CN101787185B - Heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material and preparation method thereof - Google Patents
Heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material and preparation method thereof Download PDFInfo
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- CN101787185B CN101787185B CN200910105326XA CN200910105326A CN101787185B CN 101787185 B CN101787185 B CN 101787185B CN 200910105326X A CN200910105326X A CN 200910105326XA CN 200910105326 A CN200910105326 A CN 200910105326A CN 101787185 B CN101787185 B CN 101787185B
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- free flame
- resin
- composite material
- retardant
- halogen
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Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 25
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 12
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005469 granulation Methods 0.000 claims abstract description 7
- 230000003179 granulation Effects 0.000 claims abstract description 7
- -1 poly butylene succinate Polymers 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 239000003112 inhibitor Substances 0.000 claims description 21
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 20
- 229920003232 aliphatic polyester Polymers 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 239000006096 absorbing agent Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 10
- 235000019260 propionic acid Nutrition 0.000 claims description 10
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 10
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 claims description 9
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 239000004645 polyester resin Substances 0.000 claims description 9
- 229920002961 polybutylene succinate Polymers 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 241000219198 Brassica Species 0.000 claims description 4
- 235000003351 Brassica cretica Nutrition 0.000 claims description 4
- 235000003343 Brassica rupestris Nutrition 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 235000010460 mustard Nutrition 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 claims description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 3
- 229960003742 phenol Drugs 0.000 claims description 3
- 239000004631 polybutylene succinate Substances 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004593 Epoxy Chemical class 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002270 dispersing agent Substances 0.000 abstract description 3
- 239000003431 cross linking reagent Substances 0.000 abstract 2
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 abstract 1
- 229920001225 polyester resin Polymers 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 14
- 239000011159 matrix material Substances 0.000 description 9
- 229920001296 polysiloxane Polymers 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 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 description 6
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 2
- 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 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229920006167 biodegradable resin Polymers 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000001912 cyanamides Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 238000005303 weighing Methods 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
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/918—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
- B29C48/9185—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
-
- 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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- 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
- B29C48/405—Intermeshing co-rotating screws
-
- 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
- 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
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- 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
- B29C2948/92885—Screw or gear
-
- 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
-
- 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
- B29C2948/92904—Die; Nozzle zone
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 discloses a heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material and a preparation method thereof. The composite material is prepared from the following raw materials: modified polylactic resin, aromatic polycarbonate resin, aliphatic polyster resin, a cross-linking agent, a halogen-free flame retardant, white oil, a dispersing agent, an antioxygen, and a processing aid. The preparation method comprises the following steps: a, drying the modified polylactic resin; b, uniformly mixing the dried modified polylactic resin and the white oil; c, uniformly mixing the cross-linking agent and the dispersing agent; d, continuously mixing the halogen-free flame retardant, the antioxygen, the processing aid and the mixed materials in step b and step c; and e, putting the mixed material in step d into a twin-screw extruder, and performing melt extrusion for granulation. The invention provides a composite material having the advantages of heat resistance, flame retardancy and good impact resistance, and a method for preparing the composite material, which has the advantages of simple production process, convenient operation and low cost.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material and preparation method thereof.The formed product of this matrix material can be widely used in fields such as clothes, weaving, packing, eagroforestry, health care, life are daily.
Background technology
At the petroleum resources growing tension; The 21 century that environmental stress highlights; Many countries will build the resource recycling society of Sustainable development as one of state basic policy, and development environment has good biodegradated polymer materal just to become a megatrend of 21 century material development energetically.
Polylactic resin (PLA) be unique be the chemosynthetic organism degraded macromolecular material of raw material with the renewable biological source; Renewable raw materials such as W-Gum; Yam starch, straw etc., so PLA has broken away from the dependence to petroleum resources; And the common petroleum base polymer of its manufacturing process ability loss-rate is low, is a kind of macromolecular material of low-resource carrying capacity of environment.PLA has good processibility, can equally carry out various forming process with common polymer, as extrude, injection moulding, blown film, fiberizing etc.Various sheet materials, fiber and the film products obtained therefrom after secondary processing such as thermoforming, spinning of preparation can be widely used in fields such as clothes, weaving, packing, eagroforestry, health care, life are daily.But because PLA itself is heat-resisting poor, shock resistance is low, and forming stability deficiency etc. has influenced its application as engineering plastics.Therefore, the modification that is necessary PLA is carried out aspect such as heat-resisting, durable, toughness reinforcing is to widen its Application Areas.
In order to make PLA be applied to all trades and professions as engineering plastics more widely; Forefathers have done a large amount of work; Comprising with heat-resisting and toughness all excellent aromatic copolycarbonate and PLA making matrix material, improving its thermal property and mechanical property, and obtained effect.But this wherein also has many weak points.For example, because co-mixing system consistency shortcoming or disperse unequal problem to cause production process expanded, tie rod to occur extruding to have some setbacks, bad phenomenon such as injection moulding article surface peeling has pearliness, and shock resistance is not up to standard etc.
Summary of the invention
The technical problem that the present invention will solve is, to the above-mentioned defective of prior art, a kind of heat-resisting, fire-retardant, heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material that erosion-resisting characteristics is good is provided.
The technical problem that the present invention further will solve is, the preparation method of the heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material that a kind of production technique is simple, easy to operate, cost is low is provided.
The technical solution adopted for the present invention to solve the technical problems is: a kind of heat-resistant halogen-free flame-retardant polylactic acid is many
Unit's matrix material, process by the raw material of following parts by weight:
Modified polylactic resin 25～40;
Aromatic polycarbonate resin 20～45;
Aliphatic polyester resin 10～25;
Linking agent 0.5～2;
Halogen-free flame retardants 5～20;
White oil 0.1～0.5;
Dispersion agent 0.1～1;
Oxidation inhibitor 0.2～0.6;
Processing aid 0.1～1.
Said modified polylactic resin is the poly (l-lactic acid) resin of capacity increasing modifying, and its molecular weight is 30000-200000.
Said aromatic copolycarbonate is a bisphenol A polycarbonate.
Said aliphatic polyester is to be selected from poly butylene succinate, polyethylene glycol adipate, polyethylene glycol succinate, polycaprolactone, the poly adipate succinic acid ester any.
Said linking agent is at least a in organo-peroxide, acid anhydrides, epoxy compounds and the isocyanic ester; Said halogen-free flame retardants is the mixture of at least two kinds of composite formation in phosphorus flame retardant, nitrogen flame retardant, the silicon-series five-retardant; Said oxidation inhibitor is the composite mixture of four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and tricresyl phosphite (2,4-di-t-butyl phenyl ester).
Said dispersion agent is a fatty acyl amide compound.
Said fatty acyl amide compound is any in amine hydroxybenzene, stearic amide, the mustard acid amides.
Said processing aid is at least a in hydrolysis inhibitor, the UV light absorber.
The preparation method of heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material may further comprise the steps:
A: earlier with the modified polylactic resin drying treatment;
B: modified polylactic resin, the white oil that will pass through drying treatment mix;
C: linking agent and dispersant is even;
D: mixed raw materials among aromatic polycarbonate resin, aliphatic polyester resin, halogen-free flame retardants, oxidation inhibitor, processing aid and step b and the step c is continued to be mixed to evenly;
E: the steps d mixed raw materials is put into twin screw extruder, through melt extruding granulation.
The preparation method of heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material preferably includes following steps:
A: earlier with modified polylactic resin dry 3-4 hour of 45 ℃ of vacuum drying ovens;
B: modified polylactic resin, the white oil that will pass through drying treatment mix in super mixer;
C: linking agent and dispersion agent are mixed in super mixer;
D: mixed raw materials among aromatic polycarbonate resin, aliphatic polyester resin, halogen-free flame retardants, oxidation inhibitor, processing aid and step b and the step c is continued to be mixed to evenly;
D: mixed raw materials in the steps d is put in the loading hopper of twin screw extruder, through melt extruding granulation; Its processing condition are: twin screw extruder one district temperature 200-230 ℃, two district temperature 200-230 ℃, three district temperature 200-230 ℃, four district temperature 200-230 ℃, head 200-220 ℃, engine speed is 450 rev/mins, and pressure is 12-18MPa.
The present invention adopts modified polylactic resin, aromatic polycarbonate resin, aliphatic polyester resin as blended material; Wherein, Modified polylactic resin is the polylactic resin through capacity increasing modifying; Improved the system consistency, improved the phenomenon of phase separation that blend such as pure property polylactic resin and aromatic polycarbonate resin occur greatly, and in co-mixing system, added aliphatic polyester and improve toughness of products; Aliphatic polyester is a Biodegradable resin, has not only improved the toughness of matrix material but also increased the ratio of matrix material degradable part.In above-mentioned blend composition, added the halogen-free flame retardants of highly efficiency compositional, use be that phosphorus system is a compound flame retardant with silicon, realized the purpose of halogen-free environmental, guaranteed this matrix material when having the halogen-free flameproof function, its each item physical and mechanical property excellence; Finally obtain the biodegradable based composites of each item excellent property.Also used a small amount of linking agent of organo-peroxide efficiently in the raw material, made the resin in the system slight crosslinked phenomenon occur, to improve the thermotolerance of matrix material.
The process for producing of matrix material of the present invention is simple, and cost is moderate.
Embodiment
For ease of the present invention is further understood, combine specific embodiment to describe the present invention at present:
In the matrix material raw material of the following example,
Oxidation inhibitor is four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester or tricresyl phosphites (2,4-di-t-butyl phenyl ester), the product of selecting for use Ciba company to produce, and trade names are respectively Irganox1010, and Irganox168.
Fire retardant is Resorcinol-two (two-2,6-3,5-dimethylphenyl SULPHOSUCCINIC ACID ESTER) PX-200 of big eight chemical prodn, and the silicone powder is the MDL-100 that Yunlong, Yin state, Ningbo City Man Deer plastics factory produces.Composite halogen-free flame retardants is that Resorcinol-two (two-2,6-3,5-dimethylphenyl SULPHOSUCCINIC ACID ESTER) and silicone powder are composite, and wherein the SULPHOSUCCINIC ACID ESTER consumption is 4.9-18 part by weight, and silicone powder consumption is 0.1-2 part;
Aliphatic polyester is poly butylene succinate PBS, general commercially available getting final product.
Polycarbonate is that molecular weight is the bisphenol A-type PC of 20000-30000;
Linking agent is an organo-peroxide, selects Di Cumyl Peroxide 99 (DCP) for use;
Dispersion agent is the stearic amide compounds, is specially ethylene bis stearic acid amide EBS;
The mixture of oxidation inhibitor phenolic antioxidant 1010 and phosphite antioxidant class 168.
Other auxiliary agent comprises hydrolysis inhibitor, uv-absorbing agent.
The preparation of modified polylactic resin:
With polylactic resin in dry 3-4 hour of 45 ℃ of vacuum drying ovens; Take by weighing dry good PLA resin, maleic anhydride and initiator Di Cumyl Peroxide 99 DCP; Three's part by weight is 100: 5: 0.5, mixes then, by the parallel dual-screw extruding machine extruding pelletization.The complete processing of parallel dual-screw extruding machine is following: 150～180 ℃ of district's temperature, and 150～180 ℃ of two district's temperature, 150～180 ℃ of three district's temperature, 150～180 ℃ of four district's temperature, head temperature 170, engine speed are 400 rev/mins.
Embodiment 1
A kind of heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material, process by the raw material of following parts by weight:
37.6 parts of modified polylactic resin; 45.0 parts of bisphenol A polycarbonate resins; 10.0 parts of poly butylene succinates; 0.5 part of Di Cumyl Peroxide 99; 0.1 part of white oil; PX-2004.9 part; 0.1 part in silicone powder; 1 part of ethylene bis stearic acid amide; Four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] 0.2 part of pentaerythritol ester, 0.1 part of tricresyl phosphite (2, the 4-di-tert-butyl) ester; 0.7 part of hydrolysis inhibitor (ADR-4370), 0.3 part of uv-absorbing agent (UV-5411).
The preparation of heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material may further comprise the steps
A: earlier with modified polylactic resin dry 3 hours of 45 ℃ of vacuum drying ovens;
B: modified polylactic resin, the white oil that will pass through drying treatment mix in super mixer;
C: linking agent and dispersion agent are mixed in super mixer;
D: mixed raw materials among aromatic polycarbonate resin, aliphatic polyester resin, halogen-free flame retardants, oxidation inhibitor, processing aid and step b and the step c is put in the super mixer, continued under room temperature state, to mix 5min.
E: mixed raw materials in the steps d is put in the loading hopper of twin screw extruder, through melt extruding granulation; Its processing condition are: 200 ℃ of twin screw extruder one district's temperature, and 200 ℃ of two district's temperature, 200 ℃ of three district's temperature, 200 ℃ of four district's temperature, 200 ℃ of heads, engine speed are 450 rev/mins, pressure is 12MPa.
Embodiment 2, and a kind of heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material is processed by the raw material of following parts by weight: 32.7 parts of modified polylactic resin; 28.0 parts of bisphenol A polycarbonate resins; 25.0 parts of poly butylene succinates; 0.2 part of Di Cumyl Peroxide 99; 0.2 part of white oil; PX-20010 part; 1 part in silicone powder; 0.1 part of ethylene bis stearic acid amide; Four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] 0.1 part of pentaerythritol ester, tricresyl phosphite (2,0.1 part of 4-di-t-butyl phenyl ester; 0.6 part of hydrolysis inhibitor (ADR-4370), 0.2 part of uv-absorbing agent (UV-5411).
The preparation of heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material may further comprise the steps:
A: earlier with modified polylactic resin dry 4 hours of 45 ℃ of vacuum drying ovens;
B: modified polylactic resin, the white oil that will pass through drying treatment mix in super mixer;
C: linking agent and dispersion agent are mixed in super mixer;
D: mixed raw materials among aromatic polycarbonate resin, aliphatic polyester resin, halogen-free flame retardants, oxidation inhibitor, processing aid and step b and the step c is put in the super mixer, continued under room temperature state, to mix 5min.
E: mixed raw materials in the steps d is put in the loading hopper of twin screw extruder, through melt extruding granulation; Its processing condition are: 220 ℃ of twin screw extruder one district's temperature, and 220 ℃ of two district's temperature, 220 ℃ of three district's temperature, 220 ℃ of four district's temperature, 210 ℃ of heads, engine speed are 450 rev/mins, pressure is 15MPa.
Embodiment 3, and a kind of heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material is processed by the raw material of following parts by weight: 25.0 parts of modified polylactic resin; 35.9 parts of bisphenol A polycarbonate resins; 20.0 parts of poly butylene succinates; 1 part of Di Cumyl Peroxide 99; 0.4 part of white oil; PX-20015 part; 1.5 parts in silicone powder; 0.5 part of ethylene bis stearic acid amide; Four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] 0.3 part of pentaerythritol ester, tricresyl phosphite (2,0.3 part of 4-di-t-butyl phenyl ester; 0.1 part of uv-absorbing agent (UV-5411).
The preparation of heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material may further comprise the steps:
A: earlier with modified polylactic resin dry 3.5 hours of 45 ℃ of vacuum drying ovens;
B: modified polylactic resin, the white oil that will pass through drying treatment mix in super mixer;
C: linking agent and dispersion agent are mixed in super mixer;
D: mixed raw materials among aromatic polycarbonate resin, aliphatic polyester resin, halogen-free flame retardants, oxidation inhibitor, processing aid and step b and the step c is put in the super mixer, continued under room temperature state, to mix 5min.
E: mixed raw materials in the steps d is put in the loading hopper of twin screw extruder, through melt extruding granulation; Its processing condition are: 230 ℃ of twin screw extruder one district's temperature, and 230 ℃ of two district's temperature, 230 ℃ of three district's temperature, 230 ℃ of four district's temperature, 220 ℃ of heads, engine speed are 450 rev/mins, pressure is 18MPa.
Embodiment 4, and a kind of heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material is processed by the raw material of following parts by weight: 40.0 parts of modified polylactic resin; 20.0 parts of bisphenol A polycarbonate resins; 16.2 parts of poly butylene succinates; 1.5 parts of Di Cumyl Peroxide 99s; 0.5 part of white oil; PX-20018 part; 2 parts in silicone powder; 0.8 part of ethylene bis stearic acid amide; Four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] 0.3 part of pentaerythritol ester, 0.2 part of tricresyl phosphite (2, the 4-di-tert-butyl) ester; 0.3 part of hydrolysis inhibitor (ADR-4370), 0.2 part of uv-absorbing agent (UV-5411).
The preparation method repeats no more at this with embodiment 1.
Embodiment 5, and a kind of heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material is processed by the raw material of following parts by weight: 30 parts of modified polylactic resin; 35 parts of bisphenol A polycarbonate resins; 22 parts of polyethylene glycol adipates; 1.5 parts of maleic anhydrides; 0.5 part of white oil; 12 parts of melamine cyanurates; 1 part in silicone powder; 0.8 part of amine hydroxybenzene; Four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] 0.3 part of pentaerythritol ester, 0.2 part of tricresyl phosphite (2, the 4-di-tert-butyl) ester; 0.3 part of hydrolysis inhibitor (quicklime), 0.2 part of uv-absorbing agent (UV-3346).
The preparation method repeats no more at this with embodiment 1.
Embodiment 6, and a kind of heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material is processed by the raw material of following parts by weight: 40.0 parts of modified polylactic resin; 20.0 parts of bisphenol A polycarbonate resins; 15 parts of polycaprolactones; 43701.5 parts of ADR; 0.5 part of white oil; PX-20018 part; 2 parts of melamine cyanurates; 0.4 part of mustard acid amides; Four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] 0.3 part of pentaerythritol ester, 0.2 part of tricresyl phosphite (2, the 4-di-tert-butyl) ester; 0.2 part of hydrolysis inhibitor (quicklime), 0.3 part of uv-absorbing agent (UV-3346).
The preparation method repeats no more at this with embodiment 1.
Embodiment 7, and a kind of heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material is processed by the raw material of following parts by weight: 37.0 parts of modified polylactic resin; 30.0 parts of bisphenol A polycarbonate resins; 23 parts of poly adipate succinic acid esters; 0.4 part of isocyanic ester MDI; 0.2 part of white oil; PX-2003 part; 6 parts of trimeric cyanamides; 0.7 part of mustard acid amides; Four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] 0.25 part of pentaerythritol ester, 0.2 part of tricresyl phosphite (2, the 4-di-tert-butyl) ester; 0.3 part of hydrolysis inhibitor (ADR-4370), 0.2 part of uv-absorbing agent (UV-5411).
The preparation method repeats no more at this with embodiment 1.
Performance test:
Tensile strength is tested by ASTM D-638 standard.Batten size (mm): 165 (length) * 19 (end width) * 3.05 (thickness), draw speed is 50mm/min;
Flexural strength and modulus in flexure are tested by standard A STM D-790.Specimen size (mm): 127 * 12.67 * 3.67, span is 48, rate of bending is 20mm/min;
Notched Izod impact strength is tested by ASTM D-256 standard.Specimen size (mm): 63.5 * 12.45 * 3.1; The breach residual thickness is 1.9mm;
Heat-drawn wire is tested by ASTM-648.Specimen size (mm): 128 * 13 * 6.4, maximum deformation quantity is 0.25;
Fire-retardantly test vertical combustion by the UL-94 standard.Specimen size (mm): 127 * 13 * 2.86,1.67,0.8.
Embodiment 1～4 prescription and material property are seen table 1:
Table 1 embodiment 1～4 raw material and detected result table thereof
| Form | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Modification PLA | 37.6 | 32.7 | 25.0 | 40.0 |
| PC | 45.0 | 28.0 | 35.9 | 20.0 |
| PBS | 10.0 | 25.0 | 20.0 | 16.2 |
| White oil | 0.1 | 0.2 | 0.4 | 0.5 |
| DCP | 0.5 | 2 | 1 | 1.5 |
| EBS | 1 | 0.1 | 0.5 | 0.8 |
| PX-200 | 4.9 | 10 | 15 | 18 |
| The silicone powder | 0.1 | 1 | 1.5 | 2 |
| 1010 | 0.2 | 0.1 | 0.3 | 0.3 |
| 168 | 0.1 | 0.1 | 0.3 | 0.2 |
| Other auxiliary agent | 1 | 0.8 | 0.1 | 0.5 |
| Notched Izod impact strength (KJ/m 2) | 45 | 60 | 53 | 50 |
| Tensile strength (MPa) | 58 | 45 | 51 | 53 |
| Elongation at break (%) | 75 | 120 | 92 | 83 |
| Flexural strength (MPa) | 76 | 63 | 71 | 73 |
| Modulus in flexure (MPa) | 2262 | 1980 | 2510 | 2388 |
| Heat-drawn wire (0.45MPa/ ℃) | 90 | 78 | 82 | 75 |
| Flame retardant properties (thickness 1.67) | HB | V0 | V0 | V0 |
Can find out that from last table phosphorus system and silicon are the flame retardant properties that compound flame retardant can effectively improve material; Increase with the ratio of PC resin in the system, the physical and mechanical property of material changes little, but thermal property especially thermotolerance increase obviously; Ratio with PBS resin in the system increases, and the toughness of material is obviously improved raising.
More than a kind of heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material provided by the present invention has been carried out detailed introduction; And can find out resulting product each item excellent property of the present invention by table 1; Can be used as engineering plastics and be used for multiple field, like OA equipment, information, communication equipment; Automotive material, fields such as material of construction and household electrical appliance.
Claims (1)
1. a heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material is characterized in that, is processed by the raw material of following parts by weight:
Modified polylactic resin 25 ~ 40;
Aromatic polycarbonate resin 20 ~ 45;
Aliphatic polyester resin 10 ~ 25;
Linking agent 0.5 ~ 2;
Halogen-free flame retardants 5 ~ 20;
White oil 0.1 ~ 0.5;
Dispersion agent 0.1 ~ 1;
Oxidation inhibitor 0.2 ~ 0.6;
Processing aid 0.1 ~ 1;
Said modified polylactic resin is the poly (l-lactic acid) resin of capacity increasing modifying, and its molecular weight is 30000-200000;
Said aliphatic polyester is to be selected from poly butylene succinate, polyethylene glycol adipate, polyethylene glycol succinate, polycaprolactone, the poly adipate succinic acid ester any;
Said dispersion agent is any in amine hydroxybenzene, stearic amide, the mustard acid amides.
2. heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material as claimed in claim 1 is characterized in that: said aromatic copolycarbonate is a bisphenol A polycarbonate.
3. heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material as claimed in claim 1 is characterized in that: said linking agent is at least a in organo-peroxide, acid anhydrides, epoxy compounds and the isocyanic ester; Said halogen-free flame retardants is the mixture of at least two kinds of composite formation in phosphorus flame retardant, nitrogen flame retardant, the silicon-series five-retardant; Said oxidation inhibitor is the composite mixture of four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and tricresyl phosphite (2,4-di-t-butyl phenyl ester).
4. heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material as claimed in claim 1 is characterized in that: said processing aid is at least a in hydrolysis inhibitor, the UV light absorber.
5. the preparation method of the described heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material of claim 1 is characterized in that, may further comprise the steps:
A: earlier with modified polylactic resin dry 3-4 hour of 45 ℃ of vacuum drying ovens;
B: modified polylactic resin, the white oil that will pass through drying treatment mix in super mixer;
C: linking agent and dispersion agent are mixed in super mixer;
D: mixed raw materials among aromatic polycarbonate resin, aliphatic polyester resin, halogen-free flame retardants, oxidation inhibitor, processing aid and step b and the step c is continued to be mixed to evenly;
E: mixed raw materials in the steps d is put in the loading hopper of twin screw extruder, through melt extruding granulation; Its processing condition are: twin screw extruder one district temperature 200-230 ℃, two district temperature 200-230 ℃, three district temperature 200-230 ℃, four district temperature 200-230 ℃, head 200-220 ℃, engine speed is 450 rev/mins, and pressure is 12-18MPa.
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| CN102399423B (en) * | 2010-09-14 | 2013-06-12 | 允友成有限公司 | Functional resin composition |
| CN102936403A (en) * | 2011-08-15 | 2013-02-20 | 上海金发科技发展有限公司 | Halogen-free flame-retardant polycarbonate composition and preparation method thereof |
| CN102627842B (en) * | 2012-04-19 | 2013-04-24 | 张家港柴能生物科技有限公司 | Preparation method of halogen-free and flame-retardant polylactic acid composite material |
| CN102838859A (en) * | 2012-09-28 | 2012-12-26 | 江苏嘉铂新材料有限公司 | Nanometer bentonite composite flame-retardant polylactic acid bioplastics and preparation method thereof |
| CN103146161B (en) * | 2013-03-29 | 2015-08-05 | 浙江海正生物材料股份有限公司 | A kind of modified polylactic resin composition and method of making the same and application |
| CN104387732A (en) * | 2014-11-13 | 2015-03-04 | 中国科学院长春应用化学研究所 | Transparent, tear-resistant and biodegradable polylactic acid thin film and preparation method thereof |
| CN107189368B (en) * | 2017-06-13 | 2020-07-07 | 浙江金彩新材料有限公司 | High-heat-resistance weather-resistance polyester fiber master batch and preparation method thereof |
| CN108164948A (en) * | 2018-01-19 | 2018-06-15 | 战国昌 | A kind of new energy soil matrix blown film material and production technology |
| CN109306161A (en) * | 2018-08-14 | 2019-02-05 | 太仓金凯特新材料科技有限公司 | A kind of preparation method of high performance heat resistant high molecular material |
| CN111378267A (en) * | 2018-12-28 | 2020-07-07 | 汉达精密电子(昆山)有限公司 | Halogen-free flame-retardant PC/PLA composite material and product thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1250065A (en) * | 1998-10-01 | 2000-04-12 | 株式会社岛津制作所 | Resin composition and its forming product |
| CN1793227A (en) * | 2005-12-28 | 2006-06-28 | 中国科学院长春应用化学研究所 | Process for preparing thermal resistant easy processed polylactic resin |
| CN101023133A (en) * | 2004-09-17 | 2007-08-22 | 东丽株式会社 | Resin composition and molding comprising the same |
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| CN1250065A (en) * | 1998-10-01 | 2000-04-12 | 株式会社岛津制作所 | Resin composition and its forming product |
| CN101023133A (en) * | 2004-09-17 | 2007-08-22 | 东丽株式会社 | Resin composition and molding comprising the same |
| CN1793227A (en) * | 2005-12-28 | 2006-06-28 | 中国科学院长春应用化学研究所 | Process for preparing thermal resistant easy processed polylactic resin |
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