CN1613901A - Biological degradable blow-moulding resin composition containing starch and its preparation - Google Patents
Biological degradable blow-moulding resin composition containing starch and its preparation Download PDFInfo
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- CN1613901A CN1613901A CN 200310113303 CN200310113303A CN1613901A CN 1613901 A CN1613901 A CN 1613901A CN 200310113303 CN200310113303 CN 200310113303 CN 200310113303 A CN200310113303 A CN 200310113303A CN 1613901 A CN1613901 A CN 1613901A
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- starch
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- composition
- aliphatic polyester
- ethylene
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- 229920002472 Starch Polymers 0.000 title claims abstract description 46
- 238000000071 blow moulding Methods 0.000 title claims abstract description 20
- 239000008107 starch Substances 0.000 title claims description 44
- 235000019698 starch Nutrition 0.000 title claims description 44
- 239000011342 resin composition Substances 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 53
- 239000011347 resin Substances 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 229920003232 aliphatic polyester Polymers 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 25
- -1 poly ethylene Polymers 0.000 claims abstract description 14
- 229920000573 polyethylene Polymers 0.000 claims abstract description 13
- 239000004698 Polyethylene Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 11
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 9
- 239000000600 sorbitol Substances 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 229920006228 ethylene acrylate copolymer Polymers 0.000 claims description 8
- 235000011187 glycerol Nutrition 0.000 claims description 8
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008116 calcium stearate Substances 0.000 claims description 5
- 235000013539 calcium stearate Nutrition 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 235000010216 calcium carbonate Nutrition 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
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- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 229940059574 pentaerithrityl Drugs 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- 241000276489 Merlangius merlangus Species 0.000 claims description 2
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000005015 poly(hydroxybutyrate) Substances 0.000 claims description 2
- 229920001592 potato starch Polymers 0.000 claims description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims 1
- 235000019359 magnesium stearate Nutrition 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 150000002148 esters Chemical class 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 235000019890 Amylum Nutrition 0.000 abstract 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 1
- 238000007664 blowing Methods 0.000 abstract 1
- IIPKBWQWKYOKRA-UHFFFAOYSA-N ethane;prop-1-ene Chemical compound CC.CC=C IIPKBWQWKYOKRA-UHFFFAOYSA-N 0.000 abstract 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 229940095686 granule product Drugs 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- 229920006167 biodegradable resin Polymers 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 235000012424 soybean oil Nutrition 0.000 description 4
- 239000003549 soybean oil Substances 0.000 description 4
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- 238000011161 development Methods 0.000 description 3
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- 230000007515 enzymatic degradation Effects 0.000 description 3
- 230000002255 enzymatic effect Effects 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
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- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 2
- IUPHTVOTTBREAV-UHFFFAOYSA-N 3-hydroxybutanoic acid;3-hydroxypentanoic acid Chemical class CC(O)CC(O)=O.CCC(O)CC(O)=O IUPHTVOTTBREAV-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- 102000004882 Lipase Human genes 0.000 description 2
- 108090001060 Lipase Proteins 0.000 description 2
- 239000004367 Lipase Substances 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 229940061720 alpha hydroxy acid Drugs 0.000 description 2
- 150000001280 alpha hydroxy acids Chemical class 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003413 degradative effect Effects 0.000 description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
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- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- CEFDWZDNAJAKGO-UHFFFAOYSA-N 2-hydroxy-2-sulfoacetic acid Chemical compound OC(=O)C(O)S(O)(=O)=O CEFDWZDNAJAKGO-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
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- 235000014113 dietary fatty acids Nutrition 0.000 description 1
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- FANFFPDSASGEBD-UHFFFAOYSA-N ethylidenetin Chemical compound CC=[Sn] FANFFPDSASGEBD-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
A full biotic-degradation resin assemblage containing amylum through blow moulding and its preparation method are disclosed. Its compositions (wt%) contrain 15-80% of amylum, 3-8% of polyhydric alcohol, 0-15% of ethane propene acid esters interpolymer, 0.5-2% of saline addition agent, 0.5-5% of poly ethylene wax, 5-70% of Aliphatic Polyesters, and 1-5% of other assistant. It is produced by: putting the mixture of mentioned above into the twin screw extruder, blending and screwing. It can be used for manufacturing many kinds of blowing molding product. Its advantages include: low cost, innocuous, all-biotic degradation which is better than other homogeneous materials.
Description
Technical field
The present invention relates to a kind of amyloid resin combination and preparation method thereof, particularly a kind ofly be used to prepare sheet material blow molding film amyloid resin combination based article, fully biodegradable and preparation method thereof.
Background technology
Development of modern industry, the particularly fast development of petrochemical complex, plastics industry, especially a large amount of uses of disposable plastic goods have also greatly been enriched people's material life in the development that has promoted industrial and agricultural production, also environment for human survival are caused serious " white pollution " simultaneously.In recent years, make laws one after another in countries in the world, the producing and selling and the use of restriction disposable plastic goods.Therefore, many in the world countries all come progressively to substitute the traditional use of plastics in disposable field at a kind of degredation plastic of research.
At present, degredation plastic mainly is divided into two kinds, and a kind of is the part biodegradable plastics, and what wherein play main Degradation is starch.As disclosed amyloid resin combination among WO 9102023, EP 0409789A2 and the Chinese patent application CN1113918A.This resin combination has and the essentially identical physical and mechanical properties of material resin, and cost is lower, can commercially produce.But the material resin in this resin combination can not be degraded, and only is to use its particle diameter of back to reduce greatly, therefore can't eliminate the pollution of material resin to environment fully.
In recent years, people have dropped into resin and/or its composition of great amount of manpower and material resources research and development fully biodegradable.For example, GB 2058808 and US 4293539 disclose a kind of resin combination, and said composition adopts the polymkeric substance of the alcohol ester with biodegradable or their multipolymer, as the degraded composition of PHB (poly 3-hydroxy butyrate) as composition.The advantage of this class material is can be fully by biological degradation, but owing to be subjected to the source of raw material and the restriction of synthetic method, this series products price is very expensive, be several times even tens times of common plastics, and when making film, unit elongation is little, and product is crisp.Thereby only be suitable for having the purposes of particular requirement.In addition, in recent years people also found also can be fully by biological degradation by preparation of special biology or the aliphatic polyester that adopts special chemical synthesis process to obtain.But similar with GB 2058808 and US 4293539, owing to be subjected to the source of raw material and the restriction of synthetic method, this series products price is very expensive, is several times even tens times of common plastics.Therefore, the production of its commercial scale and application also are very restricted.
The amyloid resin combination of resin combination, the especially fully biodegradable of the fully biodegradable that as mentioned above, in the prior art, can't obtain that cost is low, the preparation method is simple, biodegradability and physical and mechanical properties are good.
Summary of the invention
First purpose of the present invention is amyloid resin combination resin combination, particularly a kind of fully biodegradable, that be used to make the blow molding based article that a kind of fully biodegradable is provided for the shortcoming that overcomes prior art.
Second purpose of the present invention provides the method for amyloid the resin combination a kind of resin combination for preparing fully biodegradable of the present invention, particularly described fully biodegradable, that be used to make the blow molding based article.
The blow molding based article that the amyloid resin combination that the 3rd purpose of the present invention provides resin combination, particularly described fully biodegradable by fully biodegradable of the present invention makes.
The present invention relates to a kind of starch-containing resin combination that is used to prepare the fully biodegradable of blow molding based article, comprise:
15～80% (weight) starch;
3～8% (weight) polyvalent alcohol;
0～15% (weight) ethylene acrylate copolymer;
～2% 0.5 (weight) additive salt;
～5% 0.5 (weight) polyethylene wax;
5～70% (weight) aliphatic polyester;
1～5% (weight) other auxiliary agent.
According to second aspect of the present invention, the invention provides a kind of method for preparing the starch-containing resin combination of described fully biodegradable, this method comprises:
(1) with the ratio first low speed high-speed stirring blend 10～15 minutes again under the normal temperature in homogenizer as described above of starch, polyvalent alcohol, additive salt, polyethylene wax and other auxiliary agents, obtains the mixture powder;
(2) with the ratio mixing that in stirring mixer, stirs as described above of ethylene-acrylate copolymer, aliphatic polyester, obtain the mixture pellet;
(3) compound that step (1) and (2) are obtained is once more behind the premix, join feeder jointly, send in the reaction formula twin screw extruder by metering feeding, the length-to-diameter ratio L/D of twin screw extruder is 40～52: between 1, the maximum speed of revolution of screw rod is between 500-1200rpm, described twin screw extruder is made as I, II, III, IV, V and VI6 control section, each zone temperatures is set 120～145 ℃ respectively, 130～155 ℃, 140～170 ℃, 140～175 ℃, 140～180 ℃, 130～180 ℃, I wherein, the vacuum tightness of II and III control section is set at-0.02～-0.07Mpa, IV, the vacuum tightness of V and VI6 control section is set at-0.03～-0.08Mpa; Material after fusion, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, makes the starch-containing resin combination resin granular material of aforesaid fully biodegradable in screw rod and cylindrical shell.
According to the 3rd aspect of the present invention, the invention provides the blow molding based article that the amyloid resin combination of the resin combination by fully biodegradable of the present invention, particularly described fully biodegradable makes.
Description of drawings
Fig. 1 is the electron micrograph (amplifying 3000 times) of the composition film of the embodiment of the invention 1.
Fig. 2 discards in physical environment the electron micrograph of collected fragment (amplifying 3000 times) after 120 days for the composition film of the embodiment of the invention 1.
Embodiment
Enhancing along with environmental consciousness, to increasing blow molding based article, blown films such as agricultural mulching, light packing film, multilayer packing membrane, specific function film, refuse bag, shopping bag, industrial packaging film for example, and the blow molding goods, more and more higher as the requirement of the biodegradable of bottle container (ware) of: agricultural seedling-raising cup, various industrial, agricultural and family expenses, used for packing foods etc.
By preparation of special biology or the aliphatic polyester that adopts special chemical synthesis process to obtain be a kind of can be fully by biodegradable resin.According to the bonding mode of monomer component, aliphatic polyester can be divided into two classes: a class is a polyhydroxy acid, and it is the polymkeric substance of alcohol acid HO-R-COOH as repeating unit.Further according to the bonding position difference of oh group apart from carboxylic end group, with alcohol acid be divided into α-, β-and ω-alcohol acid.Another kind of is the polyalkylene dicarboxylic ester, and it is the polycondensation synthetic by glycol HO-R1-OH and diacid HOOC-R2-COOH.
Aliphatic polyester with biodegradable structure is divided into four classes according to chemical structure: poly-alpha hydroxy acid class aliphatic polyester, for example the EcoPLA series product of card base (Cargill) company production; Gather-(beta-hydroxy alkanoic acid ester) class aliphatic polyester, for example the Biopol series product of Zeneca company production; Gather-(ω-hydroxyalkanoate) class aliphatic polyester, for example the Placcel series product of the Tone series product of Union Carbide Corporation (UnionCarbide) production and Dai Saier chemical industrial company (Daicel ChemicalIndustries) production; With polyalkylene dicarboxylic ester class aliphatic polyester, the Bionolle series product produced of Shao watt superpolymer company (Showa Highpolymer) for example.
Lipase and PHA depolymerizing enzyme can disconnect the ester bond of aliphatic polyester, and enzyme is a globular proteins, and molecular weight from 10000 to 100000 or higher huge polymer are formed.In degradable aliphatic polyester, have common than easier degraded with higher melt than the polyester of low melting point (Tm).Though above-mentioned aliphatic polyester has favorable mechanical physicals and can complete biodegradable, owing to costing an arm and a leg (generally between 40000-70000 dollar/ton), so range of application is very limited.
The present inventor is through long term studies, utilize above-mentioned aliphatic poly ester material, by adding other cheap and biodegradable components, starch etc. for example, adopt twin screw extruder to carry out blend, dispersion, shearing, graft reaction, compression, plastify, extrude, make a kind of starch-containing resin of fully biodegradable.The starch-containing resin of fully biodegradable of the present invention can also complete biodegradable except possessing the mechanical and physical performance that is had as common polythene (PE), polypropylene (PP), polystyrene (PS) etc.
The invention provides a kind of starch-containing resin combination that is used to prepare the fully biodegradable of blow molding based article, said composition comprises:
15～80% (weight) starch;
3～8% (weight) polyvalent alcohol;
0～15% (weight) ethylene acrylate copolymer;
～2% 0.5 (weight) additive salt;
～5% 0.5 (weight) polyethylene wax;
5～70% (weight) aliphatic polyester;
1～5% (weight) other auxiliary agent.
According to composition of the present invention, wherein said starch is W-Gum, yam starch, sweet potato starch, tapioca (flour), wheat class and legume starch etc. and treated starch thereof, is preferably granularity at 80～120 orders, water content above-mentioned each kind of starch and the treated starch thereof in 12%～14% (weight).More preferably above-mentioned each amyloid treated starch.Its consumption is preferably 35～70% (weight).
According to composition of the present invention, wherein said polyvalent alcohol is ethylene glycol, glycol ether, propylene glycol, glycerine, Sorbitol Powder or its lower molecular weight condenses (molecular weight smaller or equal to 400, the incomplete esterification products of tetramethylolmethane or longer chain fatty acid such as glyceryl monostearate etc.), preferably glycerine, Sorbitol Powder and tetramethylolmethane.These polyvalent alcohols add can promote consistency between the each component, especially promotes the consistency of aliphatic polyester and other each components, thereby improves the biodegradable and the processibility of composition.Described polyvalent alcohol can use separately or be used more than two kinds, preferably is used, and its consumption is preferably 4～8% (weight).
According to composition of the present invention, wherein said additive salt is stearate, lime carbonate, Calcium hydrogen carbonate, light calcium carbonate and the oyster shell whiting etc. of alkylsulfonate, organic acid molysite, polyhydroxybutyrate salt, stearates such as Ca, Mg, Zn, Ba, Ce and Fe.Be preferably the stearate of hard acid salt such as Ca, Zn, Fe.This class additive can improve the goods that make by composition of the present invention dimensional stability, brighten and reduce the cost, can promote the biodegradability of goods again.Described additive can use separately or be used more than two kinds, is preferably two kinds and is used, and its consumption is preferably 1～2% (weight).
According to composition of the present invention, wherein said aliphatic polyester is 0.5～12g/10min for melting the body flow rate, and density is 0.910～0.965g/cm
3Poly-alpha hydroxy acid class aliphatic polyester, the EcoPLA series product produced of card base (Cargill) company for example; Gather-(beta-hydroxy alkanoic acid ester) class aliphatic polyester, for example the Biopol series product of Zeneca company production; Gather-(ω-hydroxyalkanoate) class aliphatic polyester, for example the Tone series product of Union Carbide Corporation (Union Carbide) production.
The ethylene-propylene acid resin that is adopted in the fully biodegradable resin combination of the present invention is: melting the body flow rate is 5～350g/10min, and density is 0.910～0.965g/cm
3, acrylic acid content is 5～40%.
Fully biodegradable resin combination of the present invention also can add some processing aids commonly used in this area as required, comprise oxidation inhibitor, light (heat) stablizer, photooxidant, antifogging agent, fire retardant, static inhibitor, coupling agent, whipping agent, tinting material, lubricant etc., its consumption is preferably 2-4%.For example in order to prevent and to suppress starch and compounding aid and resin alloy system thereof in the course of processing or in the use, because light, heat, oxygen, factor such as microorganism or bacterium causes too early degraded, particularly in degradative plastic film uses, control effectively and delay superpolymer autoxidation speed, or effectively suppress or slow down ultraviolet solarization etc., thereby reach effective author's preface control mulch film cracking phase (inductive phase), add oxidation inhibitor for example oxidation inhibitor four (3-(3 ', 5 '-di-t-butyl-4 '-its phenyl of hydroxyl) propionic acid pentaerythritol ester (abbreviation antioxidant 1010), thio-2 acid SUNSOFT Q-182S (being called for short oxidation inhibitor DSTP), contain the thioesters class, phosphorous acid esters, or composite antioxidant PKY, dihydroxyphenyl propane etc.; Between the general 0.5-1% of usage quantity (weight); Light (heat) stablizer is UV-series product such as Alpha-hydroxy-4-oxy-octyl benzophenone (being called for short UV531) for example, carbon black, organic tin is dibutyl tin laurate, the different monooctyl ester diformazan of dithioglycol ester group ethylidene tin (being called for short ester group tin) and ester group tin RWS-784, two (the different monooctyl ester of sulfo-glycolic acid) dioctyltin (being called for short capital tin 8831), two toxilic acid dibutyl tins, the different monooctyl ester dibutyl tin of sulfo-glycol, trisnonyl phenyl phosphite (TNPP), epoxy soybean wet goods for example, these auxiliary agents cooperate can play synergistic effect, and result of use is better.The kind of these processing aids and the selection of consumption are that those of ordinary skill in the art is known, do not give unnecessary details at this.
According to the present invention, also can be with the amyloid resin combination of described fully biodegradable as resin combination " master batch ", that is: with the macromolecular materials such as aliphatic polyester of prepared this resin combination and Wholly-degradable, perhaps mix the starch-containing resin combination of fully biodegradable that is used to prepare the blow molding based article that obtains having desirable composition with the polyolefin resin of difficult degradation, in the said composition, the content of this resin combination " master batch " is 40～60% (weight), and other resin is 60～40% (weight).
By adjusting the consumption of each component in the composition, composition of the present invention can be used for making different types of film and blown film goods, for example make blown films such as agricultural mulching, light packing film, multilayer packing membrane, specific function film, refuse bag, food pack, various industrial packagings, and blow molding goods, as family expenses, industrial, agricultural, medical, used for packing foods bottle, container ware etc., product has favorable mechanical performance and biodegradable performance.
The present invention also provides the preparation method of the amyloid resin combination of aforesaid fully biodegradable, comprising:
(1) with the ratio first low speed high-speed stirring blend 10～15 minutes again under the normal temperature in homogenizer as described above of starch, polyvalent alcohol, additive salt, polyethylene wax and other auxiliary agents, obtains the mixture powder;
(2) with the ratio mixing that in stirring mixer, stirs as described above of ethylene-acrylate copolymer, aliphatic polyester, obtain the mixture pellet;
(3) compound that step (1) and (2) are obtained is once more behind the premix, join feeder jointly, send in the reaction formula twin screw extruder by metering feeding, the length-to-diameter ratio L/D of twin screw extruder is 40～52: between 1, the maximum speed of revolution of screw rod is between 500-1200rpm, described twin screw extruder is made as I, II, III, IV, V and VI6 control section, each zone temperatures is set 120～145 ℃ respectively, 130～155 ℃, 140～170 ℃, 140～175 ℃, 140～180 ℃, 130～180 ℃, I wherein, the vacuum tightness of II and III control section is set at-0.02～-0.07Mpa, IV, the vacuum tightness of V and VI6 control section is set at-0.03～-0.08Mpa.
According to the inventive method, the length-to-diameter ratio of wherein said twin screw extruder is in that L/D40～between 52: 1, the maximum speed of revolution of screw rod is between 600～900rpm.
The degraded of the starch-containing resin of fully biodegradable of the present invention is accompanied by two kinds of degradation processes basically and carries out:
Enzymatic degradation:
Because enzyme can not be penetrated in the macromolecular system of BSR solid substrate, enzymatic degradation is merely able to carry out on the surface of solid substrate, is accompanied by surface corrosion and weightless phenomenon in its process.Enzyme is attacked selectively and is decomposed the unsetting or region of disorder, starch-containing resin base material the inside that the permission enzyme is diffused into fully biodegradable of the present invention, and crystallizing field is finally also by its degraded.Because only the polymer on the starch-containing resin base material surface of fully biodegradable of the present invention is decomposed, and low-molecular-weight degraded product is removed from base material by water medium solubilising face on every side, in the enzymatic degradation process, the molecular weight and the molecular weight distribution of the starch-containing resin superpolymer of fully biodegradable of the present invention do not change.In this degraded, two decomposition coursees are arranged, or at random point (internally-oriented degradation process) takes place along macromolecular chain, or the end of macromolecular chain is attacked (export-oriented degraded), the decomposition course of lipase or PHA depolymerizing enzyme all is mainly based on internally-oriented fracture, so its degradation process does not all rely on the distribution of molecular weight and molecular weight.
The non-enzymatic catalysis degraded:
Little non-enzymatic catalysis agent and reagent can be distributed in the starch-containing resin Polymer Systems of fully biodegradable of the present invention, have promptly formed degree of depth degraded.Crystallization, crosslinked and other polymer morphological properties can be diffused in the middle of the BSR Polymer Systems by the positive influence catalyzer.The initial stage in degraded is carried out in the non-enzymatic catalysis degraded, there is not weightlessness and inertia is obvious, " degraded at random " that this has just caused high polymer main chain simultaneous generation molecular weight to descend significantly, thereby the reduction and the forfeiture of the mechanical property of showing (as: tensile strength, elongation at break, shock strength etc.), and the destruction of form is until disappearance.So far, when the starch-containing molecular resin amount of fully biodegradable of the present invention was reduced to certain degree, the various enzymes of occurring in nature Institute of Micro-biology excretory promptly can decompose residue up hill and dale and be called CO
2And H
2O.
By the following examples to further instruction of the present invention and explanation.But it should be understood that these embodiment do not constitute limiting the scope of the invention.Unless stated otherwise, the consumption of each component is a weight part among the following embodiment.
Embodiment 1: be used to prepare the preparation of the fully biodegradable starch-resin composition of film
38 parts of starch, 7 parts of Sorbitol Powders, 3 parts of glycerine, 0.5 part of epoxy soybean oil, 0.2 part of oleic acid, 0.2 part of Zinic stearas, 0.2 part of calcium stearate, 0.5 part of 1010,0.6 parts of UV-531,0.8 part of DSTP and 1 part of ultra-fine carbon black be added in the homogenizer evenly mix at normal temperatures, at first with 100～150rpm/min low speed mixing about 7 minutes, 200～300rpm/min high-speed mixing was 8 minutes then.
40 parts of aliphatic polyesters (U.S. combinating carbide company product, trade names are Tone 7, and are as follows) and 8 parts of EAA (U.S. Tao Shi chemical company product, trade names are EAA3460, and are as follows) are stirred in mixing tank.
Above-mentioned 2 kinds of materials are mixed together evenly.
With above-mentioned two kinds of compounds, send in the twin screw extruder length-to-diameter ratio L of this twin screw extruder: D=48 by feeder: 1, screw diameter is Ф 72mm.Progressively adjust screw speed from 100prm, progressively rise to 200rpm, 300rpm, 400rpm, 500rpm, 700rpm, 900rpm, each section temperature is respectively: the I district: 145 ℃; II district: 155 ℃, III district: 165 ℃, IV district: 175 ℃, V district: 165 ℃, VI district: 170 ℃; The vacuum tightness in I, II and III district is set at-0.02～-0.07Mpa, the vacuum tightness of IV, V and VI6 control section is set at-0.03～-0.08Mpa; Melt body temperature is: 168～173 ℃; Material is in the screw rod and cylindrical shell of described forcing machine, after fusion, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, again through die head extrude, after the pelletizing of die face water ring, finally make the granule product of the amyloid resin combination of the fully biodegradable of the present invention that is used to prepare the blown film goods, its physical index is as follows:
Pellet index: MI=3.65, density=1.02 gram per centimeters
3, moisture=0.81% (weight).
Extrude the film that obtains being of a size of 950mm (wide) * 0.012mm (thick) * 10kg/roll with prepared granule product with DJ-55 forcing machine (the holy plastics machinery of Shuande, Guangdong power factory makes).Adopt ASTMD5247 to test its physicals, and degradation property.The result is as follows:
The film index:
Tensile strength: vertically=32Mpa, laterally=26Mpa.
Elongation at break: vertically=249%, laterally=390%.
Angle tear strength: vertically=78N, laterally=101N.
The electron micrograph of this film (amplifying 30000 times) as shown in Figure 1.Among Fig. 1, white portion is the starch small molecules, and its particle diameter is less than 1 micron.Show the film according to the inventive method preparation, the blend of starch and other components and polyolefin resin reaches " nanometer " level level.After this film places physical environment, begin Large Area Cracking through degraded (25～30 days) rear film inductive phase; Present fragmentation, efflorescence state (its electron micrograph (amplifying 3000 times) as shown in Figure 2) through 15 days left and right sides films again; After 3～4 months time, become superfine little powder, the grey shape except also having small part, the film of 85% above weight percent has been degraded into H
2O and CO
2After 6 months, this fully biodegradable starch-resin film is degraded fully.
Embodiment 2-3: be used to prepare the preparation of the fully biodegradable starch-resin composition of film
Adopting the method preparation identical with embodiment 1 to be used to prepare the resin combination of film, is material composition (following component content all is weight percentage) as shown in the table.
| The starting material title | Embodiment 2 | Embodiment 3 |
| Starch | ????40 | ????45 |
| Sorbitol Powder | ????5.5 | ????6 |
| Zinic stearas | ????0.2 | ????0.2 |
| Calcium stearate | ????0.2 | ????0.2 |
| Oleic acid | ????0.5 | ????- |
| 1010 | ????- | ????0.2 |
| RWS-784 | ????- | ????0.2 |
| Glycerine | ????3.5 | ????3 |
| Epoxy soybean oil | ????0.7 | ????1.5 |
| UV-531 | ????- | ????0.2 |
| Ultra-fine carbon black | ????0.8 | ????0.5 |
| Ethylene acrylic acid co polymer | ????10 | ????12 |
| Dihydroxyphenyl propane | ????- | ????0.5 |
| Jing Xi-8831 | ????- | ????1.5 |
| Aliphatic polyester | ????38.6 | ????29 |
| Total amount | ????100 | ????100 |
Adopt the granule product make thus to prepare film with the blow moulding equipment of routine, its physical and mechanical properties and the evaluation of degradable performance and detection method, standard are as follows:
1, physical and mechanical properties and sanitary index adopt following standard to test:
GB 1033-86 plastic density and relative density test method
GB 2547-84 Plastic Resin sampling method
GB 3682-83 thermoplastics melt flow rate (MFR) test method
GB 9691-88 used for packing foods polyvinyl resin hygienic standard
GB 9687-88 used for packing foods polyethylene formation product hygienic standard
GB 13022-91 stretched plastic film method for testing performance
QB/T1130-91 plastics right-angle tearing method for testing performance
The standard environment that GB 2918-82 plastic sample standard state is regulated and tested
GB/T5009.60-1996 used for packing foods polyethylene, polystyrene, the analytical procedure of polypropylene moulding product hygienic standard
The mensuration of GB 6672-86 plastics film and sheet thickness
The mensuration of GB 6673-86 plastics film and sheet length and width
Q/NSH01-1997 Biodegradable starch resin coating materials
2, biodegradability adopts following standard to test:
The specific emblem of ASTM D5247-92 (U.S.) biology under aerobic condition to the mensuration of degradative resin degradation rate
The mensuration of the biological mould degraded of ASTM G21-90 (U.S.) level
Adopt aforesaid method, the over-all properties of the film that biodegradable resin combination of the present invention is made is tested and is estimated, and the test result of embodiment 2,3 is as follows:
| Sequence number | Test event | The result | |
| ?01 | Outward appearance | Light yellow material, free from extraneous odour, different smelling, foreign matter | |
| ?02 | Starch content % | 25 (embodiment 2) | 35 (embodiment 3) |
| ?03 | Component content % easily degrades | ????100 | ???100 |
| ?04 | Water content % | ????0.82 | ???0.88 |
| ?05 | Melt flow rate (MFR) g/10min | ????3.9 | ???3.1 |
| ?06 | Density g/cm3 | ????1.01 | ???1.04 |
| ?07 | Tensile strength (longitudinal and transverse) Mpa | ????33，20 | ???26，19 |
| ?08 | Elongation at break (longitudinal and transverse) % | ????374，534 | ???352，460 |
| ?09 | Directly separate tear strength (longitudinal and transverse) N/mm | ????141，105 | ???91，75 |
| ?10 | Biological degradation rate %/14 day | ????70 | ???80 |
| ?11 | Mould degraded level 21 days | 4 grades | 4 grades |
Embodiment 4-9: be used to prepare the preparation of the fully biodegradable starch-resin composition of packing film
Adopting the method preparation identical with embodiment 1 to be used to prepare the resin combination of light packing film, is that material composition is as shown in the table.
| Raw material | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| Starch | 20 | ?30 | ?40 | ?50 | ?60 | ?70 |
| Sorbitol Powder | 7 | ?6 | ?5 | ?5 | ?4 | ?4 |
| Zinic stearas | 0.25 | ?0.25 | ?0.25 | ?0.25 | ?0.25 | ?0.25 |
| Calcium stearate | 0.25 | ?0.25 | ?0.25 | ?0.25 | ?0.25 | ?0.25 |
| Oleic acid | 1 | ?1 | ?1 | ?1 | ?- | ?1 |
| Stearic acid | 0.5 | ?0.5 | ?0.5 | ?0.5 | ?0.5 | ?- |
| Maleic anhydride | 2 | ?2.5 | ?2 | ?2 | ?- | ?1 |
| Glycerine | 5 | ?4 | ?3 | ?5 | ?2 | ?1 |
| Epoxy soybean oil | 2 | ?1.5 | ?2 | ?2 | ?1 | ?2 |
| Boric acid | 1 | ?1.5 | ?1 | ?1 | ?- | ?0.5 |
| PE | 10 | ?- | ?- | ?- | ?- | ?- |
| HDPE | 8 | ?- | ?- | ?- | ?- | ?- |
| Ethylene acrylic acid co polymer | 8 | ?7 | ?- | ?5 | ?- | ?5 |
| Aliphatic polyester | 35 | ?45.5 | ?45 | ?28 | ?32 | ?15 |
| Total amount | 100 | ?100 | ?100 | ?100 | ?100 | ?100 |
Adopt the granule product make thus to prepare light packing film with the equipment of aforementioned routine, physical and mechanical properties and degradable performance are used the method for stating evaluation, and it is as follows to get its average test result:
| Sequence number | Test event | Test result |
| ?01 | Outward appearance | A yellowly material, free from extraneous odour, different smelling, foreign matter |
| ?02 | Starch content % | ??40 |
| ?03 | Component content % easily degrades | ??100 |
| ?04 | Water content % | ??0.86 |
| ?05 | Melt flow rate (MFR) g/10min | ??3.75 |
| ?06 | Density g/cm 3 | ??1.02 |
| ?07 | Tensile strength (longitudinal and transverse) Mpa | ??26，18 |
| ?08 | Elongation at break (longitudinal and transverse) % | ??379，417 |
| ?09 | Directly separate tear strength (longitudinal and transverse) N/mm | ??71，98 |
| ?10 | Microbiological deterioration rate %/14 days | ??31 |
| ?11 | Mould degraded level 21 days | 4 grades |
| ?12 | Ignition residue % | ??0.3 |
| ?13 | N-hexane extract % | ??3.5 |
| ?14 | Potassium permanganate consumption mg/L | ??6 |
Embodiment 10-15: be used for the preparation of fully biodegradable starch-resin composition and blow molding based article thereof
Adopt the method preparation identical with embodiment 1 to be used to prepare the resin combination of blow molding based article, just material composition is as shown in the table, wherein, the composition that embodiment 13-15 uses for the preparation seedling-raising cup, embodiment 16-18 is for preparing the composition that bottle is used.
| Material name | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 |
| Starch | ??20 | ??30 | ??40 | ??50 | ??60 | ??70 |
| Sorbitol Powder | ??5 | ??5 | ??5.5 | ??6 | ??6.5 | ??6 |
| Zinic stearas | ??0.2 | ??0.2 | ??0.2 | ??0.15 | ??0.2 | ??0.2 |
| Calcium stearate | ??0.3 | ??0.3 | ??0.3 | ??0.15 | ??0.3 | ??0.3 |
| Oleic acid | ??1 | ??1 | ??0.5 | ??0.2 | ??- | ??0.5 |
| Stearic acid | ??1 | ??1.5 | ??1 | ??- | ??- | ??1 |
| Two lauric acid two are insulted tin octylate | ??1.5 | ??2 | ??1 | ??- | ??- | ??- |
| Capital WU-8831 | ??- | ??- | ??- | ??- | ??- | ??- |
| RWS-784 | ??- | ??- | ??- | ??- | ??- | ??- |
| Glycerine | ??3 | ??3 | ??3 | ??3 | ??3.5 | ??3 |
| Epoxy soybean oil | ??0.5 | ??1 | ??0.5 | ??0.5 | ??0.5 | ??1 |
| Regeneration PE utilizes | ??17.5 | ??- | ??- | ??- | ??- | ??- |
| Ethylene acrylic acid co polymer | ??4 | ??- | ??5 | ??8 | ??- | ??8 |
| Aliphatic polyester | ??46 | ??56 | ??43 | ??32 | ??29 | ??10 |
| Total amount | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 |
Adopt the granule product that makes thus to prepare seedling-raising cup, get its average physical and mechanical properties and degradable performance and estimate as follows with conventional apparatus for blow moulding:
| Sequence number | Test event | Test result | ||||
| 01 | Seal test | Do not leak | ||||
| 02 | Fall down test | Not damaged, the lid that do not jump allows bung that small amount of liquid is partly arranged with hitting when hitting, afterwards must not seepage | ||||
| 03 | Hanging test | Nominal capacity, L | -5 | 10-15 | 20-40 | 50-200 |
| Residual deformation amount mm | 2 | ≤3 | ≤4 | Do not split | ||
| 04 | Stacking test | Casting not | ||||
| 05 | The stress cracking test | Rimose sample number＜50% | ||||
| 06 | The hydraulic pressure split test | Do not have breakage, do not leak | ||||
| 07 | Microorganism fell rate 14 days, % | ＞77 | ||||
| 08 | Mould degraded level 21 days, level | 〉=4 grades | ||||
Claims (12)
1, a kind ofly can be used for preparing the starch-containing resin combination blow molding based article, fully biodegradable, comprise:
15～80% (weight) starch;
3～8% (weight) polyvalent alcohol;
0～15% (weight) ethylene acrylate copolymer;
～2% 0.5 (weight) additive salt;
～5% 0.5 (weight) polyethylene wax;
5～70% (weight) aliphatic polyester;
1～5% (weight) other auxiliary agent.
2, composition as claimed in claim 1, wherein said starch are that granularity 80～120 orders, water content are W-Gum, yam starch, sweet potato starch, tapioca (flour) and the treated starch thereof of 12%～14% (weight).
3, composition as claimed in claim 1, wherein said polyvalent alcohol are lower molecular weight condenses, ethylene glycol, glycol ether, propylene glycol, glycerine, the tetramethylolmethane of Sorbitol Powder, Sorbitol Powder.
4, composition as claimed in claim 3, wherein said polyvalent alcohol are Sorbitol Powder, glycerine.
5, composition as claimed in claim 1, wherein said additive salt comprise alkylsulfonate, organic acid molysite, polyhydroxybutyrate salt, stearates, lime carbonate, light calcium carbonate, Calcium hydrogen carbonate and oyster shell whiting.
6, composition as claimed in claim 5, wherein said additive salt comprises calcium stearate, Zinic stearas, Magnesium Stearate and barium stearate.
7, composition as claimed in claim 1, wherein said ethylene-acrylate copolymer are that to melt the body flow rate be 5～350g/10min, and density is 0.910～0.965g/cm
3, acrylic acid content is 5～40% ethylene-acrylate copolymer.
8, composition as claimed in claim 1, wherein said aliphatic polyester are that to melt the body flow rate be 0.5～12g/10min, and density is 0.910～0.965g/cm
3Aliphatic polyester.
9, composition as claimed in claim 1, wherein said other auxiliary agents comprise: oxidation inhibitor, light (heat) stablizer, photooxidant, antifogging agent, tinting material, lubricant, whipping agent, coupling agent, linking agent etc.
10, a kind of method of starch-containing resin combination of the fully biodegradable that is used to prepare the blow molding based article, this method comprises:
(1) with starch, polyvalent alcohol, additive salt, polyethylene wax and other auxiliary agents according to the first low speed high-speed stirring blend 10～15 minutes again under the normal temperature in homogenizer of the described ratio of claim 1, obtain the mixture powder;
(2) with ethylene-acrylate copolymer, aliphatic polyester according to the mixing that in stirring mixer, stirs of the described ratio of claim 1, obtain the mixture pellet;
(3) compound that step (1) and (2) are obtained is once more behind the premix, join feeder jointly, send in the reaction formula twin screw extruder by metering feeding, the length-to-diameter ratio L/D of twin screw extruder is 40～52: between 1, the maximum speed of revolution of screw rod is between 500-1200rpm, described twin screw extruder is made as I, II, III, IV, V and VI be totally 6 control sections, each zone temperatures is set 120～145 ℃ respectively, 130～155 ℃, 140～170 ℃, 140～175 ℃, 140～180 ℃, 130～180 ℃, I wherein, the vacuum tightness of II and III control section is set at-0.02～-0.07Mpa, IV, the vacuum tightness of V and VI6 control section is set at-0.03～-0.08Mpa.
11, method as claimed in claim 10, the length-to-diameter ratio of wherein said twin screw extruder is in that L/D40～between 52: 1, the maximum speed of revolution of screw rod is between 600～900rpm.
12, the blown film goods that make with the described fully biodegradable starch-resin composition of each claim among the claim 1-9.
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| CNB2003101133036A CN1307246C (en) | 2003-11-07 | 2003-11-07 | Biological degradable blow-moulding resin composition containing starch and its preparation |
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| CNB2003101133036A CN1307246C (en) | 2003-11-07 | 2003-11-07 | Biological degradable blow-moulding resin composition containing starch and its preparation |
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| CN1307246C CN1307246C (en) | 2007-03-28 |
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| CN100572433C (en) * | 2006-05-16 | 2009-12-23 | 广东上九生物降解塑料有限公司 | Fully biodegradable plastic resin and production method of film products thereof |
| CN101910283A (en) * | 2007-12-17 | 2010-12-08 | 丰田自动车株式会社 | Resin composition and molded article using the same |
| CN1931908B (en) * | 2005-09-16 | 2011-07-06 | 李小鲁 | Biodegradable composition and its prepn process and injection molded product |
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| CN1935886B (en) * | 2005-09-21 | 2011-09-28 | 李小鲁 | Water-soluble biodegradable material, and its preparing method and injection moulded product |
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| CN1039648C (en) * | 1991-08-01 | 1998-09-02 | 诺瓦蒙特股份公司 | Biodegradable polymeric compositions based on starch and thermoplastic polymers |
| IT1272871B (en) * | 1995-01-10 | 1997-07-01 | Novamont Spa | THERMOPLASTIC COMPOSITIONS INCLUDING STARCH AND OTHER COMPONENTS OF NATURAL ORIGIN |
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