CN102153831A - Acrylonitrile-chlorinated polyethylene-styrene resin composition and preparation method of acrylonitrile-chlorinated polyethylene-styrene resin composition - Google Patents
Acrylonitrile-chlorinated polyethylene-styrene resin composition and preparation method of acrylonitrile-chlorinated polyethylene-styrene resin composition Download PDFInfo
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- CN102153831A CN102153831A CN2011100995374A CN201110099537A CN102153831A CN 102153831 A CN102153831 A CN 102153831A CN 2011100995374 A CN2011100995374 A CN 2011100995374A CN 201110099537 A CN201110099537 A CN 201110099537A CN 102153831 A CN102153831 A CN 102153831A
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- acrylonitrile
- composition
- styrene resin
- weight
- chloride polyethylene
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000011342 resin composition Substances 0.000 title abstract 4
- 239000011347 resin Substances 0.000 claims abstract description 67
- 229920005989 resin Polymers 0.000 claims abstract description 67
- 239000000203 mixture Substances 0.000 claims abstract description 53
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 29
- 239000000314 lubricant Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- QSAMQSXFHVHODR-UHFFFAOYSA-N Cl.C=CC#N Chemical compound Cl.C=CC#N QSAMQSXFHVHODR-UHFFFAOYSA-N 0.000 claims description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 24
- 239000003112 inhibitor Substances 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 18
- 229920002379 silicone rubber Polymers 0.000 claims description 15
- 239000003381 stabilizer Substances 0.000 claims description 15
- 238000005453 pelletization Methods 0.000 claims description 13
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 11
- 239000006096 absorbing agent Substances 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000005060 rubber Substances 0.000 claims description 6
- -1 siloxanes Chemical class 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002466 imines Chemical class 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid group Chemical group C(CCC(=O)O)(=O)O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- XULIXFLCVXWHRF-UHFFFAOYSA-N 1,2,2,6,6-pentamethylpiperidine Chemical class CN1C(C)(C)CCCC1(C)C XULIXFLCVXWHRF-UHFFFAOYSA-N 0.000 claims description 2
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- HSKPBPOFACXOCC-UHFFFAOYSA-N OC1=C(C(=CC=C1)CN)N1N=C2C(=N1)C=CC=C2 Chemical compound OC1=C(C(=CC=C1)CN)N1N=C2C(=N1)C=CC=C2 HSKPBPOFACXOCC-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 2
- 150000001565 benzotriazoles Chemical class 0.000 claims description 2
- 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 claims description 2
- 238000012662 bulk polymerization Methods 0.000 claims description 2
- TYAJHXFESOFURV-UHFFFAOYSA-N butane-1-thiol;tin Chemical compound [Sn].CCCCS TYAJHXFESOFURV-UHFFFAOYSA-N 0.000 claims description 2
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 claims description 2
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 claims description 2
- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- NGDPCAMPVQYGCW-UHFFFAOYSA-N dibenzothiophene 5-oxide Chemical compound C1=CC=C2S(=O)C3=CC=CC=C3C2=C1 NGDPCAMPVQYGCW-UHFFFAOYSA-N 0.000 claims description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 7
- 239000004566 building material Substances 0.000 abstract description 3
- 238000004891 communication Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 238000001125 extrusion Methods 0.000 abstract 3
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 238000005469 granulation Methods 0.000 abstract 1
- 230000003179 granulation Effects 0.000 abstract 1
- 239000012760 heat stabilizer Substances 0.000 abstract 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000004075 alteration Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 206010051246 Photodermatosis Diseases 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008845 photoaging Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- 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
-
- 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
- B29C2948/9258—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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an acrylonitrile-chlorinated polyethylene-styrene resin composition and a preparation method of the acrylonitrile-chlorinated polyethylene-styrene resin composition. The composition comprises the following components in part by weight: 30 to 60 parts of acrylonitrile-chlorinated polyethylene-styrene grafting powder, 30 to 50 parts of SAN resin 1, 5 to 15 parts of weather resistance master batch, 0.3 to 3 parts of lubricant, 0.05 to 0.5 part of antioxidant and 0.5 to 1.5 parts of heat stabilizer. The composition is prepared by stirring and mixing the components except for the weather resistance master batch, adding the mixture from a main feed inlet of a double screw extrusion machine, adding the weather resistance master batch from a side feed inlet of the double screw extrusion machine and carrying out extrusion and granulation to obtain a sample. The obtained composition has excellent weather resistance, high low-temperature impact property and good antistatic property, size stability and processing property and is particularly suitable for the field of electrons, electrical appliances, communication, instruments, building materials, decorative materials, automobile parts and the like with high requirements on weather resistance, impact resistance and surface antistatic property.
Description
Technical field
The present invention relates to a kind of resin combination and preparation method thereof, especially a kind of high weatherable acrylonitrile-chloride polyethylene-composition of styrene resin and preparation method thereof.
Background technology
What ABS resin was used when synthetic is polybutadiene rubber, and wherein contained undersaturated carbon-carbon double bond is easy to be subjected to ultraviolet attack and ruptures, and causes the ABS resin product in use to produce phenomenons such as xanthochromia, efflorescence, cracking easily.ABS resin can't be directly used in the exterior product, must improve its weather resistance through surface-treated methods such as spraying, plating, but further surface treatment procedure is not only wasted time and energy, also can bring the serious environmental pollution problem, deterioration along with global environment, the application of high pollution technologies such as spraying, plating will be restricted, and this just need solve the problem of its weather-proof difference from the ABS resin base-material.ASA resin, AES resin have substituted undersaturated polybutadiene rubber in the ABS resin with saturated acrylic elastomer, terpolymer EP rubber, and weather resistance improves greatly, but cost is also very high.
The ACS resin has substituted undersaturated polybutadiene rubber in the ABS resin with saturated polyvinyl chloride rubber, and weathering resistance is not so good as ASA resin and AES resin, but improves much than the ABS resin weathering resistance, and cost is also lower.The ACS resin also has the surface of good antistatic property, is widely used in the fields such as electronics, electrical equipment, communication, instrument, building materials and finishing material, automobile component, office machinery.But compare with the AES resin with the ASA resin, the weathering resistance of ACS resin needs further to improve.And compare with ABS resin, the low temperature impact strength of ACS resin is lower.
Find in the prior art retrieval, as publication number is the Chinese invention patent of CN1908059, this invention relates to that " a kind of is base material with vinyl cyanide-styrene copolymerized resin (SAN) and vinyl cyanide-chlorinatedpolyethylene-styrene terpolymer resin fat (ACS); with 100 parts of vinyl cyanide-styrene copolymerized resins (to call SAN in the following text) and vinyl cyanide-chlorinatedpolyethylene-styrene terpolymer resin fat (to call ACS in the following text) mixture; 0.5-3 part organo-tin het stabilizer; 0-2 part plastics oxidation inhibitor; 0-2 part plastic processing additives is put into homogenizer and mixed and be warming up to 60 ℃-90 ℃; the discharging postcooling is to room temperature, then mixture is added extruding pelletization in the plastics extruder, extrude controlled temperature 170-230 ℃, get the SAN/ACS plastic alloy particle." though the product that obtains of this patent has good weather, the weather-proof and low temperature resistant requirement that can't satisfy simultaneously.
Summary of the invention
The objective of the invention is to solve above-mentioned deficiency of the prior art, a kind of acrylonitrile-chloride polyethylene-composition of styrene resin and preparation method thereof is provided, adopt weather-proof master batch and add the polymkeric substance of silicon rubber, the weather-proof and low temperature resistant requirement that can satisfy simultaneously.
For achieving the above object, the present invention by the following technical solutions:
The invention provides a kind of high weatherable acrylonitrile-chloride polyethylene-composition of styrene resin, the component that comprises and the parts by weight of each component are as follows:
Acrylonitrile-chloride polyethylene-styrene-grafted powder 30-60 part
SAN resin 1 30-50 part
Weather-proof master batch 5-15 part
Lubricant 0.3-3 part
Oxidation inhibitor 0.05-0.5 part
Thermo-stabilizer 0.5-1.5 part
Described acrylonitrile-chloride polyethylene-styrene-grafted powder is chlorinated polyethylene rubber and vinylbenzene and GRAFT COPOLYMERIZATION OF ACRYLONITRILE thing, can be one or more synthetic method gained in aqueous suspension polymerization, emulsion polymerization, solution polymerization process, the mass polymerization, the scope of its weight-average molecular weight is 50,000-200,000, rubber content is 20-50wt%, cl content 5-25wt%, and relative density is 1.04-1.11 g/cm
3
Described SAN resin 1 is vinyl cyanide and cinnamic graft copolymer, and its weight-average molecular weight is 100,000-250, and 000, acrylonitrile content is 28-38 wt %.
Described lubricant is that EBS, siloxanes, PE are cured, in Zinic stearas, Magnesium Stearate or the barium stearate one or more.
Described oxidation inhibitor is the mixture of single phenol, bis-phenol or polyphenolic substance and phosphite ester compound of being obstructed.
Described thermo-stabilizer is one or more in dibenzoic acid dibutyl tin, Mono-n-butyltin, butanethiol tin, Dibutyltin oxide DBTO, the three sad butyl tin.
The component that described weather-proof master batch comprises and the parts by weight of each component are as follows:
SAN resin 2 10-50 parts
Methyl methacrylate polymer 30-50 part
Polymkeric substance 5-15 part of silicon rubber
Compatilizer 3-8 part
Light absorber 3-7 part
Photostabilizer 3-6 part
Oxidation inhibitor 3-6 part
Described SAN resin 2 is superelevation mobile vinyl cyanide and cinnamic multipolymer, and its acrylonitrile content is 15-25%, and weight-average molecular weight is 30,000-80,000.
The weight-average molecular weight of described methyl methacrylate polymer is 50,000-200,000.
The silicon rubber content of the polymkeric substance of described silicon rubber is 60-80%, and the second-order transition temperature of rubber is lower than subzero 100 ℃.
Described compatilizer is one or more in ethylene-methyl acrylate-maleic anhydride, ethylene-butyl acrylate-maleic anhydride, ethylene-methyl acrylate-glycidyl methacrylate or ethylene-butyl acrylate-glycidyl methacrylate ternary atactic copolymer.
Described light absorber is 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole, 2-(2' hydroxyl-6'-aminomethyl phenyl) benzotriazole, 2,4-dihydroxy benzophenone, 3-[3-(benzotriazole-2-yl)-5-tert-butyl-hydroxy phenyl] methyl propionate, 3,5-di-tert-butyl-4-hydroxybenzoic acid-2, one or more in 4-di-t-butyl phenyl ester, 2-(2H-benzotriazole-2-yl) p-cresol etc.
Described photostabilizer is Succinic Acid and (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines alcohol) polymkeric substance, poly-[[6-[(1,1,3, the 3-tetramethyl butyl) amine]-1,3,5-triazines-2,4-two bases] [(2,2,6,6-tetramethyl--4-piperidines) imines]-1,6-two dihexyls [(2,2,6,6-tetramethyl--4-piperidines) imines]]], sebacic acid two (2,2,6,6-tetramethyl-piperidyl) ester, sebacic acid (1,2,2,6,6-pentamethyl-piperidines alcohol) ester, two (1-octyloxy-2,2,6,6-tetramethyl--4-piperidyl) one or more in sebate etc.
Described weather-proof master batch adopts following method to be prepared from:
(1) with 10-50 weight part SAN resin 2,30-50 parts by weight of methylmethacrylate polymkeric substance, the polymkeric substance of the silicon rubber of 5-15 weight part, 3-8 weight part compatilizer and 3-7 weight part oxidation inhibitor are put into homogenizer and are stirred that discharging obtains mixture after 5-30 minute;
(2) the main charging opening of mixture from twin screw extruder added, with 3-6 weight part light absorber and 3-6 weight part photostabilizer elder generation mixing, from the side loading mouth of twin screw extruder, add again, the barrel zone temperature of control forcing machine is 150-200 ℃, screw speed is 180-600rpm, and extruding pelletization obtains weather-proof master batch.
The present invention also provides a kind of preparation method of high weatherable acrylonitrile-chloride polyethylene-composition of styrene resin, and this method comprises the steps:
(1) get the raw materials ready, prepare material according to the parts by weight of following component and each component:
Acrylonitrile-chloride polyethylene-styrene-grafted powder 30-60 part
SAN resin 1 30-50 part
Weather-proof master batch 5-15 part
Lubricant 0.3-3 part
Oxidation inhibitor 0.05-0.5 part
Thermo-stabilizer 0.5-1.5 part
(2) acrylonitrile-chloride polyethylene-styrene-grafted powder, SAN resin 1, lubricant, oxidation inhibitor and thermo-stabilizer are put into homogenizer and are stirred 5-30min after discharging obtain mixture;
(3) the main charging opening of mixture from twin screw extruder added, weather-proof master batch is added from the side loading mouth of twin screw extruder, and through the twin screw extruder extruding pelletization, the barrel zone temperature of control forcing machine is 150-200 ℃, screw speed is 180-600rpm, and extruding pelletization obtains sample.
Above-mentioned all compounds are the commercial goods.
Compared with prior art, the present invention has the following advantages:
(1) adopt the method for weather-proof master batch can solve light absorber on the one hand and photostabilizer disperses uneven problem.Adopt polymkeric substance, the methyl methacrylate polymer of the silicon rubber of Gao Naihou in the weather-proof on the other hand master batch, mobile high, when injection moulding, can be distributed to the surface of product, thereby effective weather-proof composition is taken and be dispersed in uniformly to the surface of goods, farthest bring into play its weather resistance.
(2) adding in the side direction charging opening of weather resisting agent from twin screw extruder, can be when guaranteeing light absorber and photostabilizer dispersiveness and thermolysis do not take place.
(3) polymkeric substance that adds silicon rubber has very high low-temperature impact-resistant performance, thereby can make product satisfy application in the low temperature environment.
(4) select for use the SAN resin of suitable AN content and molecular weight under the prerequisite of assurance and ACS resin compatible, to improve its rigidity and toughness.
(5) select for use organotin as thermo-stabilizer, protection ACS resin can not decomposed by hot oxygen.
To sum up, acrylonitrile-chloride polyethylene-the composition of styrene resin of gained of the present invention has more excellent weathering resistance, higher low temperature impact properties, also have good antistatic performance, dimensional stability and processing characteristics, field such as electronics, electrical equipment, communication, instrument, building materials and the finishing material that is specially adapted to weathering resistance, shock-resistance and antistatic surface are had relatively high expectations, automobile component, office machinery.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with specific embodiment, further set forth the present invention.
Embodiment 1
Polymkeric substance, 4Kg compatilizer, the 3Kg oxidation inhibitor of 30Kg SAN resin 2,43Kg methyl methacrylate, 10Kg silicon rubber are joined stirring discharging after 20 minutes in the high-speed mixer, obtain mixture A.
Mixture A is added from the main charging opening of twin screw extruder, with 5Kg light absorber and 5Kg photostabilizer elder generation mixing, from the side loading mouth of twin screw extruder, add again, extruding pelletization obtains weather-proof master batch, the barrel zone temperature of forcing machine is 150-200 ℃, and screw speed is 180-600rpm.
45KgACS resin, 45KgSAN resin 1,0.5Kg lubricant, 0.3Kg oxidation inhibitor, 0.8Kg thermo-stabilizer are put into homogenizer stir that discharging obtains mixture B after 5-30 minute.
Mixture B is added from the main charging opening of twin screw extruder, the weather-proof master batch of 10Kg is added from the side loading mouth of twin screw extruder, extruding pelletization obtains the finished product, and the barrel zone temperature of forcing machine is 150-200 ℃, and screw speed is 180-600rpm.
Embodiment 2-4
In order to embody the characteristics of the weather-proof acrylonitrile-chloride polyethylene-composition of styrene resin of above-mentioned height preferably, the present invention has used embodiment 2-4, select the weather-proof master batch identical for use with embodiment 1, compared of the influence of the different amounts of weather-proof master batch and ACS resin to product performance, concrete material prescription sees table 1 for details, and step is with embodiment 1.
Comparative Examples 1-2
In order to embody the characteristics of the weather-proof acrylonitrile-chloride polyethylene-composition of styrene resin of above-mentioned height preferably, the present invention has also used the prescription that does not add weather-proof master batch and do not add thermo-stabilizer, and as a comparative example, concrete major ingredient prescription sees table 1 for details.
The formula table of table 1 embodiment 1-4 and Comparative Examples 1-2
For the above high weatherable acrylonitrile-chloride polyethylene-composition of styrene resin for preparing according to embodiment 1-4 and Comparative Examples 1-2, prepare test bars according to identical injecting condition, concrete physicals test item is as follows:
Tensile strength: measure tensile strength according to ASTM D 638 standards.
Normal temperature notched Izod impact strength: measure the normal temperature notched Izod impact strength according to ASTM D256 standard (1/8 " breach, 23 ℃).
Low temperature notched shock strength: batten is placed in-30 ℃ of cryogenic refrigerators and places 6h, in-30 ℃ of cryostat,s, measure the low temperature notched shock strength then according to ASTM D256 standard (1/8 " breach ,-30 ℃).
Melt flow rate (MFR): (220 ℃ of temperature, load 10Kg) measures melt flow rate (MFR) according to ASTM D 1238 standards.
Aberration after the photoaging: carry out light aging test, 1000KJ/m according to standard A STM G155-7
2After, measure the aberration of product surface before and after illumination according to standard A STM D2244.
The performance comparison of table 2 embodiment 1-4 and Comparative Examples 1-2
Performance by table 2 compares, and as can be seen, along with the raising of weather-proof master batch consumption, the weather resistance of material obviously improves, and the flowability of material improves, and the normal temperature shock strength has raising slightly, and low temperature impact strength then significantly improves; ACS grafting powder consumption improves, and the normal temperature shock strength of material improves, but low temperature impact strength when not adding quite; The interpolation of weather-proof master batch and thermo-stabilizer can increase substantially the weather resistance of material.
Embodiment 5
Polymkeric substance, 8Kg compatilizer, the 3Kg oxidation inhibitor of 10Kg SAN resin 2,50Kg methyl methacrylate, 15Kg silicon rubber are joined stirring discharging after 20 minutes in the high-speed mixer, obtain mixture A.
Mixture A is added from the main charging opening of twin screw extruder, with 3Kg light absorber and 6Kg photostabilizer elder generation mixing, from the side loading mouth of twin screw extruder, add again, extruding pelletization obtains weather-proof master batch, the barrel zone temperature of forcing machine is 150-200 ℃, and screw speed is 180-600rpm.
30KgACS resin, 50KgSAN resin 1,3Kg lubricant, 0.05Kg oxidation inhibitor, 0.5Kg thermo-stabilizer are put into homogenizer stir that discharging obtains mixture B after 5-30 minute.
Mixture B is added from the main charging opening of twin screw extruder, the weather-proof master batch of 15Kg is added from the side loading mouth of twin screw extruder, extruding pelletization obtains the finished product, and the barrel zone temperature of forcing machine is 150-200 ℃, and screw speed is 180-600rpm.
Embodiment 6
Polymkeric substance, 3Kg compatilizer, the 3Kg oxidation inhibitor of 50Kg SAN resin 2,30Kg methyl methacrylate, 5Kg silicon rubber are joined stirring discharging after 20 minutes in the high-speed mixer, obtain mixture A.
Mixture A is added from the main charging opening of twin screw extruder, with 7Kg light absorber and 3Kg photostabilizer elder generation mixing, from the side loading mouth of twin screw extruder, add again, extruding pelletization obtains weather-proof master batch, the barrel zone temperature of forcing machine is 150-200 ℃, and screw speed is 180-600rpm.
60KgACS resin, 30KgSAN resin 1,3Kg lubricant, 0.5Kg oxidation inhibitor, 1.5Kg thermo-stabilizer are put into homogenizer stir that discharging obtains mixture B after 5-30 minute.
Mixture B is added from the main charging opening of twin screw extruder, the weather-proof master batch of 5Kg is added from the side loading mouth of twin screw extruder, extruding pelletization obtains the finished product, and the barrel zone temperature of forcing machine is 150-200 ℃, and screw speed is 180-600rpm.
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof
Claims (15)
1. an acrylonitrile-chloride polyethylene-composition of styrene resin is characterized in that, the component that comprises and the parts by weight of each component are as follows:
Acrylonitrile-chloride polyethylene-styrene-grafted powder 30-60 part
SAN resin 1 30-50 part
Weather-proof master batch 5-15 part
Lubricant 0.3-3 part
Oxidation inhibitor 0.05-0.5 part
Thermo-stabilizer 0.5-1.5 part.
2. acrylonitrile-chloride polyethylene-composition of styrene resin according to claim 1, it is characterized in that, described acrylonitrile-chloride polyethylene-styrene-grafted powder is chlorinated polyethylene rubber and vinylbenzene and GRAFT COPOLYMERIZATION OF ACRYLONITRILE thing, be by one or more synthetic method gained in aqueous suspension polymerization, emulsion polymerization, solution polymerization process, the mass polymerization, the scope of its weight-average molecular weight is 50,000-200,000, rubber content is 20-50wt%, cl content 5-25wt%, relative density is 1.04-1.11 g/cm
3
3. acrylonitrile-chloride polyethylene-composition of styrene resin according to claim 1 is characterized in that, described SAN resin 1 is vinyl cyanide and cinnamic multipolymer, and its weight-average molecular weight is 130,000-250, and 000, acrylonitrile content is 28-38 wt %.
4. acrylonitrile-chloride polyethylene-composition of styrene resin according to claim 1 is characterized in that, described lubricant is that EBS, siloxanes, PE are cured, in Zinic stearas or Magnesium Stearate, the barium stearate one or more.
5. acrylonitrile-chloride polyethylene-composition of styrene resin according to claim 1 is characterized in that, described oxidation inhibitor is the mixture of single phenol, bis-phenol or polyphenolic substance and phosphite ester compound of being obstructed.
6. acrylonitrile-chloride polyethylene-composition of styrene resin according to claim 1, it is characterized in that described thermo-stabilizer is one or more in dibenzoic acid dibutyl tin, Mono-n-butyltin, butanethiol tin, Dibutyltin oxide DBTO, the three sad butyl tin.
7. acrylonitrile-chloride polyethylene-composition of styrene resin according to claim 1 is characterized in that, the component that described weather-proof master batch comprises and the parts by weight of each component are as follows:
SAN resin 2 10-50 parts
Methyl methacrylate polymer 30-50 part
Polymkeric substance 5-15 part of silicon rubber
Compatilizer 3-8 part
Light absorber 3-7 part
Photostabilizer 3-6 part
Oxidation inhibitor 3-6 part.
8. acrylonitrile-chloride polyethylene-composition of styrene resin according to claim 7 is characterized in that, described SAN resin 2 is superelevation mobile vinyl cyanide and cinnamic multipolymer, its acrylonitrile content is 15-25%, weight-average molecular weight is 30,000-80,000.
9. acrylonitrile-chloride polyethylene-composition of styrene resin according to claim 7 is characterized in that, the weight-average molecular weight of described methyl methacrylate polymer is 50,000-200,000.
10. acrylonitrile-chloride polyethylene-composition of styrene resin according to claim 7, it is characterized in that, the polymkeric substance of described silicon rubber is silicon rubber and vinyl cyanide and cinnamic multipolymer, and wherein silicon rubber content is 60-80%, and the second-order transition temperature of rubber is lower than subzero 100 ℃.
11. acrylonitrile-chloride polyethylene-composition of styrene resin according to claim 7, it is characterized in that described compatilizer is one or more in ethylene-methyl acrylate-maleic anhydride, ethylene-butyl acrylate-maleic anhydride, ethylene-methyl acrylate-glycidyl methacrylate or ethylene-butyl acrylate-glycidyl methacrylate ternary atactic copolymer.
12. acrylonitrile-chloride polyethylene-composition of styrene resin according to claim 7, it is characterized in that, described light absorber is 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole, 2-(2' hydroxyl-6'-aminomethyl phenyl) benzotriazole, 2,4-dihydroxy benzophenone, 3-[3-(benzotriazole-2-yl)-5-tert-butyl-hydroxy phenyl] methyl propionate, 3,5-di-tert-butyl-4-hydroxybenzoic acid-2, one or more in 4-di-t-butyl phenyl ester, 2-(2H-benzotriazole-2-yl) p-cresol etc.
13. acrylonitrile-chloride polyethylene-composition of styrene resin according to claim 7 is characterized in that, described photostabilizer is Succinic Acid and (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines alcohol) polymkeric substance, poly-[[6-[(1,1,3, the 3-tetramethyl butyl) amine]-1,3,5-triazine-2,4-two bases] [(2,2,6,6-tetramethyl--4-piperidines) imines]-1,6-two dihexyls [(2,2,6,6-tetramethyl--4-piperidines) imines]]], sebacic acid two (2,2,6, the 6-tetramethyl-piperidyl) ester, sebacic acid (1,2,2,6,6-pentamethyl-piperidines alcohol) ester, two (1-octyloxies-2,2,6,6-tetramethyl--4-piperidyl) one or more in sebate etc.
14. acrylonitrile-chloride polyethylene-composition of styrene resin according to claim 7 is characterized in that, described weather-proof master batch adopts following method to be prepared from:
(1) with 10-50 weight part SAN resin 2,30-50 parts by weight of methylmethacrylate polymkeric substance, the polymkeric substance of the silicon rubber of 5-15 weight part, 3-8 weight part compatilizer and 3-7 weight part oxidation inhibitor are put into homogenizer and are stirred that discharging obtains mixture after 5-30 minute;
(2) the main charging opening of mixture from twin screw extruder added, with 3-6 weight part light absorber and 3-6 weight part photostabilizer elder generation mixing, from the side loading mouth of twin screw extruder, add again, the barrel zone temperature of control forcing machine is 150-200 ℃, screw speed is 180-600rpm, and extruding pelletization obtains weather-proof master batch.
15. the preparation method of an acrylonitrile-chloride polyethylene-composition of styrene resin is characterized in that, this method comprises the steps:
(1) get the raw materials ready, prepare material according to the parts by weight of following component and each component:
Acrylonitrile-chloride polyethylene-styrene-grafted powder 30-60 part
SAN resin 1 30-50 part
Weather-proof master batch 5-15 part
Lubricant 0.3-3 part
Oxidation inhibitor 0.05-0.5 part
Thermo-stabilizer 0.5-1.5 part
(2) acrylonitrile-chloride polyethylene-styrene-grafted powder, SAN resin 1, lubricant, oxidation inhibitor and thermo-stabilizer are put into homogenizer and are stirred 5-30min after discharging obtain mixture;
(3) the main charging opening of mixture from twin screw extruder added, weather-proof master batch is added from the side loading mouth of twin screw extruder, and through the twin screw extruder extruding pelletization, the barrel zone temperature of control forcing machine is 150-200 ℃, screw speed is 180-600rpm, and extruding pelletization obtains sample.
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