CN102268144B - Biodegradable polylactic acid-starch thermal-resistance composite material and preparation method thereof - Google Patents
Biodegradable polylactic acid-starch thermal-resistance composite material and preparation method thereof Download PDFInfo
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- CN102268144B CN102268144B CN2011101584336A CN201110158433A CN102268144B CN 102268144 B CN102268144 B CN 102268144B CN 2011101584336 A CN2011101584336 A CN 2011101584336A CN 201110158433 A CN201110158433 A CN 201110158433A CN 102268144 B CN102268144 B CN 102268144B
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- starch
- parts
- polylactic acid
- heat
- biodegradable polylactic
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- 229920002472 Starch Polymers 0.000 title claims abstract description 50
- 239000008107 starch Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 235000019698 starch Nutrition 0.000 claims abstract description 24
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 22
- 239000003607 modifier Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 poly(lactic acid) Polymers 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 8
- 239000004902 Softening Agent Substances 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000008188 pellet Substances 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 235000013311 vegetables Nutrition 0.000 claims description 3
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 235000012222 talc Nutrition 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 abstract description 7
- 239000004033 plastic Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 abstract 1
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 239000002667 nucleating agent Substances 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 abstract 1
- 239000004626 polylactic acid Substances 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 5
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 2
- 239000002361 compost Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229940100486 rice starch Drugs 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 241000234435 Lilium Species 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 244000151018 Maranta arundinacea Species 0.000 description 1
- 235000010804 Maranta arundinacea Nutrition 0.000 description 1
- 240000002582 Oryza sativa Indica Group Species 0.000 description 1
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 235000012419 Thalia geniculata Nutrition 0.000 description 1
- 240000001085 Trapa natans Species 0.000 description 1
- 235000014364 Trapa natans Nutrition 0.000 description 1
- 240000006677 Vicia faba Species 0.000 description 1
- 235000010749 Vicia faba Nutrition 0.000 description 1
- 235000002098 Vicia faba var. major Nutrition 0.000 description 1
- 235000010726 Vigna sinensis Nutrition 0.000 description 1
- 244000042314 Vigna unguiculata Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000009165 saligot Nutrition 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to a biodegradable polylactic acid-starch thermal-resistance composite material and a preparation method thereof. The biodegradable polylactic acid-starch thermal-resistance composite material consists of the following raw material components in part by weight: 20 to 80 parts of natural starch, 10 to 70 parts of polylactic acid, 1 to 10 parts of polyvinyl alcohol, 1 to 5 parts of plasticizer, 1 to 10 parts of water, 1 to 5 parts of thermal-resistance modifier, 1 to 5 parts of nucleating agent, 1 to 5 parts of compatilizer and 1 to 5 parts of crosslinking agent. The preparation process comprises: mixing raw material; extruding to form grains; irradiating by gamma rays; and the like. The composite material disclosed by the invention has high mechanical properties. The tensile strength of the composite material is 20 to 35MPa, the elongation at break is 10 to 20 percent and the heat distortion temperature is 90 to 120 DEG C. In addition, the composite material has high environmental degradability, high forming and processing performance, and can be formed into various products by extrusion, plastic injection, thermal pressing and other means on common plastic processing equipment.
Description
Technical field
The present invention relates to field of high polymer material processing, relate to particularly biodegradable polylactic acid-starch matrix material of a kind of heat resistant type and preparation method thereof.
Background technology
A large amount of excellent performances, cheap common petrochemical industry plastics, severe contamination the mankind's living environment, the Global Oil resource is day by day exhausted simultaneously, making and utilizing the renewable resources preparation biodegradable material to be the inevitable choice that solves environment and energy problem, and also becoming in recent years the focus of many countries and Corporation R ﹠ D and concern, some biodegradable materials continue to bring out.
In existing Biodegradable Materials, derive from the poly(lactic acid) of natural resource and starch because the advantage of himself is especially noticeable.Starch is as natural polymer, have advantages of that the source is wide, price is low, fully biodegradable and the regeneration period short, but starch is polyhydroxylated polymer, itself does not possess thermoplasticity.Poly(lactic acid) is the amylofermentation derivative, derives from renewable resources, has the Industrial products of mass-producing both at home and abroad, and as novel linear aliphatic adoption ester, it has good degradation property, thermoplastic processability and good biocompatibility.But to be matter hard and toughness is relatively poor for its mechanical property, lacks flexibility and flexible, and heat-drawn wire is low, only 55～60 ℃, is very easy to be badly deformed.Production cost is also high than conventional plastic in addition, and is poor with the starch consistency, and this has also limited its application.
The report of domestic and international existing polylactic acid-starch blending and modifying relates generally to the raising of mechanical property, for the high thermal resistance of poly(lactic acid), only has a small amount of news report, there is not yet disclosed technical scheme.More existing heat-resisting level poly(lactic acid) and other biomass plastics price are higher, do not have the advantage of daily use, can't scale operation.Patent CN1793229A discloses a kind of take poly(lactic acid) as carrier, by poly(lactic acid), starch, inorganic powder, vegetable fibre are carried out respectively modification, then on forcing machine granulation make can be degradable material, overcome the low temperature brittleness of poly(lactic acid), also greatly reduce cost, but do not solve the problem of the non-refractory of poly(lactic acid).Patent CN101343406A is take poly(lactic acid), starch as main raw material, by treated starch, polydactyl acid and add various auxiliary agents, prepared heat-resistance type polylactic acid-starch alloy full-biodegradable material, but temperature tolerance is only brought up to 85 ℃, still can not need the high goods of heat resisting temperature for the manufacture of meal dish, soup bowl, cup etc.
Summary of the invention
Technical problem to be solved by this invention is to provide the lower heat-proof macromolecule matrix material of a kind of mechanical property and biodegradability excellence and price.
Another technical problem to be solved by this invention is to provide the preparation method of above-mentioned polymer composite.
The biological biodegradable heat-proof macromolecule matrix material of polylactic acid-starch of the present invention, described polylactic acid-starch heat-resisting composite is white or faint yellow solid, its tensile strength 20～35MPa, elongation at break 10～20%, 90～120 ℃ of heat-drawn wires are mixed with by the raw materials by weight portion of following component and form: 20～80 parts of native starches, 10～70 parts of poly(lactic acid), 1～10 part of polyvinyl alcohol, 1～5 part, softening agent, 1～10 part, water, 1～5 part of heat-proof modifier, 1～5 part of nucleator, 1～5 part of compatilizer, 1～5 part of linking agent.
Biodegradable polylactic acid-starch heat-resisting composite of the present invention, its described native starch is selected from W-Gum, sorghum starch, wheat starch, barley starch, rye starch, tapioca (flour), sweet potato starch, yam starch, arrowroot starch, glutinous rice starch, polished rice starch, Indica Rice Starch, Rhizoma Dioscoreae starch, green starch, Faba bean starch, pea starch, cowpea starch, lily starch, sago starch.
Preferably, the mesomeric content parts by weight of described poly(lactic acid) are lower than 5%, and viscosity-average molecular weight is 10～300,000.
Described softening agent is one or more in glycerine, ethylene glycol, sorbyl alcohol, Xylitol, maltose alcohol, glycol ether, polyoxyethylene glycol, fatty acid monoglyceride or urea.
Described heat-proof modifier is a kind of in α-methylstyrene based polyalcohol, heat distortion properties-correcting agent.The S700N of the logical Co., Ltd. of the Blendex 587S of described α-methylstyrene based polyalcohol such as U.S. Compton Co.,Ltd or Japanese space water chestnut.Heat distortion properties-correcting agent is as the Biomax Thermal 300 of du pont company.
Described nucleator is selected from one or more in aryl phosphate ester aluminium salt, clay, mica, calcium carbonate, silicon-dioxide, talcum, vegetable fibre.The ADK Stab Na-21 of described aryl phosphate ester aluminium salt such as Japanese Asahi Kasei Corporation.
Described compatilizer is maleic anhydride graft copolymer, is preferably a kind of in styrene-maleic anhydride copolymer, and described styrene-maleic anhydride copolymer as above maritime affairs must reach the SMA of petrochemical industry Hitek Ltd.
Described linking agent is selected from a kind of in dicumyl peroxide DCP, benzoyl peroxide BPO, ditertiary butyl peroxide DTBP.
The preparation method of Biodegradable polylactic acids of the present invention-starch heat-resisting composite comprises the following steps:
(1) water of the starch of 20～80 parts, the polyvinyl alcohol of 1～10 part, the softening agent of 1～5 part and 1～10 part is joined in high-speed mixer with strong cyclic by proportioning, mix at 50-70 ℃, cooling discharge, stand-by;
(2) step (1) gained raw material, the poly(lactic acid) of 10～70 parts, the nucleator of 1～5 part, the heat-proof modifier of 1～5 part, the compatilizer of 1～5 part, the linking agent of 1～5 part are added in high-speed mixer, mix at 50 ℃-70 ℃, drying obtains mixture;
(3) said mixture being joined in twin screw extruder, is 140～180 ℃ in each zone temperatures of described twin screw extruder, under the condition that each section vacuum tightness is 0.03～0.06 MPa with mixture extruding pelletization obtained above;
(4) utilize gamma-rays with this pellet radiation 60～70KGy, namely get described biodegradable polylactic acid-starch matrix material.
Preferably, in described step (3), each zone temperatures of described twin screw extruder is respectively 140～150 ℃, 150～165 ℃, 165～170 ℃, 170～180 ℃, 160～170 ℃, and die head district temperature is 150～160 ℃.
The Biodegradable polylactic acids of the present invention's preparation-starch heat-resisting composite is white in color or faint yellow solid, has following characteristics:
A, good mechanical property and resistance toheat.Its tensile strength 20～35MPa, elongation at break 10～20%, 90～120 ℃ of heat-drawn wires.
B, biodegradable.The Biodegradable polylactic acids of the present invention's preparation-starch heat-resisting composite, 12 all compost artifact degradation rates are more than 90%.
C, moulding processability are good.The Biodegradable polylactic acids of the present invention's preparation-starch heat-resisting composite, melt flow rate (MFR) is (190 ℃ of 5～15g/10min, 2.16kg), can be on the processing units of common plastics by extrude, the method such as injection moulding, hot pressing is shaped to various goods.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1:
By weight the water of the W-Gum of 20 parts, the polyvinyl alcohol of 1 part, the maltose alcohol of 1 part and 1 part is joined in high-speed mixer with strong cyclic by proportioning, stir 20min at 55 ℃, mix cooling discharge.
Above-mentioned gained mixture, poly(lactic acid), the ADK Stab Na-21 of 1 part, Biomax Thermal 300, the SMA of 3 parts, the BPO that crosses of 1 part of 2 parts of 70 parts are added in high-speed mixer, mix at 50 ℃, drying obtains mixture,
Then said mixture is joined in twin screw extruder, it is 35: 1 in length-to-diameter ratio, screw speed 200-300 rev/min, each zone temperatures is respectively 150 ℃, 165 ℃, 170 ℃, 180 ℃, 170 ℃, 160 ℃, the vacuum tightness of each section under the condition of 0.03 MPa with mixture extruding pelletization obtained above
The recycling gamma-rays is with this pellet radiation 70KGy.
The tensile strength of gained matrix material is 30MPa, elongation at break 18%, 105 ℃ of heat-drawn wires, melt flow rate (MFR) is (190 ℃ of 11g/10min, 2.16kg), moulding processability is good, can be on the processing units of common plastics by extrude, the method such as injection moulding, hot pressing is shaped to various goods.
Embodiment 2～16 courses of processing are identical with embodiment 1, and difference is to fill a prescription, the performance of processing conditions and gained matrix material is different, as shown in the table respectively:
Embodiment 2～4 tables
Embodiment 5～7 tables
Embodiment 8～10 tables
Embodiment 11～13 tables
Embodiment 14～16 tables
Embodiment 1～16 gained matrix material, all by the described method of U.S. ASTM D6400 standard, biological degradability is tested, test result shows the Biodegradable polylactic acids that the present invention prepares-starch heat-resisting composite, and 12 all compost artifact degradation rates are all more than 90%.
Claims (7)
1. biodegradable polylactic acid-starch heat-resisting composite, it is characterized in that, described polylactic acid-starch heat-resisting composite is white or faint yellow solid, its tensile strength 20～35MPa, elongation at break 10～20%, 90～120 ℃ of heat-drawn wires are mixed with by the raw materials by weight portion of following component and form: 20～80 parts of native starches, 10～70 parts of poly(lactic acid), 1～10 part of polyvinyl alcohol, 1～5 part, softening agent, 1～10 part, water, 1～5 part of heat-proof modifier, 1～5 part of nucleator, 1～5 part of compatilizer, 1～5 part of linking agent; The mesomeric content parts by weight of described poly(lactic acid) are lower than 5%, and viscosity-average molecular weight is 10～300,000; Described heat-proof modifier is a kind of in α-methylstyrene based polyalcohol, heat distortion properties-correcting agent.
2. biodegradable polylactic acid-starch heat-resisting composite according to claim 1, it is characterized in that, described softening agent is one or more in glycerine, ethylene glycol, sorbyl alcohol, Xylitol, maltose alcohol, glycol ether, polyoxyethylene glycol, fatty acid monoglyceride or urea.
3. biodegradable polylactic acid-starch heat-resisting composite according to claim 1, it is characterized in that, described nucleator is selected from one or more in aryl phosphate ester aluminium salt, clay, mica, calcium carbonate, silicon-dioxide, talcum, vegetable fibre.
4. biodegradable polylactic acid-starch heat-resisting composite according to claim 1, is characterized in that, described compatilizer is a kind of in maleic anhydride graft copolymer.
5. biodegradable polylactic acid-starch heat-resisting composite according to claim 1, is characterized in that, described linking agent is selected from a kind of in dicumyl peroxide DCP, benzoyl peroxide BPO, ditertiary butyl peroxide DTBP.
6. the preparation method of the described biodegradable polylactic acid-starch heat-resisting composite of one of claim 1-5, is characterized in that, comprises the following steps:
(1) water of the starch of 20～80 parts, the polyvinyl alcohol of 1～10 part, the softening agent of 1～5 part and 1～10 part is joined in high-speed mixer with strong cyclic by proportioning, mix at 50-70 ℃, cooling discharge, stand-by;
(2) step (1) gained raw material, the poly(lactic acid) of 10～70 parts, the nucleator of 1～5 part, the heat-proof modifier of 1～5 part, the compatilizer of 1～5 part, the linking agent of 1～5 part are added in high-speed mixer, mix at 50 ℃-70 ℃, drying obtains mixture;
(3) said mixture being joined in twin screw extruder, is 140～180 ℃ in each zone temperatures of described twin screw extruder, under the condition that each section vacuum tightness is 0.03～0.06 MPa with mixture extruding pelletization obtained above;
(4) utilize gamma-rays with this pellet radiation 60～70KGy, namely get described biodegradable polylactic acid-starch matrix material.
7. the preparation method of biodegradable polylactic acid-starch heat-resisting composite according to claim 6, it is characterized in that, in described step (3), each zone temperatures of described twin screw extruder is respectively 140～150 ℃, 150～165 ℃, 165～170 ℃, 170～180 ℃, 160～170 ℃, and die head district temperature is 150～160 ℃.
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