture a)-e) improves its processing characteristics, and do not damage its mechanical property and biological degradability.This improvement is effective especially for having 40～100 ℃ low melting point temperature polymkeric substance.
Relative proportion between starch ingredients and polymeric constituent can change in very wide scope, and it depends on the end-use that blend of the present invention is fit to, and generally uses 1: 9 to 9: 1 ratio, is preferably 1: 4 to 4: 1, more preferably 1.5: 1 to 1: 1.5.
Preferred example comprises that the polymeric constituent in the composition is by poly-epsilon-caprolactone (preferably its molecular weight is higher than 40000) or by the multipolymer of 6-caprolactone and fat or aromatic isocyanate, constitute as multipolymer Estane (registered trademark, BF Goodrich) or their mixture (weight ratio is preferably 5: 1 to 1: 1).
According to another embodiment of the present invention, the synthetic polymer component contains component A and B component, component A by the polymkeric substance of quoting as proof herein a) to e) or their mixture constitute, B component contains one or more by ethylenically unsaturated monomer derived polymers or multipolymer, polymkeric substance or multipolymer have at least one polar functional group that offers repeating unit, as preferred hydroxyl or carboxyl, carboxyalkyl, alkyl carboxyl, pyrrolidyl and acetal, (alkyl of indication preferably contains C
1～C
4).
The polymkeric substance of B component comprise have fusing point between 80 ℃ and 130 ℃ and ethylene content be higher than the ethylene copolymer of 50% (weight), for example, especially ethene-acrylic copolymer, ETHYLENE-VINYL ALCOHOL COPOLYMER thing, ethylene-vinyl acetate ester copolymer and their mixture.Yet, particularly preferably be the higher melt polymkeric substance, polyvinyl alcohol and have an ETHYLENE-VINYL ALCOHOL COPOLYMER thing that ethylene content is 10～44% (weight) for example, they are generated by corresponding polyvinyl acetate and the hydrolysis of ethylene-vinyl acetate ester copolymer, and its degree of hydrolysis is 50～100%.
Described the blend of starch and ETHYLENE-VINYL ALCOHOL COPOLYMER thing among the EP-A-400532, introduced as reference here.
The generation that can partly or entirely be modified of the alcohol groups of above-mentioned polymkeric substance: 1) generate ether with following component reaction:---oxyethane---is used up to C
20Alkyl replacement or oxyethane---the vinyl cyanide (Ce that replaces with aryl
2+Initiator)---acrylamide---aralkyl halogen---Mono Chloro Acetic Acid---methylchlormethyl ether---silane 2) inorganic and organic ester, as sulfuric ester, nitric ether, phosphoric acid ester, arsenate, xanthate, carbamate, urethanum, boric acid ester, titanic acid ester, 3) by using fat or aromatic acid, the chloropropene acyl, the organic ester that particularly fatty acid or anhydride generates, 4) acetal and the ketal that generates by following component reaction------contain unsaturated aliphatic aldehyde---chloro acetaldehyde---the alicyclic aldehyde of oxalic dialdehyde---aromatic aldehyde---, aliphatic ketone---aralkyl ketone---the cycloalkyl aryl ketone that contains aliphatic aldehyde up to 22 carbon atoms up to 22 carbon atoms
As by editing and publishing by C.A.Finch described in the document of quoting as proof in the thing " polyvinyl alcohol " and the 9th chapter, can carry out the reaction of above-mentioned generation ether, organic and inorganic ester and acetal at an easy rate.
Also can use polyvinyl alcohol and ethene-vinyl alcohol (to contain ethene up to 40% (weight), wherein the degree of hydrolysis of acetic ester is between 100 and 50%) the polyfunctional poly compound, wherein can be replaced by the common monomer that is selected from following component: propylene up to 50% ethene, iso-butylene, vinylbenzene, vinylchlorid, 1, the 1-Ethylene Dichloride, molecular formula is CH
2The vinyl ether of=CR-OR ' (wherein R is hydrogen or methyl, and R ' is the alkyl that contains 1 to 18 carbon atom), cycloalkyl or polyether, vinyl cyanide, methacrylonitrile, molecular formula is CH
2=CR-CO-CH
2(wherein R is hydrogen or methyl to-R ', and R ' is hydrogen or C
1～C
6Alkyl) vinyl ketone, molecular formula are CH
2(R is hydrogen or methyl to=CR-COOR ' in the formula, and R ' is hydrogen or C
1～C
6Alkyl) acrylic or methacrylic acid and their ester, basic metal that these are sour or alkaline earth salt, molecular formula is CH
2(wherein R is hydrogen or methyl to-CR-OCOR ', and R ' is hydrogen, methyl, with chlorine or fluorine list, two or trisubstituted methyl, or C
2～C
6Alkyl) ethenyl derivatives, molecular formula are CH
2=CR-CONR ' R " (wherein R is hydrogen or methyl, R ' and R " is identical or different and is hydrogen or C
1～C
3Alkyl) amino methylvinyl acid esters, maleic anhydride, rich horse acid anhydride, vinyl pyrrolidone, vinyl pyridine, or 1-vinyl imidazole.
As described in 17 406 pages of the volumes and subsequent cited literature 2 and " Polymerisation processes ofvinylesters " chapters and sections of " Encyclopedic of polymer Science and Engineering ", use radical initiator such as hydrogen peroxide, persulphate and benzoyl peroxide to realize copolymerization.
Preferred composition of the present invention contains, as component A poly-epsilon-caprolactone or its multipolymer are arranged, the preferred isocyanate multipolymer, poly butyric ester, poly butyric ester/valerate, or lactic acid polymer or their mixture have polyethylene-vinyl alcohol as B component, can be above-mentioned modification, polyvinyl alcohol or polyethylene-vinylformic acid or polyethylene-ethyl acetate or their mixture.
According to further embodiment, the present invention includes blend, wherein the synthetic polymer component contains: A has aliphatic polyester as component, comprises that above-mentioned polymkeric substance is a) to e) and the polymkeric substance that obtains by the polyreaction of aliphatic diol and dicarboxylic acid as the oxalic acid ester or the sebate of poly-ethylidene and polybutylene; As B component the identical polymkeric substance described in the leading portion is arranged.
The biological degradation polyalcohol composition that contains starch and ETHYLENE-VINYL ALCOHOL COPOLYMER thing is known, said composition can generate has outstanding mechanicalness and goodish water-proof film, but some shortcoming of said composition, this shortcoming is special in lose mechanicalness owing to the humidity variation relevant; Particularly, there is the loss of undesirable crisp growth and shock strength, makes to be restricted aspect its use in making packing articles and similar application below 10 ℃ and under the low humidity.On the other hand, as previously mentioned, the polymkeric substance that generally has good biodegradability properties is a) to e) be difficult to processing, and because its low melting point makes it to use in the temperature range that limits.
According to the present invention, found to form sediment material component and polymer B component are added to has suitably improved mechanical property in the polymer A, and has reached the low-permeability to water vapor and liquid water.Particularly starch and polymer B component are added to and have nucleating effect in the polymer A, and under the processing conditions of blend of the present invention, this nucleating effect makes the polymer A crystallization rate obtain significant growth.By film blowing, extrude, melt spinning, blowing and injection molding produce in film, sheet material, fiber and silk and the moulded product, this advantage is effective especially.
The blend that contains starch, polymer B and softening agent can have been bought on market, trade mark is Mater Bi (by the Novamont registration), and the raw material that this blend can be used as starch and polymer B offers composition of the present invention.
The component A and the weight ratio between the B of synthetic polymer component are preferably 1: 6 to 6: 1, more preferably 1: 4 to 4: 1.
The preferred composition that is particularly suitable for injection molding comprises :-about 20～60% (weight) starch ingredients, and about 10～80% (weight), the component A of especially about 10～50% (weight) ,～about 0～45%, the B component of especially about 2～30% (weight),
Represented percentage composition is with respect to the summation of starch and all synthetic component.
About being applicable to the composition of producing film, sheet material and analogous material, preferred compositions comprises :-about 5～60% (weight) starch ingredients ,-about 40～80% (weight) component A ,-about 0～35% (weight), especially about 5～30% (weight) B component.
Represented percentage composition is with respect to the summation of starch and all synthetic component.
When product Mater Bi (Novamont trade mark) was buied in use as the raw material of starch and polymer B type, the preferred weight ratio between polymer A and the Mater Bi was 80: 20 to 30: 70.
The starch that uses in polymer composition is preferably from plant, and as the native starch that extracts in potato, rice, tapioca (flour), corn and the cereal, under any circumstance, term starch also means the starch that comprises physics and chemical modification.
Have found that, use the starch ingredients that contains at least 78% (weight) amylopectin to obtain film by extrusion-blown modling.When with scanning electronic microscope (* 2000 times) when observation, its section is stratiform or laminar structure, and this structure is by constituting with the many simple linear polymer microfacies of starch microfacies alternative, and wherein the crystalline texture of starch can not recognize again.The realization of laminate structure makes the film that made by such polymer blend and sheet material obtain significant growth to the barrier of gas and liquid like this.
In this respect, it is preferred containing the starch ingredients that the amylopectin amount is higher than 90% (weight) and more wishes to be higher than 94% (weight).Unique starch material or amylopectin, waxy starches by using waxy starches (about 95% weight of amylopectin amount) conduct and/or the mixture that contains the common starch (as W-Gum and yam starch) of low amylopectin amount can obtain meeting the starch ingredients of above-mentioned requirements.
On the other hand, under the processing conditions of extruding with blown film, contain the amylopectin amount and be lower than the starch ingredients that 78% (weight) and corresponding amylose starch amount be higher than 22% (weight) and appear to help interpenetrating between starch ingredients and synthetic polymer component.
By in the mixture of extruding, adding any material, this material has the complex ability that reduces amylose starch or has by hydrophilic interaction (as boric acid, borax, first boric acid, aluminium hydroxide and an alkali metal salt especially muriate) and starch interaction ability, and the starch that contains low amylopectin content (being higher than about 70% weight) by use also can obtain above-mentioned stratiform or flaky texture.For this purpose, relative starch ingredients, the significant quantity of this material is 0.01～10%, is preferably 0.05～5% (weight).
As applying for that in the U.S. for the transparency of improving starch/polymer blend can add boron-containing compound, the document is quoted for referencial use at this described in 734492 on July 23rd, 1991.
Polymer composition preferably contains softening agent, the relative gross weight of the composition that constitutes of starch and polymeric constituent, and the concentration of softening agent is 1～50% (weight), and is preferred 5～40%, more preferably 5～25% (weight).
The polyvalent alcohol that is selected from following component can be used as softening agent: a) polyvalent alcohol that is formed by 1 to 20 hydroxylation repeating unit (each contains 2 to 6 carbon atoms), b) ether, thioether, organic and inorganic ester, the aminoderivative of acetal and the polyvalent alcohol that forms by 1 to 20 hydroxylation repeating unit (each contains 2 to 6 carbon atoms), c) contain the polyvalent alcohol of 1 to 20 hydroxylation repeating unit (each contains 2 to 6 carbon atoms) and the reaction product of chain extension agent, d) oxidation products of polyvalent alcohol, this polyvalent alcohol contains 1 to 20 hydroxylation repeating unit, and each repeating unit contains 2 to 6 carbon atoms and contains at least one aldehyde or carboxylic acid functional or their mixture.
Softening agent is extracted out from the finished product that obtained by composition of the present invention or the phenomenon of migration in order to reduce, envrionment temperature (25 ℃) down the vapour pressure vapour pressure and the water-soluble compound that are lower than glycerine be preferred.
A) the type aliphatic polyol comprises the compound of following chemical formula:
OH-CH
2-(CHOH)
n-CH
2N is 0 to 4 in OH (I) formula, for example, and ethylene glycol, glycerine, erythritol, arabitol, adonitol, Xylitol, mannitol, iditol, melampyrum, sorbyl alcohol and allitol, and the not polyvalent alcohol in the following formula given range, for example propylene glycol, polyoxyethylene glycol, TriMethylolPropane(TMP), tetramethylolmethane, contain the polyvinyl alcohol of 2 to 10 repeating units and by 2 to 10, the Polyglycerine that preferred 2 to 5 monomeric units (comprising various oligomer mixtures) form.
B herein) many no alcohol derivate of aliphatic series preferably have and can be substituted the structural formula that obtains by at least one alcohol functional group in equation, those that in epimere, quote as proof preferably, and replacement functional group is selected from :-O-(CH
2)
n-H, n=1～18 wherein, preferred 1～4 ,-O-CH=CH-R
1, R wherein
1=H or CH
3,-O-(CH
2-CHR
1-O)
n-H, wherein R
1=H or CH
3, n=1～20 ,-O-(CH
2)
n-Ar, wherein Ar is unsubstituted, replacement or heterocyclic aryl, n=0～4 ,-OCO-H ,-OCO-CR
1R
2R
3, R wherein
1, R
2And R
3Group is identical or different and is selected from H, Cl and F ,-OCO-(CH
2)
n-H, n=2～18 wherein, preferred 2～5 ,-ONO
2,-OPO
3M
2, wherein M can be H, ammonium, basic metal, and alkaline-earth metal, or organic cation, especially trimethyl ammonium, pyrrole form sediment or picoline-SO
3-Ar, wherein Ar is benzene or toluene-OCO-CH (SO
3M)-and COOH, wherein M is identical or different and is selected from H, the basic metal earth metals, ammonium, and organic cation, especially pyridine, picoline or ammonium methyl ,-OCO-B-COOM, B is (CH in the formula
2)
n, n=1 wherein～6 or-CH=CH-, M can be H, basic metal, alkaline-earth metal, or-(CH
2)
nH, wherein n=1～6 or aryl ,-OCONH-R
1, R wherein
1-and H or fat base or aryl ,-O-(CH
2)
n-COOM, n=1～6 wherein, M can be H, basic metal, alkaline-earth metal, ammonium or organic cation, especially pyridine, trimethyl ammonium or picoline ,-O-(CH
2)
n-COOR
1, n=1～6 wherein, R
1=H (CH
2)
m, n=1～6 wherein ,-NR
1R
2, R wherein
1And R
2=H, CH
3-, CH
3CH
2-, CH
2-CH
2OH or salinization amino ,-O-(CH
2)
n-NR
1R
2, n=1-4 wherein, R
1And R
2=H, CH
3-, CH
3CH
2-, or CH
2-CH
2-CH
2OH, wherein amino can be salinization.
-O-CH
2-CHOH-CH
2-NR
1R
2, R wherein
1And R
2Be identical or different, and be selected from H, H (CH
2)
n, n=1～6 wherein, amino salinization wherein ,-O-CH
2-CHOH-CH
2-R
1 +CL
-, R wherein
1 +Be trialkyl ammonium, pyridine or picolyl ,-O-(CH
2)
nR
+Cl
-, n=1～6 wherein, R
+Be trimethyl ammonium, pyridine or picolyl ,-O-(CH
2)
n-CN, n=1～6 wherein ,-O-(CH
2)
n-CONH2, n=1～6 wherein ,-O-(CH
3)
m-SO
2-(CH
2)
n-H, m and n=1～4 wherein ,-SCSNH
2,-OSiX
3With-O-SiOX
3, wherein X is aliphatic group or aryl.
The list of above-mentioned formula (I) polyvalent alcohol and diether and single and diester are particularly preferred, monosubstituted ethoxy thing, single propoxylated glycerine and monoacetate derivatives, particularly glucitol derivative monosubstituted ethoxy thing, are most preferred.
, chain propagation agent (especially as dicarboxylic acid, aldehyde and isocyanic ester) generates the component C compound of this paper by means of being connected two or more polyvalent alcohol molecules.
The structural formula of preferred compound is:
R-CH
2-(CHR)
n-CH
2-O-A-O-CH
2-(CHR)
m-CH
2N and m are identical or different in-the R formula, and its value is 1～6, and the R base is identical or different, and are hydroxyls or have above-mentioned given implication, and the A in the formula is selected from following gene :-CHR
1, R wherein
1=H or H-(CH
2)
n-, n=1 wherein～5 (acetal) ,-(CH
2)
n-, n=1～6 wherein ,-(CH
2-O-CH
2)
n, n=1～20 wherein ,-(CH
2CH
2-O)
n-CH
2-CH
2-, n=1～20-OC-(CH wherein
2)
n-CO-, n=0～6 wherein ,-OC-Ar-CO-, wherein Ar is aryl (it also heterocycle) ,-PO
2--CONH-(CH
2)
nNHCO-, and the compound of following formula:
R-CH
2-(CHR)
n-CH
2-A-CH
2-(CHR)
m-CH
2N and m are identical or different in-the R formula, and are 1～6 integers, and the R base is identical or different, and have top given implication, in the formula A be selected from NH-and-NH-(CH
2-CH
2-NH)
n, wherein n is 1～6 integer.
In the above-mentioned given compound, it is that the compound that forms the group of ether or ester is preferred that a R base is only arranged.
Term " polyol " means and comprises list or the many saccharidess that has up to 20 monosaccharide units, considers following monose especially:
The pentose of following formula and its derivative:
Wherein the R base is identical or different, and is hydroxyl or has above-mentioned given implication.
The example of these compounds is arabinoses, lyxose, ribose and wood sugar, preferably their monoether and monoesters.
The aldohexose of following formula and derivative thereof:
The tagatose of following formula and derivative thereof:
Wherein the R base is identical or different, and is hydroxyl or has above-mentioned given implication.
The example of these monose is glucose, fructose, seminose, allose, altrose, semi-lactosi, gulose, idose, inositol, sorbose and talitol.
The etherificate of these compounds or esterified derivative, monosubstituted ethoxy thing and single propoxylated glycerine and monoesters (especially acetic ester) are preferred.
Many saccharidess comprise contain up to 20 formulas (II), (III) or (IV) repeating unit and molecular weight up to the compound of dextrin molecular weight.
Use currently known methods, for example described in document of in edit and publish thing " Polyvinyl alco-hol " by C.A.Finch, quoting as proof and the chapter 9 joint, R functional group can be incorporated in the basic structure of many alcohol.
Preferred plasticizer comprises glycerine, Polyglycerine, glycerol ethoxylate, ethylene glycol or propylene glycol, ethylidene or propylidene glycol ether, ethylidene or propylidene triglycol, polyoxyethylene glycol or polypropylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1,2-, 1,3-, 1,4-butyleneglycol, 1, the 5-pentanediol, 1,6-, 1, the 5-hexylene glycol, 1,2,6-, 1,3, the 5-hexanetriol, neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, the acetate sorbitol ester, oxalic acid sorbitol ester, sorbyl alcohol monosubstituted ethoxy thing, sorbyl alcohol dipropoxy thing, sorbyl alcohol diethoxy thing, sorbyl alcohol six ethoxylates, amino sorb ferment, trihydroxy methyl aminomethane, glucose/polyoxyethylene glycol (PEG), the product of oxyethane and glucose response, TriMethylolPropane(TMP) monosubstituted ethoxy thing, seminose ferment monoacetate, N.F,USP MANNITOL monosubstituted ethoxy thing, butyl glucoside, glucose monosubstituted ethoxy thing, α-Jia Jiputanggan, the sodium salt of carboxymethyl sorbyl alcohol, Polyglycerine monosubstituted ethoxy thing and their mixture.
If use have dystectic synthetic polymer for example polyvinyl alcohol and ETHYLENE-VINYL ALCOHOL COPOLYMER thing (contain the ethene amount and be not more than 44% weight) as B component, described softening agent can also play important effect by work in-process, causes resultant or composition to have (at least in part) and runs through structure mutually.The fusing point of these polymkeric substance (160～200 ℃) so high so that finish with running through mutually of starch molecule be impossible, reduced the fusing point of synthetic polymer with starch and the common softening agent that adds of synthetic polymer, changed their rheological characteristics simultaneously.
Polymer materials also can comprise auxiliary agent, and as the oxyhydroxide of urea or basic metal or alkaline-earth metal, they can destroy hydrogen bond, and the amount of adding auxiliary agent in starch and multipolymer is 0.5～20% (with respect to the weight of whole composition).
Add urea (preferred amounts is 5～20% weight) and be particularly useful for of the production of suitable blown film with blend.
The present composition also can contain hydrophobic polymer such as polyethylene, polypropylene and the polystyrene of low relatively amount; But in order not damage biological degradability, the amount of polymkeric substance preferably is no more than about 5% (weight) of total composition like this.
Composition of the present invention also can contain linking agent (as aldehyde, ketone and oxalic dialdehyde) processing aid and releasing agent, usually mix the lubricant of the composition that is used for molding or extrudes, lipid acid for example, fatty acid ester, higher alcohols, polyethylene wax, LDPE and sterilant, fireproofing agent, weedicide, oxidation inhibitor, fertilizer, opalizer and stablizer.
Other additive comprises Polyvinylpyrolidone (PVP) Ju oxazoline, rhodia and nitrocellulose, regenerated cellulose, alkylcellulose, carboxymethyl cellulose, casein type protein and salt thereof, natural gum such as Sudan Gum-arabic, ammonium alginate and alginate, chitin and chitosan.
Preferably by the method described in patent application EP-A-413798 and the EP-A-400532 (being incorporated herein by reference in addition), be generally that mixing said ingredients prepares polymer composition in the forcing machine between 100 and 220 ℃ being heated to top temperature.Because the intrinsic water-content (9 ∽, 15% weight) of used starch also will suitably add water, contain water so supply with the composition of forcing machine.
When extruding, the preferred water content of composition of the present invention is 1.5 to 5% (weight), and before adjusting, this amount is that the initial water content by centre degassing minimizing total composition obtains in extrusion.
For the extruding at list or twin screw extruder, the mixture withstanding pressure is representational in hot-work is handled.Although processing is preferably carried out in forcing machine, from the rheology viewpoint, starch, synthetic polymer and softening agent can mix in any equipment, are suitable for making form sediment material and polymer-compatible as long as this equipment can guarantee the condition of temperature and shear-stress.
Under optimum condition, the method for preparing the present composition comprises the steps:-by softening agent and possible water, temperature be between 80 and 180 ℃ and its fusing point and rheological characteristics medium power learn change under, swollen starches component and synthetic polymer component; For example, in the first step that forcing machine is carried, can realize this effect in component through about 2 to 50 seconds.-under the condition that is equivalent to plasticized starch and synthetic polymer component identical viscosities value, make composition stand to shear,-free or outgas under pressure or vacuum with control mode, be created on temperature 140-180 ℃ of melt that contains liquid, wherein content liquid can under atmospheric pressure not produce bubble, that is, for example do not produce bubble at outlet of extruder.-in water-bath or air, cool off the finished product.
Entire method requires pressure between 0.5 and 10 MPas, preferably between 1 and 5 MPas.
As mentioned above, preferably prepare thermoplastic compounds by direct mixing said ingredients, but, also can in the presence of softening agent and the water that may add, anticipate starch, temperature condition is 100 to 200 ℃, generate thermoplastic starch thus, this starch can mix with synthetic polymer in second step also with other softening agent again and mix.For polyvinyl alcohol and ETHYLENE-VINYL ALCOHOL COPOLYMER thing, because must being used to improve the fusing point and the rheological of polymkeric substance, softening agent make it compatible, therefore the part of adding softening agent total amount when pretreated starch and synthetic polymer blended begin with starch.
Direct blending (preferably by common forcing machine) by starch and polymeric constituent A and B (when the latter uses) obtains composition of the present invention, embodiment according to the back, by blending component A polymkeric substance a) to e) and be pre-mixed the blend that obtains by starch and B polymkeric substance, also can obtain blend of the present invention.
Example 1
With 38 parts of W-Gum Globe 03401 (Cerestar, registered trademark, intrinsic water-content 12% weight), 38 parts contain the ethene molar weight be 44% and the acetate groups degree of hydrolysis be that 99.5% ETHYLENE-VINYL ALCOHOL COPOLYMER thing, 5 parts of ureas, 0.3 part of Armide E, 12 parts of sorbyl alcohol monosubstituted ethoxy things, 3.7 parts of glycerine and 3 parts of water are added among the twin screw extruder OMC, the diameter of this forcing machine is 58mm, L/D=36, be provided with 9 heating zone and have discharge portion, extrusion is selected following operational condition:
Screw speed (rev/min): 170
Exhaust pressure (handkerchief): 9 * 10
4
The position of discharge portion: the 8th district
Heat distribution: cooling zone/90 ℃/140 ℃/180 ℃/180 ℃/180 ℃
/180℃/175℃/165℃
Head temperature: 145 ℃, melt temperature: 145 ℃
Head pressure (handkerchief): 2.7 * 10
6
Absorb (A): 67～69
Cool off the extrudate of macaroni shape and be processed into particle in tank, the intrinsic water-content of particulate is that (to call this product in the following text is particle A to 3.5% weight
1).
With following composition: 30 parts of particle A of 70 parts of poly-epsilon-caprolactones (Pcl " TONE P-787 ", registered trademark Union Carbid-e)
14 parts of glycerine are added to OM, and (in the forcing machine, diameter is 20mm, and compression ratio 1: 3 has four temperature control districts, no intermediate exhaust part, operation under the following conditions: spiro rod rate: 45 rev/mins of heat distributions: 140/145/150/155 ℃
Macaroni shape extrudate is processed into particle (particle (A
2).Particle A
2Be added in the HAAke forcing machine, diameter is 19mm and L/D=25, and operation rate is 45 rev/mins, heat distribution is 140 ℃/145 ℃/150 ℃/155 ℃, be provided with the blowing head, be processed into and have the film of thickness between 30 and 50 microns, the mechanical property of gained film is listed in the table 1.
Example 2
Repeat the process of example 1, at particle A
2Use following composition in the prescription: 30 parts of particle A of 70 parts of PCL " TONE P-787 " (Union Carbide)
16 parts of glycerine mechanical propertys and penetrating quality are listed in the table 1.
Example 3
Repeat the process of example 1, at particle A
2Use following composition in the prescription: 40 parts of particle A of 60 parts of PCL " TONE P-787 " (Union Carbide)
1Mechanical property is listed in the table 1.
Example 4
Repeat the process of example 1, at particle A
2Use following composition in the prescription: 50 parts of particle A of 50 parts of PCL " TONE P-787 " (Union Carbide)
1Mechanical property and perviousness are listed in the table 1.
Example 5
With 50 parts of particle A
1Be fed to production particle A with 50 parts of poly-epsilon-caprolactone P-787 (Union Carbide)
1In the used identical OMC forcing machine, do not have the intermediate exhaust district, with following conditional operation: screw speed: 130 rev/mins of heat distributions: first cooling zone/90 ℃/130 ℃/150 ℃/155 ℃/160 ℃/160 ℃/160 ℃/150 ℃ head temperatures: 145 ℃ of pressure: 3.2 MPas absorb: 105A productive rate: 60kg/h
The particle of such gained is fed in the blow moulding equipment with diameter 44mm and L/D=30, and provide the blown film head that following feature is arranged: die diameter: the 100mm die gap: the 0.5mm port mould forming section: the condition of 10 film blowings is as follows: spiro rod rate: the heat distribution of 65rpm forcing machine: 135 ℃/140 ℃/140 ℃/140 ℃ eck heat distributions: 140 ℃ of head heat distributions: 135 ℃ of stretch ratios: 3.1 blow-up ratios: 3.2
Obtain having the film of 50 microns of mean thicknesss, the stretching of gained film and lancinating perviousness are listed in the table 2 like this.
Repeat the process of example 5, the composition of supplying with blown film equipment comprises the particle A of 47.5% weight
1, 50% weight poly-epsilon-caprolactone and 2.5% weight polyethylene.The characteristic of gained film is listed in the table 2.
Example 7
Repeat the process of example 5, the composition of supplying with blown film equipment comprises the particle A of 47.5% weight
1, 50% weight poly-epsilon-caprolactone and 2.5% weight urea, the performance of film is listed in the table 2.
Example 8
Repeat the process of example 5, the particle of supplying with blown film equipment contains 48.5% weight particles A
1, 48.5% weight poly-epsilon-caprolactone, 2.4% weight water and 0.6% weight glycerine, the performance of gained film is listed in the table 2.
Example 9～16
Repeat the process of example 1～8, replace independent poly-epsilon-caprolactone P-787 (UnionCarbide), using this polyester and multipolymer (polyester/polyurethane) ratio of mixture is 4: 1 mixture, wherein multipolymer is (to be produced by BF Goodrich by 6-caprolactone and bifunctional isocyanate, Estane, registered trademark) the deutero-multipolymer; The performance of the performance of gained film and example 1～8 gained film compares like this.
Example 17～23
In the twin screw extruder APV of diameter 30mm and L/D=25, directly add listed composition in the following table 3.(representing with asterisk in the table 3) in some cases, by forcing machine with poly-epsilon-caprolactone polymkeric substance and hexenol multipolymer (the ethene molar content is 44%, and degree of hydrolysis is 99.5%) pre-mixing.By following conditional operation APV forcing machine: spiro rod rate: 170rpm productive rate: 13.1kg/h heat distribution: first cooling zone/60 ℃/160 ℃/165 ℃/170 ℃/170 ℃/170 ℃/170 ℃/160 ℃/150 ℃ head temperatures: 140 ℃
With the granulation of macaroni shape extrudate, then it being added among the injection molding press Sandretto with preparation dumbbell specimen (ASTM 638) serve as its mechanical property of detection, and sample is tested.The gained mechanical property is listed in the table 3.
Example 24～25 blowings
Directly process following composition to produce Plastic Bottle with blowing:
Example 24 examples, 25 starch (※) % weight 44.6 44.6PCLP-787 (※ ※) % weight 41.1-Estane (※ ※ ※) % weight-41.1 glycerine % weight 11.8 11.8 water (interpolation) % weight 2.5 2.5 ※: starch Globe 03401 (Cerester, water-content are 12% weight) ※ ※: Union Carbide ※ ※ ※: BF Goodrich
Above-mentioned composition is added in the AEMME blow moulding equipment, this equipment has constant taper screw rod (compression ratio is 1: 3), and diameter is 30mm, L/D=25, use following operational condition: model: round vase, diameter 50mm cooling system: 17 ℃ of air pressures of water: (6～7) * 10
5Handkerchief
Example 24 examples 25 machine barrel T
1℃ 100 150
T
2℃ 100 150
T
3℃ 195 150 head T
4℃ 110 150
T
5℃ 115 150 spiro rod rates: rev/min 42 42 parison speed rice/minute 0.7 0.7 melt T (T
3) heavily restrain 22.9 21.8 wall thickness millimeters 0.75 0.75 ℃ 106 147 11 10 bottles of seconds blowing time
Produce bottle with blowing under these conditions and do not find corresponding difficulty, and the simultaneous test of using poly-epsilon-caprolactone P-787 to carry out separately under same operational condition has produced difficulty, for example needs to increase significantly the problem of blowing time and wall thickness.
Example 26～27
Repeat example 1 and produce particle A
1Process, it is that about 95% weight and the intrinsic water yield are about 12% weight (Snowflake 04201 starch, registered trademark) that use therein waxy starches contains the amylopectin amount.
In blown film equipment Ghioldi such gained particle is directly mixed with poly-epsilon-caprolactone P-787 (Union Carbide) under the following conditions, wherein wt is respectively 50/50 (example 26) and 60/40 (example 27) than (particle/polycaprolactone).Ghilodi equipment: diameter is that 40mm and L/D are 30 screw rods: constant taper, compression ratio are 1: 2.8 shape: the spiral die diameter: the 100mm die gap: the 0.5mm port mould forming section: 10 blown film conditions: spiro rod rate: the heat distribution of 65rpm forcing machine: 135/135/140/140 ℃ (melt temperature: 152 ℃) eck heat distribution: 140-140 ℃ of (152 ℃ of melt temperatures) head heat distribution: 135-135 ℃ of (140 ℃ of melt temperatures) eck pressure: 27.4 MPa die orifice pressure: 7.3 MPa stretch ratios: 3 blow-up ratios: 3.2
The mechanicalness of gained film and to water vapor (by 39 ℃ of liaay, the method for R.H.90% measure) and as follows like this to the perviousness of liquid water (20 ℃ are lower than 10% lower section at R.H. and do not contact with water):
Example 26 examples 27 rupture stress MPa 29.4 33.2 breaking strain % 765 864 starting tear strength N/mm 43 (y) 76 (x) 47 (y) 90 (x) spread tear strength N/mm 43 (y) 76 (x) 47 (y) 90 (x) energy to fracture kj/m
2The perviousness of 425 365 pairs of steam of 6764 8441E (Young's modulus) MPa (μ m/m g.30,24h) perviousness of 170 252 pairs of liquid waters (μ m/m g.30,24h) 90 101 (x) laterally (y) vertical
Carry out biological degradability test expression on by above-mentioned example products obtained therefrom and significant improvement is arranged than known compositions.Especially the composition that under mixing condition, contains starch, polyethylene-vinyl alcohol and poly-epsilon-caprolactone only 10 days artifact degrees of degradation up to 80%.
By injection molding, extrude, for example film, sheet village, stack membrane and sheet, silk, fiber and injection-molded item be all within the scope of the invention by the moulded products of preparation of compositions described in the present invention for the method for blowing, extrusion-blown modling, thermoforming and similar common process thermoplastic material.
Special application comprises the film that is used for absorbent article (as towel etc.), common covering and film for packaging, protective coating film or the film that generates with biodegradable and not biodegradable polymkeric substance coextrusion.
Described absorbent goods in 91112942.7 applications of U.S.'s application on August 1st, 1991, the document is incorporated herein as reference.
Stack membrane is described among the WO 92/02363, is incorporated herein as reference.
The present composition that contains A type and Type B polymkeric substance can be used for the selective membrane of production pervaporation technology, this film is as being entitled as in European application described in " selectively permeable membrane and application thereof ", the right of priority of the document is IT TO 91 A 000327, on May 3rd, 1991, the document is incorporated herein as reference.
Table 1
Routine number rupture stress breaking strain E modulus energy to fracture portraitlandscape of tear strength to water vapour
Perviousness ※
gr?30μ/m MPa (％) (MPa) Kj/m N/mm?N/mm
24h1 - 38 830 290 8480 - -2 485 38 925 272 9370 107 1093 - 25 1020 262 8450 - -4 408 27 840 310 7560 - -※ASTM?E?398-83；T＝38℃ U.R.90％
Table 2
The starting of tear strength perviousness example rupture stress breaking strain E modulus energy to fracture spreads the water vapour liquid water
(MPa) (％) MPa (Kj/m) N/mm N/mm (gr30μ/m24h)5 27.6 1080 339 10120 59.7(y)?59.7(y)?234 101
73(x) 73(x)6 27.2 680 341 6012 41.3(x)?41.3(x)?212 104
67(y) 67(y)7 31.5 651 414 6090 40.4(y)?40.4(y)?189 98
77(x) 77(x)8 34.9 701 433 7260 49.5(y)?49.5(y)?270 90
The horizontal y=of 91 (x) 91 (x) x=is vertical
Table 3 embodiment 17 18* 19* 20* 21* 22 23 starch 44.6 41.2 41.2 41.2 41.2 33 49EVOH-32.9 24.66 32.9 24.66 32.9 20EAA-3.1 3.1 3.1 3.1 2.5-Armide E-, 0.3 0.3 0.3 0.3 0.2 0.3 glycerine, 11.8 11.8 11.8 11.8 11.8 9.4 11.8H2Poly-41.1 (a) 8.2 (b), 16.44 (b) 8.2 (c), 16.44 (c) 20 (b) 16.4 (b) compound moments of torsion (%), 56 63 63 ÷, 68 64 ÷, 68 70 74 ÷, the 76 82-85 pressure (* 10 of O 2.5 2.5 2.5 2.5 2.5 2 2.5PCL base
5Handkerchief) the final H of 21-31 18 18 ÷, 23 17 ÷ 18 21 17 ÷, 20 25-27
2O, (%wt) 3.8 3.97 3.46 3.23 3.26 2.12 3.7MFR, (g/10) 1.59 1.1 0.6 1.25 0.4 0.34-6b, (MPa) 9 20 15.6 19.7 16 23.2 17 ∑ b, (%) 529 277 221 312.4 302 422 131E, (MPa) 344 996 646 888 579 949 1158Er, (Kj/m
2) 2,382 2,385 1,485 2,595 2,003 4,062 1048 starch: GLOBE 03401 (Cerester), intrinsic water-content own is 12% weight EVOH: polyethylene-vinyl alcohol, 44% ethene molar content, degree of hydrolysis 99.5%EAA: polyethylene-vinylformic acid, Pow 5981,20% vinylformic acid 6b: rupture stress ∑ b: breaking strain (a): poly-epsilon-caprolactone P-787 (Union Carbide) is (b): 6-caprolactone/vulcabond multipolymer, Estane PCL 54353 BF Goodrich (c): 6-caprolactone/vulcabond multipolymer, Estane PCL 54351 BF GoodrichES.18 ※: pre-blending 80%EVOH+20% PCL 54353ES.19 ※: pre-blending 60%EVOH+40%PCL 54353ES.20 ※: pre-blending 80%EVOH+20%PCL 54351ES.21 ※: pre-blending 60%EVOH+40%PCL 54351MrR: melt flow rate (MFR) (restraining/10 fens) under 170 ℃ of 49N loads
Claims (20)
1. polymer composition that can obtain from melt, wherein contain with respect to the destructurized starch component and all the summations of synthetic components count the destructurized starch component of 5～60% weight and count synthesising thermoplastic copolymer's component of 10～80% weight and count the softening agent of 1～50% weight with respect to destructurized starch component and synthesized polymer objects system with respect to the summations of destructurized starch component and all synthetic components, wherein synthetic component contains at least a polymkeric substance or the polymeric blends that is selected from following component:
A) have the aliphatic hydroxy acid of 2 to 24 carbon atoms, the lactone of correspondence or the homopolymer of rac-Lactide; With
B) have the aliphatic hydroxy acid of 2 to 24 carbon atoms, corresponding lactone or rac-Lactide and be not the monomeric aliphatic hydroxy acid that contains 2 to 24 carbon atoms of first kind of formation, corresponding lactone or the monomeric multipolymer of rac-Lactide, aromatics hydroxy acid, aliphatic series or aromatic isocyanate with being selected from.
2. according to the composition of claim 1, wherein synthetic component comprises ε-hydroxy acid or is selected from 6 hydroxycaproic acid, 6-Hydroxyoctanoic acid and 3, the polymkeric substance of the corresponding lactone that the 7-dimethyl hydroxyl is sad.
3. according to the composition of claim 2, wherein synthetic component is the multipolymer of ε-hydroxy acid and isocyanic ester, said isocyanic ester is selected from 4,4 '-diphenylmethanediisocyanate, toluene cyanic acid two isocyanic acids, isophorone diisocyanate and hexamethylene diisocyanate.
4. according to the composition of claim 1, wherein synthetic component comprises the multipolymer of poly-epsilon-caprolactone or 6-caprolactone and aliphatic series or aromatic isocyanate or its mixture.
5. according to the composition of claim 2, wherein synthetic component comprises that weight ratio is 5: 1 to 1: 1 the poly-epsilon-caprolactone and the mixture of 6-caprolactone and aliphatic series or aromatic isocyanate multipolymer.
6. according to the composition of claim 1, wherein to contain weight ratio be 1: 6 to 6: 1 component A and B component to the synthetic polymer component, component A be selected from polymkeric substance a), b) and composition thereof, B component comprises by the ethylenically unsaturated monomer derived polymers, be selected from polyvinyl alcohol, ethylene-acrylic acid copolymer, vinyl-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, and their mixture.
7. according to the composition of claim 6, wherein B component comprises the polythene-ethenol that is obtained by the corresponding polyethylene-vinyl-acetic ester of hydrolysis, and its ethylene content is lower than 44% weight, and the degree of hydrolysis of acetate groups is 50 to 100%.
8. according to the composition of claim 6, comprising: the destructurized starch component of-20～60% weight, the B component of-2～45% weight,
Represented percentage composition is with respect to the summation of destructurized starch component and all synthetic component.
9. according to the composition of claim 6, comprising the component A of 10～50% weight and 2～30% B component.
10. according to the composition of claim 6, comprising: the component A of-40～80% weight, the B component of-5～35% weight,
Represented percentage composition is with respect to the summation of destructurized starch component and all synthetic component.
11. according to the composition of claim 6, comprising the B component of 5～30% weight.
12. according to the composition of claim 1 or 6, wherein, softening agent is selected from glycerine, Polyglycerine, glycerol ethoxylate, ethylene glycol or propylene glycol, ethylidene or propylidene glycol ether, ethylidene or propylidene triglycol, polyoxyethylene glycol or polypropylene glycol, 1,2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1, the 3-butyleneglycol, 1,4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 1,5-hexylene glycol, 1,2,6-hexanetriol, 1,3,5-hexanetriol, neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, acetate sorbitol ester, the oxalic acid sorbitol ester, sorbyl alcohol monosubstituted ethoxy thing, sorbyl alcohol dipropoxy thing, sorbyl alcohol diethoxy thing, sorbyl alcohol six ethoxylates, amino sorbyl alcohol and their mixture.
13. according to the composition of claim 12, wherein with respect to the total composition weight that is made of destructurized starch component and polymeric constituent, the amount of softening agent is 5～25% weight.
14. according to the composition of claim 12, wherein softening agent is selected from glycerine and sorbyl alcohol ethoxylate and composition thereof.
15.,, contain the urea of 0.5-20% weight wherein with respect to total polymer weight according to the composition of claim 12.
16. according to the composition of claim 1 or 6, wherein with respect to total composition, contain the hydrophobic polymer up to 5% weight, this polymkeric substance is selected from polyethylene, polypropylene and polystyrene.
17.,, contain the water of 1.5～5% weight wherein with respect to total composition according to the composition of claim 1 or 6.
18. according to the composition of claim 1 or 6, wherein the destructurized starch component contains the amylopectin more than 78% weight.
19. thermoplastic poly polymeric composition, said composition contain with respect to the destructurized starch component and all the summations of synthetic components count 5～60% weight the destructurized starch component, with respect to the destructurized starch component and all the summation of synthetic component count synthesising thermoplastic copolymer's component of 10-80% weight and the softening agent of counting 1～50% weight with respect to destructurized starch component and synthesized polymer objects system, wherein the synthetic thermoplastic component is ethylene-vinyl alcohol copolymer and polyvinyl alcohol and aliphatic polyester, and softening agent is selected from the defined compound of claim 12.
20. according to the composition of claim 6, wherein the weight ratio of component A and B is 1: 4 to 4: 1.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP91112942A EP0525245A1 (en) | 1991-08-01 | 1991-08-01 | Disposable absorbent articles |
| ITTO920199A IT1256693B (en) | 1992-03-10 | 1992-03-10 | FILMABLE AMIDACEA POLYMERIC COMPOSITION, AND SHAPED ITEMS, PARTICULARLY FILMS AND LEAVES OBTAINED FROM SUCH COMPOSITION, HAVING HIGH BARRIER EFFECT AND RELATED PROCEDURE. |
| IT92A000282 | 1992-03-27 | ||
| ITTO920282A IT1263114B (en) | 1992-03-27 | 1992-03-27 | Biodegradable amide polymer composition |
| US07/876,474 US5412005A (en) | 1991-05-03 | 1992-04-30 | Biodegradable polymeric compositions based on starch and thermoplastic polymers |
| US876,474 | 1992-04-30 | ||
| EPPCT/EP92/00959 | 1992-05-04 | ||
| PCT/EP1992/000959 WO1992019680A1 (en) | 1991-05-03 | 1992-05-04 | Biodegradable polymeric compositions based on starch and thermoplastic polymers |
| IT92A000199 | 1992-10-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1077966A CN1077966A (en) | 1993-11-03 |
| CN1039648C true CN1039648C (en) | 1998-09-02 |
Family
ID=27513009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93104044A Expired - Fee Related CN1039648C (en) | 1991-08-01 | 1993-03-09 | Biodegradable polymeric compositions based on starch and thermoplastic polymers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1039648C (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051564C (en) * | 1996-02-06 | 2000-04-19 | 雷鸣 | Decompositable material for package and method for producing food container |
| DE19908561A1 (en) * | 1998-03-26 | 1999-09-30 | Henkel Kgaa | Adhesive pencil with high tack and good setting and strength properties etc., useful for bonding paper or as general-purpose adhesive |
| ATE342936T1 (en) * | 2001-08-01 | 2006-11-15 | Fuller H B Licensing Financ | BREATHABLE BIODEGRADABLE HOT MEL COMPOSITION |
| EP1342408A1 (en) * | 2002-03-08 | 2003-09-10 | Ciuffo Gatto S.r.L. | Chewable toy for animals |
| ITMI20020866A1 (en) * | 2002-04-22 | 2003-10-22 | Novamont Spa | BIODEGRADABLE SATURATED / UNSATURED THERMOPLASTIC COPOLYESTERS |
| MY144738A (en) * | 2002-07-26 | 2011-10-31 | Malaysian Inst For Nuclear Technology Res Mint | Starch hydrogels |
| CN1294192C (en) * | 2002-12-30 | 2007-01-10 | 沈阳农业大学 | Manihot powder compound degradable material and its preparing method and use |
| CN1230466C (en) * | 2003-02-25 | 2005-12-07 | 丁少忠 | Fully bio-degradable plastic master batch and preparing process thereof |
| CN1307246C (en) * | 2003-11-07 | 2007-03-28 | 李小鲁 | Biological degradable blow-moulding resin composition containing starch and its preparation |
| CN1303154C (en) * | 2003-12-05 | 2007-03-07 | 成都新柯力化工科技有限公司 | Total-starch type biodegradable plastic |
| JP2005255743A (en) * | 2004-03-10 | 2005-09-22 | Agri Future Joetsu Co Ltd | Polyolefin resin composition, manufacturing method therefor, molded article thereof and molding method for molded article |
| EP2677000A3 (en) * | 2006-07-28 | 2014-05-21 | Biograde (Hong Kong) Pty Ltd. | Masterbatch and polymer composition |
| US10077333B2 (en) * | 2016-04-20 | 2018-09-18 | Elevance Renewable Sciences, Inc. | Renewably derived polyesters and methods of making and using the same |
| KR102388870B1 (en) * | 2016-05-13 | 2022-04-20 | 메르크 파텐트 게엠베하 | Use of amino sugars as plasticizers |
| CN113396039A (en) * | 2019-01-30 | 2021-09-14 | 巴斯夫欧洲公司 | Process for preparing starch blends |
| CN111763302B (en) * | 2020-07-08 | 2022-01-07 | 清远新力化机有限公司 | TPU (thermoplastic polyurethane) formula for thin film and preparation method thereof |
| CN115505254B (en) * | 2022-11-01 | 2023-09-19 | 黄河三角洲京博化工研究院有限公司 | Photo-biodegradable polyketone starch composite material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0255752A2 (en) * | 1986-08-05 | 1988-02-10 | Chisso Corporation | Granular fertilizer with a decomposable coating and process for producing the same |
-
1993
- 1993-03-09 CN CN93104044A patent/CN1039648C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0255752A2 (en) * | 1986-08-05 | 1988-02-10 | Chisso Corporation | Granular fertilizer with a decomposable coating and process for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1077966A (en) | 1993-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1039648C (en) | Biodegradable polymeric compositions based on starch and thermoplastic polymers | |
| JP2527523B2 (en) | Biodegradable polymer composition based on starch and thermoplastic polymer | |
| EP0670863B1 (en) | Biodegradable compositions comprising starch | |
| US5412005A (en) | Biodegradable polymeric compositions based on starch and thermoplastic polymers | |
| US20090018235A1 (en) | Environmentally degradable polymeric composition and process for obtaining an environmentally degradable polymeric composition | |
| US5852114A (en) | Biodegradable thermoplastic polymer blend compositions with accelerated biodegradation | |
| US5322866A (en) | Method of producing biodegradable starch-based product from unprocessed raw materials | |
| CN1043777C (en) | Biodegradable polymeric compositions based on starch and thermoplastic polymers | |
| CN101392073B (en) | All bio-decomposable starch-resin, preparation method thereof, film products and resin composition for preparing starch-resin | |
| EP0606923A2 (en) | Melt processable biodegradable compositions and articles made therefrom | |
| CN1898323A (en) | Blends of aliphatic-aromatic copolyesters with ethylene-vinyl acetate copolymers | |
| KR20060115648A (en) | Starch-vegetable oil graft copolymers and their biofiber composites, and a process for their manufacture | |
| CN1059345A (en) | Be particularly suitable for making the starchy polymeric mixture and the production method thereof of film etc. | |
| CA2217541A1 (en) | Biologically degradable polymer mixture | |
| EP0581843A1 (en) | Biodegradable compositions comprising starch | |
| JPH06184358A (en) | New thermoformable composition, its preparation and its use for obtaining thermoformed article | |
| EP0409783B1 (en) | Polymer base blend compositions containing destructurized starch | |
| CN112708246A (en) | Multi-component biodegradable mulching film and preparation method thereof | |
| US5691403A (en) | Biodegradable compositions | |
| CN109988400A (en) | A kind of environment-friendly type degradable packaging composite film and preparation method thereof | |
| WO2011090964A1 (en) | Biodegradable starch-containing composition with improved tear strength | |
| EP4071211A1 (en) | Biodegradable resin composition and method for producing same | |
| EP0781807A2 (en) | Biodegradable composition, a process and equipment for preparing the same | |
| RU2318006C1 (en) | Biologically degradable thermoplastic composition with using of rye flour | |
| CN1939965A (en) | Hydrophobic degradable biological material, its production and sheet forming products |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 19980902 Termination date: 20110309 |