CN100439444C - Preparation method for acrylonitrile-styrene copolymerized resin/acrylonitrile-chlorided polyethylene-styrene copolymerized resin_plastic alloy - Google Patents
Preparation method for acrylonitrile-styrene copolymerized resin/acrylonitrile-chlorided polyethylene-styrene copolymerized resin_plastic alloy Download PDFInfo
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Abstract
the invention discloses a manufacturing method of flame-proof SAN/ACS plastic alloy, which comprises the following steps: blending 100% composition of styrene-acrylon-copolymerized resin (SAN), acrylon-chlorinated polyethylene-styrene (ACS), 0.5-3% organic tin heat-stabilizer, 0-2% plastic anti-oxidant, 0-2% plastic manufacturing adjuvant in the high-speed stirrer; heating to 60-90 deg.c; cooling to indoor temperature; graining the mixed material from plastic squeezer; controlling the squeezing temperature at 170-230 deg.c to obtain the SAN/ACS plastic alloy grain.
Description
Technical field
The present invention relates to the manufacture method of a kind of acrylonitrile-styrene copolymerized resin/acrylonitrile-chloride polyethylene-styrene copolymerized resin polyblend, it belongs to the organic chemical industry field.
Background technology
Acrylonitrile-styrene copolymerized resin is SAN, be a kind of with vinyl cyanide St and two kinds of monomer copolymerizations of vinylbenzene AN and the synthetic resins that forms, mechanical property and processing characteristics are preferably arranged, but fragility is very big, influenced its range of application, big in order to overcome SAN resin fragility, the defective that erosion-resisting characteristics is low uses ABS resin to come modification in addition, to improve its shock resistance usually, but because the polybutadiene rubber that contains among the ABS is unsaturated structure, therefore ageing resistance is poor, resistance to impact shock is little, and weathering resistance is poor, ultraviolet resistance is poor, ozone resistance is poor, shortcomings such as static resistance difference, and work-ing life is shorter, thus, its Application Areas is also narrow.
Summary of the invention
Technical problem to be solved by this invention provide a kind of technological design rationally, product has that ageing resistance is good, resistance to impact shock is big, good weatherability, ultraviolet resistance is good, ozone resistance is good, static resistance is good, the manufacture method of the acrylonitrile-styrene copolymerized resin/acrylonitrile-chloride polyethylene of long service life-styrene copolymerized resin polyblend.
The present invention solves the problems of the technologies described above the manufacture method that the technical scheme that is adopted is this acrylonitrile-styrene copolymerized resin/acrylonitrile-chloride polyethylene-styrene copolymerized resin polyblend, and manufacture method is:
A, get acrylonitrile-styrene copolymerized resin and acrylonitrile-chloride polyethylene-styrene copolymerized resin that the total mass umber is 92-99.5 part, wherein, the massfraction of acrylonitrile-styrene copolymerized resin is 10-90%, mass fraction is the organo-tin het stabilizer of 0.5-4, and powdered acrylonitrile-chloride polyethylene-styrene copolymerized resin and organo-tin het stabilizer are mixed;
B, the mixture of acrylonitrile-chloride polyethylene-styrene copolymerized resin and organo-tin het stabilizer is put into the plastics high-speed stirring mixer stir and to be warming up to 70 ℃-90 ℃, the discharging postcooling is to room temperature, the hopper that the more acrylonitrile-styrene copolymerized resin of particulate state and above-mentioned pulverulent mixture is added two weight-loss type feeding machines of plastics extruder respectively, adding forcing machine then extrudes and makes material, extruder temperature is provided with: 160230 ℃, so just obtained acrylonitrile-styrene copolymerized resin/acrylonitrile-chloride polyethylene-styrene copolymerized resin polyblend.
Acrylonitrile-chloride polyethylene-styrene copolymerized resin of the present invention is meant that chlorinated polyethylene rubber content is the ACS terpolymer resin of 20-45% content, or add the quarternary copolymerized resin of the 4th component, the 4th monomer can be, methyl methacrylate, acrylate, poly-isocyanuric acid three allyl fat (TAIC), N-phenylmaleimide.
Organic tin thermo-stabilizer of the present invention is meant one or more in dibutyl tin laurate, toxilic acid dibutyl tin, lauric acid toxilic acid dibutyl tin, the thio-alcohol trioctylphosphine tin.
It is of the present invention when powdered acrylonitrile-chloride polyethylene-styrene copolymerized resin and organo-tin het stabilizer are mixed, the plastics oxidation inhibitor that adds the 0-2 mass parts, plastics oxidation inhibitor is for referring to amine antioxidants, Hinered phenols antioxidant, as antioxidant BHT, 425,2,2 '-in methylene radical-two (the 4-methyl-6-tert butyl phenol), 1076,245, CA, 300, TNPP, DLT.DP one or more.
Of the present invention when powdered acrylonitrile-chloride polyethylene-styrene copolymerized resin and organo-tin het stabilizer are mixed, the plastic processing additives that adds the 0-2 mass parts refers to-vinyl toluene polycondensate, processing aids acrylic resin ACR.
The present invention compares with prior art and has the following advantages and effect: because acrylonitrile-styrene copolymerized resin is improved with acrylonitrile-chloride polyethylene-styrene copolymerized resin, make, final product resistance to impact shock, its weathering resistance, ultraviolet resistance, ozone resistance, static resistance also improve greatly, and work-ing life is than 3-7 times of the prolongation that improves with ABS resin; Because the optimal process temperature through overtesting draws has guaranteed the plasticizing fully of resin, avoid causing the resin degraded because of excessive temperature; Owing to used plastic processing additives in the course of processing, two kinds of resin dispersion are good under plastic processing additives and forcing machine high shear, guaranteed the mechanical property and the good surface appearance smooth finish of resin; Owing in the course of processing, used plastics oxidation inhibitor, make product at strong ultraviolet radiation, the ozone corrosion can not cause mechanical property to descend down, has guaranteed the work-ing life of goods, can use than under the severe environment outdoor; Owing to added the organic tin thermo-stabilizer, guaranteed that the hydrogenchloride that chlorinatedpolyethylene produces because of degraded is in time absorbed in high-temperature heating process, avoided because of taking off color of resin variation and the physical strength reduction that HCl causes; In addition, acrylonitrile-styrene copolymerized resin/acrylonitrile-chloride polyethylene-styrene copolymerized resin polyblend can be the colour batch dyeing of base-material by acrylonitrile-styrene copolymerized resin or chlorine compound material, and respond well.The ratio of acrylonitrile-styrene copolymerized resin and acrylonitrile-chloride polyethylene-styrene copolymerized resin of adjusting in the polyblend can make from rigidity to semi-rigid, the different size of impact and with the polyblend of purposes.Select for use the acrylonitrile-styrene copolymerized resin of different molecular weight and acrylonitrile-chloride polyethylene-styrene copolymerized resin to make to use extrude, mold pressing or the different size of injecting method machine-shaping and the polyblend of purposes.Because above advantage, the polyblend that present method is produced can be used for scheduler, industrial electrical equipment or household electrical appliance, office electrical equipment, shell and spare and accessory parts, and Application Areass such as automobile and motorcycle spare and accessory parts are extensive.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, and following examples are explanation of the invention and the present invention is not limited to following examples.Umber in following examples all is meant weight part.
Embodiment 1
With 40 parts of ACS (CPE content 25%), 0.8 part of dibutyl tin laurate.0.5 part alpha-methyl styrene condenses (model M80), 0.5 part of oxidation inhibitor, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), 0.2 part TNPP, put 70 ℃ in high-speed stirring mixture, discharging is cooled to 45 ℃, this mixture and 55 parts of particulate state SAN resins are put into two weight-loss type feeding machines on forcing machine top respectively, and press mixture than SAN=1: 0.95 weight ratio average rate adds, and extrudes in the twin screw extruder and makes material.Extruder temperature is set to:
Extruder temperature section 123456789 10
Temperature is provided with 180 185 190 200 210 220 230 210 200 195
The good test physicals of the particulate state SAN/ACS polyblend of making is:
Tensile strength 55MPa
Shock strength 10.6KJ/M2
86 ℃ of heat-drawn wires
This kind polyblend meets the requirement of high rigidity SAN/ACS polyblend.
Embodiment 2:
With 48 parts of ACS (CPE content 30%), (MI=1.7g/min) 1 part of toxilic acid dibutyl tin, 0.7 part processing aids acrylic resin ACR, 0.5 part of antioxidant BHT place homogenizer to mix and are warming up to 80 ℃, discharging is cooled to 45 ℃, this mixture and 50 parts of particulate state SAN resins are put respectively in two weight-loss type feeding machines of forcing machine, pressed mixture than SAN=1: 1.04 weight ratio average rate adds the twin screw extruder extruding pelletization.Extruder temperature is put with example 1, and the particulate state SAN/ACS polyblend of making physicals after tested is:
Anti-impact temperature 48MPa
Shock strength 14.7KJ/M2
84 ℃ of heat-drawn wires
This kind polyblend meets the requirement of medium resistance to impact shock SAN/ACS polyblend.
Embodiment 3:
With 20 parts of poly-triallyl isocyanurate-acrylonitrile-chloride polyethylenes-vinylbenzene quarternary copolymerized resin (CPE content 35%, TAIC content 1.5%, MI=2.6g/mm), 2 parts of toxilic acid dibutyl tins, 1.5 part alpha-methyl styrene polycondensate (model M80), 0.5 putting to mix in the homogenizer, part oxidation inhibitor 425 is warming up to 80 ℃, discharging cooling back is to room temperature, this mixture and 80 parts of particulate state SAN resins are added respectively in two the weight-loss type feeding machines in forcing machine top, by mixture than SAN=1: 2.43 weight ratio average rate adds to extrude in the twin screw extruder makes material.Extruder temperature is provided with example 1, the particulate state SAN/ACS plastic metal test physicals that causes:
Tensile strength 41MPa
Shock strength 20.3KJ/M2
82 ℃ of heat-drawn wires
Above technical indicator meets the technical requirements of HI high impact SAN/ACS polyblend.
Embodiment 4
With 11 parts of ACS (CPE content 30%), 0.8 part of lauric acid toxilic acid dibutyl tin.2 parts of alpha-methyl styrene condensess (model M80), 1.5 parts of oxidation inhibitor, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), 0.2 part TNPP, put 75 ℃ in high-speed stirring mixture, discharging is cooled to 45 ℃, this mixture and 90 parts of particulate state SAN resins are put into two weight-loss type feeding machines on forcing machine top respectively, and press mixture than SAN=1: 0.95 weight ratio average rate adds, and extrudes in the twin screw extruder and makes material.Extruder temperature is set to:
Extruder temperature section 123456789 10
Temperature is provided with the good test physicals of the 160 175 190 200 210 220 220 210 200 195 particulate state SAN/ACS polyblends of making:
Tensile strength 55MPa
Shock strength 10.7KJ/M2
86 ℃ of heat-drawn wires
This kind polyblend meets the requirement of high rigidity SAN/ACS polyblend.
Embodiment 5:
With 77 parts of ACS (CPE content 40%), (MI=1.7g/min) 1 part of thio-alcohol trioctylphosphine tin and a lauric acid toxilic acid dibutyl tin, 1.8 part processing aids acrylic resin ACR, 2 parts of antioxidant 1076s place homogenizer to mix and are warming up to 78 ℃, discharging is cooled to 45 ℃, this mixture and 20 parts of particulate state SAN resins are put respectively in two weight-loss type feeding machines of forcing machine, pressed mixture than SAN=1: 1.04 weight ratio average rate adds the twin screw extruder extruding pelletization.Extruder temperature is put with example 1, and the particulate state SAN/ACS polyblend of making physicals after tested is:
Anti-impact temperature 48MPa
Shock strength 14.7KJ/M2
84 ℃ of heat-drawn wires
This kind polyblend meets the requirement of medium resistance to impact shock SAN/ACS polyblend.
Embodiment 6:
With 91 parts of poly-triallyl isocyanurate-acrylonitrile-chloride polyethylenes-vinylbenzene quarternary copolymerized resin (CPE content 30%, TAIC content 1.5%, MI=2.6g/mm), 2.8 part toxilic acid dibutyl tin, 1.3 part alpha-methyl styrene polycondensate (model M80), 0.1 putting to mix in the homogenizer, a part antioxidant CA is warming up to 82 ℃, discharging cooling back is to room temperature, this mixture and 10 parts of particulate state SAN resins are added respectively in two the weight-loss type feeding machines in forcing machine top, by mixture than SAN=1: 2.43 weight ratio average rate adds to extrude in the twin screw extruder makes material.Extruder temperature is provided with example 1, the particulate state SAN/ACS plastic metal test physicals that causes:
Tensile strength 41MPa
Shock strength 18.3KJ/M2
82 ℃ of heat-drawn wires
Above technical indicator meets the technical requirements of HI high impact SAN/ACS polyblend.
Embodiment 7:
With 73 parts of poly-triallyl isocyanurate-acrylonitrile-chloride polyethylenes-vinylbenzene quarternary copolymerized resin (CPE content 35%, TAIC content 1.5%, MI=2.6g/mm), 4 parts of toxilic acid dibutyl tins, 1.1 putting to mix in the homogenizer, a part oxidation inhibitor DLT is warming up to 87 ℃, discharging cooling back is to room temperature, this mixture and 30 parts of particulate state SAN resins are added respectively in two the weight-loss type feeding machines in forcing machine top, by mixture than SAN=1: 2.43 weight ratio average rate adds to extrude in the twin screw extruder makes material.Extruder temperature is provided with together
Example 1, the particulate state SAN/ACS plastic metal test physicals that causes are:
Tensile strength 41MPa
Shock strength 20.3KJ/M2
82 ℃ of heat-drawn wires
Above technical indicator meets the technical requirements of HI high impact SAN/ACS polyblend.
Embodiment 8:
With 49.5 parts of ACS (CPE content 40%), (MI=1.7g/min) 0.5 part of dibutyl tin laurate, 0.2 a part processing aids acrylic resin ACR places homogenizer to mix and is warming up to 90 ℃, discharging is cooled to 45 ℃, this mixture and 50 parts of particulate state SAN resins are put respectively in two weight-loss type feeding machines of forcing machine, pressed mixture than SAN=1: 1.04 weight ratio average rate adds the twin screw extruder extruding pelletization.Extruder temperature is put with example 1, and the particulate state SAN/ACS polyblend of making physicals after tested is:
Anti-impact temperature 48MPa
Shock strength 14.9KJ/M2
82 ℃ of heat-drawn wires
This kind polyblend meets the requirement of medium resistance to impact shock SAN/ACS polyblend.
Claims (5)
1, the manufacture method of a kind of acrylonitrile-styrene copolymerized resin/acrylonitrile-chloride polyethylene-styrene copolymerized resin polyblend, it is characterized in that: manufacture method is:
A, get acrylonitrile-styrene copolymerized resin and acrylonitrile-chloride polyethylene-styrene copolymerized resin that the total mass umber is 92-99.5 part, wherein, the massfraction of acrylonitrile-styrene copolymerized resin is 10-90%, mass fraction is the organo-tin het stabilizer of 0.5-4, and powdered acrylonitrile-chloride polyethylene-styrene copolymerized resin and organo-tin het stabilizer are mixed;
B, the mixture of acrylonitrile-chloride polyethylene-styrene copolymerized resin and organo-tin het stabilizer is put into the plastics high-speed stirring mixer stir and to be warming up to 70 ℃-90 ℃, the discharging postcooling is to room temperature, the hopper that the more acrylonitrile-styrene copolymerized resin of particulate state and above-mentioned pulverulent mixture is added two weight-loss type feeding machines of plastics extruder respectively, adding forcing machine then extrudes and makes material, extruder temperature setting: 160-230 ℃; So just obtained acrylonitrile-styrene copolymerized resin/acrylonitrile-chloride polyethylene-styrene copolymerized resin polyblend.
2, the manufacture method of acrylonitrile-styrene copolymerized resin/acrylonitrile-chloride polyethylene according to claim 1-styrene copolymerized resin polyblend is characterized in that: described acrylonitrile-chloride polyethylene-styrene copolymerized resin is meant that chlorinated polyethylene rubber content is the ACS terpolymer resin of 20-45% content.
3, the manufacture method of acrylonitrile-styrene copolymerized resin/acrylonitrile-chloride polyethylene according to claim 1-styrene copolymerized resin polyblend is characterized in that: described organic tin thermo-stabilizer is meant one or more in dibutyl tin laurate, toxilic acid dibutyl tin, the lauric acid toxilic acid dibutyl tin.
4, the manufacture method of acrylonitrile-styrene copolymerized resin/acrylonitrile-chloride polyethylene according to claim 1-styrene copolymerized resin polyblend, it is characterized in that: described when powdered acrylonitrile-chloride polyethylene-styrene copolymerized resin and organo-tin het stabilizer are mixed, the plastics oxidation inhibitor that adds the 0-2 mass parts, this plastics oxidation inhibitor is one or more among BHT, 425,2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), 1076,245,300, TNPP, the DLT.DP.
5, the manufacture method of acrylonitrile-styrene copolymerized resin/acrylonitrile-chloride polyethylene according to claim 1-styrene copolymerized resin polyblend, it is characterized in that: described when powdered acrylonitrile-chloride polyethylene-styrene copolymerized resin and organo-tin het stabilizer are mixed, the plastic processing additives that adds the 0-2 mass parts refers to alpha-methyl styrene polycondensate, processing aids acrylic resin.
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| CN102153831B (en) * | 2011-04-20 | 2013-06-26 | 上海锦湖日丽塑料有限公司 | Acrylonitrile-chlorinated polyethylene-styrene resin composition and preparation method of acrylonitrile-chlorinated polyethylene-styrene resin composition |
| CN102153830B (en) * | 2011-04-20 | 2013-10-09 | 上海锦湖日丽塑料有限公司 | ACS (acrylonitrile-chlorinated polyethylene-styrene) resin composition and method for preparing same |
| CN103772873B (en) * | 2014-01-20 | 2016-02-10 | 太仓市晨洲塑业有限公司 | A kind of ameliorative AS resin formula |
| CN107814989B (en) * | 2016-09-14 | 2020-07-24 | 中国石油化工股份有限公司 | Anti-aging agent composition and application thereof, polymer composition, oil-extended rubber and application thereof, and vehicle tire |
| CN107226873B (en) * | 2017-06-27 | 2019-07-23 | 湖南师范大学 | A kind of method and products thereof preparing 2,6 di t butyl phenol anti-oxidation resin |
| CN111057191A (en) * | 2018-10-16 | 2020-04-24 | 杭州新元化工技术开发有限公司 | Chlorinated polymethyl methacrylate-butadiene-styrene copolymer and gas-solid phase reaction preparation method thereof |
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| CN1247203A (en) * | 1999-09-10 | 2000-03-15 | 华南理工大学 | Processf or preparing isolative plastic alloy |
| CN1587290A (en) * | 2004-07-09 | 2005-03-02 | 浙江大学 | Process for preparing acrylonitrile-chlorinated polyethylene styrene resin copolymer |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247203A (en) * | 1999-09-10 | 2000-03-15 | 华南理工大学 | Processf or preparing isolative plastic alloy |
| CN1587290A (en) * | 2004-07-09 | 2005-03-02 | 浙江大学 | Process for preparing acrylonitrile-chlorinated polyethylene styrene resin copolymer |
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| Title |
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Address after: Hangzhou City, Zhejiang province 311215, Xiaoshan economic and Technological Development Zone Road No. 39 Patentee after: Hangzhou Keli Chemical Co., Ltd. Address before: Hangzhou City, Zhejiang province 311215, Xiaoshan economic and Technological Development Zone Road No. 39 Patentee before: Keli Chemical Co., Ltd., Hangzhou |