CN102020834A - Polyactic acid/polycarbonate alloy material, and preparation method and application thereof - Google Patents
Polyactic acid/polycarbonate alloy material, and preparation method and application thereof Download PDFInfo
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- CN102020834A CN102020834A CN2010105553370A CN201010555337A CN102020834A CN 102020834 A CN102020834 A CN 102020834A CN 2010105553370 A CN2010105553370 A CN 2010105553370A CN 201010555337 A CN201010555337 A CN 201010555337A CN 102020834 A CN102020834 A CN 102020834A
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- lactic acid
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- polycarbonate
- polycarbonate alloy
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 63
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 63
- 239000000956 alloy Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002253 acid Substances 0.000 title abstract 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 4
- 238000012545 processing Methods 0.000 claims abstract description 4
- -1 poly(lactic acid) Polymers 0.000 claims description 108
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 64
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 26
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 24
- 239000003063 flame retardant Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 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 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229930182843 D-Lactic acid Natural products 0.000 claims description 4
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 229940022769 d- lactic acid Drugs 0.000 claims description 4
- 229920005668 polycarbonate resin Polymers 0.000 claims description 4
- 239000004431 polycarbonate resin Substances 0.000 claims description 4
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005453 pelletization Methods 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
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-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
- 239000011707 mineral Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 238000005452 bending Methods 0.000 abstract description 2
- 238000004891 communication Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 2
- 238000012360 testing method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000004626 polylactic acid Substances 0.000 description 7
- 238000007493 shaping process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000035882 stress Effects 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
- B29C48/03—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
- B29C48/92—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
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
-
- 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
Abstract
The invention discloses a polyactic acid/polycarbonate alloy material, and a preparation method and application thereof. The polyactic acid/polycarbonate alloy material comprises the following raw materials in part by weight: 10 to 90 parts of polycarbonate, 10 to 90 parts of polyactic acid, 1 to 20 parts of liquid crystal high polymer and 1 to 25 parts of flexibilizer. The polyactic acid/polycarbonate alloy material is prepared by adding the raw materials into a double-screw extruder to be melted and blended. The polyactic acid/polycarbonate alloy material provided by the invention has environmentally-friendly characteristics and excellent physical and mechanical properties, and greatly improves impact strength, bending modulus and heat distortion temperature. The liquid crystal high polymer is added to promote the quick crystallization of the polyactic acid, so that the prepared polyactic acid/polycarbonate alloy can be formed quickly, the forming cycle is reduced from 80 seconds to 50 seconds, processing cost is reduced, flowability and fire resistance are improved, and the polyactic acid/polycarbonate alloy material is applicable in the fields of office automation (OA) equipment, communication equipment, automobile parts, domestic appliances and the like.
Description
Technical field
The present invention relates to a kind of poly(lactic acid)/polycarbonate alloy material, its preparation method and application thereof, this poly(lactic acid)/polycarbonate alloy material has high-performance, and environmental friendliness, can be used for fields such as office automation (OA) equipment, signal equipment, trolley part, household electrical appliance, belong to technical field of polymer processing.
Background technology
Polycarbonate has advantages such as excellent thermotolerance, outstanding impact property, broad use temperature, dimensional stability are good, has obtained application widely at each industrial sector, especially in automobile making and electronic apparatus industry.But polycarbonate has following weak point simultaneously, and melt viscosity is big, machine-shaping is difficult, and particularly stress cracking takes place massive article easily, and poor solvent resistance, thereby makes its application be subjected to certain limitation.
In recent years, from environmental angle, aspect materials used in auto manufacturing and electronic communication equipment, the poly(lactic acid) that derives from plant has been subjected to great attention.Polylactic resin can use plants such as corn, sugarcane, Ipomoea batatas to be prepared as raw material, cheap, do not rely on petroleum resources, and can carry out complete biodegradable under certain condition, thereby can save petroleum resources, and the minimizing environmental stress is a kind of extraordinary ep-type material.
Poly(lactic acid) and polycarbonate are carried out blend prepare poly(lactic acid)/polycarbonate alloy material, on the one hand because the excellent flowability that poly(lactic acid) had, can improve the problem that polycarbonate is difficult to forming process, can improve the resistance toheat and the physical strength of poly(lactic acid) on the other hand, but in the alloying preparation process of poly(lactic acid) and polycarbonate, there is following difficult point,, viscosity poor as the two consistency outward appearance of causing that has big difference has pearl effect, easily the moisture absorption and problems such as hydrolysis, poly(lactic acid) crystal property difference.Therefore, people have carried out very careful research in these areas.
CN101671476A discloses a kind of by adding the transesterification reaction between two components in tetrabutyl titanate promotion polycarbonate and the polylactic acid blend, thereby improve the consistency of each composition in the blend, reach the method that improves polycarbonate and polylactic acid blend mechanical property.
CN101280101A discloses a kind of method of coming reinforced polycarbonate and polylactic acid blend hydrolytic resistance by the adding end-capping reagent.
CN101747611A discloses a kind of method of improving polycarbonate and polylactic acid blend thermotolerance, resistance to impact shock, flame retardant resistance and mechanical property.
CN101103074A discloses and has a kind ofly improved the method for polycarbonate and polylactic acid blend hydrolytic resistance, shock-resistance by adding the olefinic graft copolymer.
CN 101035861A discloses a kind of method that improves conduction (antistatic) property by the adding carbon nanotube.
CN 101280101 discloses a kind of method of improving the alloy thermostability by the adding end-capping reagent.
CN 101671476A discloses and has a kind ofly improved the method for poly(lactic acid) and polycarbonate consistency by adding transesterification catalyst, and the alloy material that makes has excellent physical strength and resistance toheat.
But; people's research mostly concentrates on aspects such as the consistency of improving poly(lactic acid)/polycarbonate alloy, hydrolytic resistance, electroconductibility; and ignored an important problem; have crystal property though that is exactly a poly(lactic acid) itself, crystallization rate is very slow, and this will cause material rate of cooling in molding process slow; shaping cycle is long; tooling cost increases, poor dimensional stability, problem such as heat-drawn wire is on the low side, and this will limit the widespread use of this alloy material greatly.
Summary of the invention
The purpose of this invention is to provide a kind of poly(lactic acid)/polycarbonate alloy material, this alloy material shaping cycle shortens, tooling cost reduces, heat-drawn wire improves, has solvent resistance, flowability and flame retardant resistance are good, and the intensity of alloy material, rigidity and resistance toheat all have raising in various degree.
In order to achieve the above object, the invention provides a kind of poly(lactic acid)/polycarbonate alloy material, this alloy material comprises the following raw material of meter by weight:
Poly(lactic acid) 10-90 part;
Polycarbonate 10-90 part;
Liquid crystal polymer 1-20 part;
Toughner 1-25 part.
Above-mentioned poly(lactic acid)/polycarbonate alloy material, wherein, described alloy material also comprises the following raw material of meter by weight:
Halogen-free flame retardants 1-30 part;
Inorganic filler 1-50 part;
Other auxiliary agent 0.5-10 part;
Described other auxiliary agent is selected from following one or more: oxidation inhibitor, lubricant, photostabilizer, dispersion agent, releasing agent, stablizer, static inhibitor, pigment, dyestuff, UV light absorber.
Above-mentioned poly(lactic acid)/polycarbonate alloy material, wherein, described poly(lactic acid) is L-lactic acid, D-lactic acid or L, the D-lactic acid composition, the weight-average molecular weight of this poly(lactic acid) is 60000g/mol-600000g/mol.
Above-mentioned poly(lactic acid)/polycarbonate alloy material, wherein, described polycarbonate comprises linear polycarbonate resin, branched polycarbonate resin, polyester carbonate copolymer or their mixture, weight-average molecular weight is 12000g/mol-80000g/mol.
Above-mentioned poly(lactic acid)/polycarbonate alloy material, wherein, described liquid crystal polymer is a thermotropic liquid crystalline polymer, this liquid crystal polymer is pure polymeric liquid crystal copolymer or passes through glass, mineral enhanced modification liquid crystal polymer.
Above-mentioned poly(lactic acid)/polycarbonate alloy material, wherein, described toughner is any one or a few the mixture in acrylonitrile-butadiene-styrene terpolymer, MBS, esters of acrylic acid, silicon rubber modification acrylate class, ethylene-acrylate-glycidyl ester terpolymer, the glycidyl methacrylate graft ethylene-octene copolymer.
Above-mentioned poly(lactic acid)/polycarbonate alloy material, wherein, described halogen-free flame retardants is phosphoric acid ester fire retardant, silicone flame retardant, contain one or more the mixture in the nitrogen combustion inhibitor.
Above-mentioned poly(lactic acid)/polycarbonate alloy material, wherein, described inorganic filler is selected from a kind of or several mixture in glass fibre, carbon fiber, carbon nanotube, wollastonite, talcum powder, mica, granulated glass sphere, the kaolin.
The present invention also provides a kind of poly(lactic acid)/polycarbonate alloy preparation methods, this preparation method comprises following concrete steps: all raw materials are joined melt blending in the twin screw extruder, the processing temperature scope is 210 ℃-260 ℃, screw speed is 250-800 rev/min, the residence time is 1-3 minute, through cooling, drying and pelletizing, make described poly(lactic acid)/polycarbonate alloy material.
Poly(lactic acid)/polycarbonate alloy material that the present invention also provides is in the application of business automation equipment, signal equipment, trolley part, household appliance technical field.
Technical scheme of the present invention is to add liquid crystal polymer in poly(lactic acid)/polycarbonate alloy, because liquid crystal polymer has played the effect of heterogeneous nucleation and the self-strengthening that itself has in alloy, we pass through X-ray diffraction, differential scanning calorimeter and polarizing microscope are as can be seen, the crystallization rate of polylactic acid PLA is accelerated greatly in the alloy material, degree of crystallinity increases, find by injection moulding again, the adding liquid crystal polymer aftershaping cycle shortens greatly in alloy, be reduced to 50 seconds from original 80 seconds, tooling cost reduces, and the dimensional stability of goods is good.We exist a certain amount of fibrous texture the alloy as can be seen from stereoscan photograph simultaneously, this is the result of liquid crystal polymer orientation, therefore liquid crystal polymer has enhancement, the shock strength of the poly(lactic acid)/polycarbonate alloy that makes, modulus in flexure and heat-drawn wire all are improved largely, and the fluidity of molten and the flame retardant properties of material increase, and can be used for fields such as office automation (OA) equipment, signal equipment, trolley part, household electrical appliance.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is further described.
The employed raw material sources of embodiments of the invention are as follows:
Polycarbonate is bisphenol A polycarbonate (hereinafter to be referred as the PC) NF-2200 of bright dipping company, and molecular weight is 25000-28000g/mol.
Poly(lactic acid) is used the PLA 4032D(of U.S. NATURE WORKS company hereinafter to be referred as PLA).
That liquid crystal polymer (hereinafter to be referred as LCP) uses is the E5002L of Sumitomo.
Toughner uses is that the organic-silicon-modified acrylate S-2001(of the beautiful sun of Mitsubishi is hereinafter to be referred as S-2001).
Fire retardant uses is that the phosphate flame retardant PX-220(of Zhejiang Wan Sheng company is hereinafter to be referred as PX-220).
That inorganic filler uses is the glass fibre HP3786 of PPG company.
What antioxidant used is the hindered phenol anti-oxidants 1010 and the phosphorous acid esters antioxidant 168 of BASF AG.
The ZE-25 twin screw extruder that the present invention uses German Berstorff company to produce.
Salient features testing method of the present invention is as follows:
Notched Izod impact strength is tested by ASTM D256, and specimen size is 64mm*12.7mm*3.2mm, and notch depth is 2.2mm, and testing apparatus is the shock-testing machine of Britain Ray-Ran company.
The tensile property test is tested by ASTM D638, and specimen size is 168mm*13mm*3.2mm, and test speed is 50mm/min, and testing apparatus is the Instron4456 electronic tension tester of Britain Instron company.
The bending property test is tested by ASTM D790, and specimen size is 64mm*12.7mm*3.2mm, and span is 50mm, and test speed is 3mm/min, and testing apparatus is the Instron4456 electronic tension tester of Britain Instron company.
Heat-drawn wire test is tested by ASTM D648, and specimen size is 64mm*12.7mm*3.2mm, and heat-up rate is 120 ℃/h, and testing apparatus is the dimension card heat-drawn wire tester of Italian CEAST company.
The melting index test is tested according to ASTM D12438.Temperature is 230 ℃, 2.16kg.
The injection moulding machine that the present invention adopts is the SA1200/370 injection moulding machine that Ningbo Haitian Plastics Machinery Group Co., Ltd produces
Comparative Examples 1 and Comparative Examples 2 are respectively polycarbonate and polylactic acid raw material directly to be injection molded into the testing standard batten to test, and test result sees Table 1.
Embodiment 1-10 and Comparative Examples 3-7:
Formula ratio according to table 1 and table 2, with polycarbonate, poly(lactic acid), liquid crystal polymer, fire retardant, toughner, inorganic filler, antioxidant is pre-mixed even back joining from main spout and carries out melt blending the twin screw extruder, one district's temperature is 210 ℃, two district's temperature are 225 ℃, three district's temperature are 230 ℃, four district's temperature are 240 ℃, five district's temperature are 245 ℃, six district's temperature are 245 ℃, seven district's temperature are 245 ℃, eight district's temperature are 245 ℃, nine district's temperature are 245 ℃, and screw speed is 250 rev/mins, and the residence time is 2 minutes, through extruding postcooling, drying and pelletizing obtain a kind of high-performance, environmentally friendly poly(lactic acid)/polycarbonate alloy.The The performance test results of embodiment 1-5 and Comparative Examples 3 gained alloys sees Table 1, and the The performance test results of embodiment 6-10 and Comparative Examples 4-7 gained alloy sees Table 2.
Table 1: embodiment 1-5 and Comparative Examples 1-3
By embodiment 1-5 and Comparative Examples 1-3 as can be known:
Polycarbonate has notched Izod impact strength and heat-drawn wire preferably, yet its fluidity of molten (being embodied by melting index) is relatively poor.
Poly(lactic acid) has fluidity of molten and higher modulus in flexure preferably, yet its elongation at break and notched Izod impact strength, heat-drawn wire are all relatively poor.
Add liquid crystal polymer in poly(lactic acid)/polycarbonate alloy after, the 80s when shaping cycle never adds liquid crystal polymer is reduced to 50s, and heat-drawn wire, shock strength, flexural strength, modulus in flexure, melting index, flame retardant resistance all increase.
Table 2: embodiment 6-10 and Comparative Examples 4-7
From embodiment 6-8 and Comparative Examples 4-7 as can be seen, no matter be that polycarbonate (PC) is when ratio is high, still poly(lactic acid) (PLA) is when ratio is higher, we can obtain the fire retardant alloy material of over-all properties the best by adding liquid crystal polymer and toughner, the adding of toughner increases substantially the toughness of alloy material, the adding of liquid crystal polymer all is improved largely flame retardant properties, fluidity of molten, flexural strength, the modulus in flexure of alloy material, and shaping cycle shortens greatly.From embodiment 9-10 as can be seen, flame retardant properties, fluidity of molten, flexural strength, modulus in flexure that improves alloy material and the effect of shortening shaping cycle are played in the adding of liquid crystal polymer equally in glass enhancing system.
Technical scheme of the present invention promotes the rapid crystallization of poly(lactic acid) on the one hand by add liquid crystal polymer in poly(lactic acid)/polycarbonate alloy, shortens the shaping cycle of material, cuts down finished cost, improves heat-drawn wire and solvent resistance.On the other hand because liquid crystal polymer can become fine by microcosmic in the course of processing, poly(lactic acid)/polycarbonate alloy is played the enhanced effect, thereby improve intensity and rigidity, resistance toheat and the flowability of alloy material, and because liquid crystal polymer itself has very outstanding flame retardant resistance, so that the flame retardant properties of alloy also increase.
Although content of the present invention has been done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple modification of the present invention with to substitute all will be conspicuous.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. poly(lactic acid)/polycarbonate alloy material is characterized in that, this alloy material comprises the following raw material of meter by weight:
Poly(lactic acid) 10-90 part;
Polycarbonate 10-90 part;
Liquid crystal polymer 1-20 part;
Toughner 1-25 part.
2. poly(lactic acid) as claimed in claim 1/polycarbonate alloy material is characterized in that, described alloy material also comprises the following raw material of meter by weight:
Halogen-free flame retardants 1-30 part;
Inorganic filler 1-50 part;
Other auxiliary agent 0.5-10 part;
Described other auxiliary agent is selected from following one or more: oxidation inhibitor, lubricant, photostabilizer, dispersion agent, releasing agent, stablizer, static inhibitor, pigment, dyestuff, UV light absorber.
3. poly(lactic acid) as claimed in claim 1/polycarbonate alloy material is characterized in that, described poly(lactic acid) is L-lactic acid, D-lactic acid or L, the D-lactic acid composition, and the weight-average molecular weight of this poly(lactic acid) is 60000g/mol-600000g/mol.
4. poly(lactic acid) as claimed in claim 1/polycarbonate alloy material, it is characterized in that, described polycarbonate comprises linear polycarbonate resin, branched polycarbonate resin, polyester carbonate copolymer or their mixture, and weight-average molecular weight is 12000g/mol-80000g/mol.
5. poly(lactic acid) as claimed in claim 1/polycarbonate alloy material is characterized in that, described liquid crystal polymer is a thermotropic liquid crystalline polymer, and this liquid crystal polymer is pure polymeric liquid crystal copolymer or passes through glass, mineral enhanced modification liquid crystal polymer.
6. poly(lactic acid) as claimed in claim 1/polycarbonate alloy material, it is characterized in that described toughner is any one or a few the mixture in acrylonitrile-butadiene-styrene terpolymer, MBS, esters of acrylic acid, silicon rubber modification acrylate class, ethylene-acrylate-glycidyl ester terpolymer, the glycidyl methacrylate graft ethylene-octene copolymer.
7. poly(lactic acid) as claimed in claim 1/polycarbonate alloy material is characterized in that, described halogen-free flame retardants is phosphoric acid ester fire retardant, silicone flame retardant, contain one or more the mixture in the nitrogen combustion inhibitor.
8. poly(lactic acid) as claimed in claim 1/polycarbonate alloy material, it is characterized in that described inorganic filler is selected from a kind of or several mixture in glass fibre, carbon fiber, carbon nanotube, wollastonite, talcum powder, mica, granulated glass sphere, the kaolin.
9. poly(lactic acid) according to claim 1 and 2/polycarbonate alloy preparation methods, it is characterized in that, this preparation method comprises following concrete steps: all raw materials are joined melt blending in the twin screw extruder, the processing temperature scope is 210 ℃-260 ℃, screw speed is 250-800 rev/min, the residence time is 1-3 minute, through cooling, drying and pelletizing, makes described poly(lactic acid)/polycarbonate alloy material.
10. poly(lactic acid) according to claim 1/polycarbonate alloy material is in the application of business automation equipment, signal equipment, trolley part, household appliance technical field.
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| CN103013107A (en) * | 2012-11-21 | 2013-04-03 | 合肥杰事杰新材料股份有限公司 | Use of liquid crystal polymer as polymer high-temperature lubricant |
| CN103122134A (en) * | 2012-09-10 | 2013-05-29 | 重庆可益荧新材料有限公司 | Special polycarbonate engineering composite material and preparation method thereof |
| CN103205104A (en) * | 2013-05-06 | 2013-07-17 | 湖南工业大学 | Preparation method of POSS (Polyhedral Oligomeric Silsesquioxane) hybridized polylactic acid/polycarbonate alloy |
| CN103665808A (en) * | 2012-09-11 | 2014-03-26 | 富士施乐株式会社 | Resin composition and resin molded article |
| CN104086961A (en) * | 2014-07-01 | 2014-10-08 | 南京理工大学 | Flame-retardant heat-resistant reinforced polylactic acid composition and preparation method thereof |
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| CN102558798A (en) * | 2012-01-16 | 2012-07-11 | 奇瑞汽车股份有限公司 | Polylacti acid compound material for vehicles and preparing method thereof |
| CN103122134A (en) * | 2012-09-10 | 2013-05-29 | 重庆可益荧新材料有限公司 | Special polycarbonate engineering composite material and preparation method thereof |
| CN103665808A (en) * | 2012-09-11 | 2014-03-26 | 富士施乐株式会社 | Resin composition and resin molded article |
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| CN103013107A (en) * | 2012-11-21 | 2013-04-03 | 合肥杰事杰新材料股份有限公司 | Use of liquid crystal polymer as polymer high-temperature lubricant |
| CN103013107B (en) * | 2012-11-21 | 2016-12-21 | 合肥杰事杰新材料股份有限公司 | A kind of liquid crystal polymer is as the purposes of high polymer high-temperature lubricant |
| CN103205104A (en) * | 2013-05-06 | 2013-07-17 | 湖南工业大学 | Preparation method of POSS (Polyhedral Oligomeric Silsesquioxane) hybridized polylactic acid/polycarbonate alloy |
| CN104086961A (en) * | 2014-07-01 | 2014-10-08 | 南京理工大学 | Flame-retardant heat-resistant reinforced polylactic acid composition and preparation method thereof |
| CN104086961B (en) * | 2014-07-01 | 2016-03-02 | 南京理工大学 | A kind of flame-proof heat-resistant strengthens poly (lactic acid) composition and preparation method thereof |
| CN106832829A (en) * | 2017-01-09 | 2017-06-13 | 沈阳工业大学 | A kind of preparation method of halogen-free flame-proof toughening lactic acid composite material |
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