CN100402603C - Preparation method for flame-proof acrylonitrile-styrene copolymerized resin/acrylonitrile-chlorided polyethylene-styrene copolymerized resinplastic alloy - Google Patents
Preparation method for flame-proof acrylonitrile-styrene copolymerized resin/acrylonitrile-chlorided polyethylene-styrene copolymerized resinplastic alloy Download PDFInfo
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- CN100402603C CN100402603C CNB2006100529650A CN200610052965A CN100402603C CN 100402603 C CN100402603 C CN 100402603C CN B2006100529650 A CNB2006100529650 A CN B2006100529650A CN 200610052965 A CN200610052965 A CN 200610052965A CN 100402603 C CN100402603 C CN 100402603C
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Abstract
the invention discloses a manufacturing method of flame-proof SAN/ACS plastic alloy, which is characterized by the following: adding Br-system flame proof agent, antimony oxide, heat stabilizer, manufacturing adjuvant and anti-oxidant; heating; graining to obtain the product. the invention possesses excellent mechanic strength and manufacturing property, which can be made into different SAN/ACS plastic alloys to resist flame.
Description
Technical field
The present invention relates to the manufacture method of a kind of fire-retardant 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 AN and two kinds of monomer copolymerizations of vinylbenzene St 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.And in the present practical application,, needing plastics to have flame retardant properties for security against fire, above-mentioned improved resins does not all reach this requirement.
Summary of the invention
Technical problem to be solved by this invention provide a kind of technological design rationally, product has very high flame retardant resistance, 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 fire-retardant acrylonitrile-styrene copolymerized resin of long service life/acrylonitrile-chloride polyethylene-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 fire-retardant 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 73-92 part, wherein, the massfraction of acrylonitrile-styrene copolymerized resin is 10-90%, mass fraction is the organo-tin het stabilizer of 0.5-4, mass fraction is the bromide fire retardant of 4-12 part, mass fraction is 2-6 part antimonous oxide, and powdered acrylonitrile-chloride polyethylene-styrene copolymerized resin, organo-tin het stabilizer, bromide fire retardant and antimonous oxide are mixed;
B, with acrylonitrile-chloride polyethylene-styrene copolymerized resin, organo-tin het stabilizer, the mixture of bromide fire retardant and antimonous oxide is put into the stirring of plastics high-speed stirring mixer and is 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: 160-230 ℃, so just obtained fire-retardant 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% quality, or adding the quarternary copolymerized resin of the 4th component, the 4th monomer is methyl methacrylate or acrylate or poly-triallyl isocyanurate TAIC or 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.
Bromide fire retardant of the present invention is meant in tetrabromo-bisphenol epoxy oligomer, decabrominated dipheny base ethane, two (tetrabromo phthalimide) ethane, octa-BDE, decabromodiphenyl oxide, two (tribromophenoxy) ethane, the tetrabromo-bisphenol one or more.
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 refers to amine antioxidants and Hinered phenols antioxidant, be 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;
Owing to added the bromide fire retardant that has excellent compatibility with acrylonitrile-chloride polyethylene-styrene copolymerized resin, can play the particulate effect that coats antimonous oxide, two kinds of resins and bromide fire retardant and antimonous oxide good dispersion under plastic processing additives and forcing machine high shear have guaranteed the mechanical property and the good surface appearance smooth finish of resin; Because it is thermally-stabilised to have added organic tin, guaranteed that the hydrogen halide that bromide fire retardant and chlorinatedpolyethylene produce because of degraded is in time absorbed in high-temperature heating process, the color of resin of having avoided causing because of dehydrohalogenation changes and the physical strength reduction, the adding of oxidation inhibitor makes fire-retardant acrylonitrile-styrene copolymerized resin/acrylonitrile-chloride polyethylene-styrene copolymerized resin polyblend system more reliable and more stable, and fire-retardant acrylonitrile-styrene copolymerized resin/acrylonitrile-chloride polyethylene-styrene copolymerized resin polyblend can be used than under the severe environment outdoor.
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 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; 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 flame retardant plastics alloy 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 flame retardant plastics alloy of purposes.Since above advantage, flame retardant plastics alloy particularly suitable that present method is produced and high temperature, the special occasions that oxygen concentration is big, and product also meets the needs of security against fire more.
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 35 parts of ACS (CPE content 40%, MI=0.7g/10min), 10 parts of tetrabromo-bisphenols, 4 parts of antimonous oxides, 2.0 parts of dibutyl tin laurates.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 50 parts of particulate state SAN resins (MI=0.5g/10min) 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 160 175 190 200 210 220 230 210 200 195
The particulate state SAN/ACS polyblend of making physicals after tested is:
Draft temperature 46MPa
Shock strength 9.4KJ/M
2
87 ℃ of heat-drawn wires
Fire-retardant Ul94-VO
This kind polyblend meets the requirement of the fire-retardant SAN/ACS polyblend of high rigidity extrusion grade.
Embodiment 2:
With 45 parts of ACS (CPE content 40%, MI=1.7g/min), 8 part of ten bromic acid phenylate, 4 parts of antimonous oxides, 2 parts of toxilic acid dibutyl tins, 1.5 parts of dibutyl tin laurates, 0.8 part alpha-methyl styrene polycondensate (model M80), 1.8 parts of antioxidant CAs place homogenizer to mix and are warming up to 70 ℃, discharging is cooled to 45 ℃, this mixture and 45 parts of particulate state SAN resins (MI=2.7g/10min) 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:
Draft temperature 46MPa
Shock strength 10.7KJ/M
2
83 ℃ of heat-drawn wires
Fire-retardant Ul94-VO
This kind polyblend meets the requirement of the fire-retardant SAN/ACS polyblend of medium resistance to impact shock injection stage.
Embodiment 3:
With 68 parts of poly-triallyl isocyanurate-acrylonitrile-chloride polyethylenes-vinylbenzene quarternary copolymerized resin (CPE content 35%, TAIC content 1.5%, MI=2.6g/mm), 2.8 part thio-alcohol trioctylphosphine tin tin, 5 parts of antimonous oxides, 6 parts of two (tetrabromo phthalimide) ethane, 1.5 part alpha-methyl styrene polycondensate (model M80), 1.2 putting to mix in the homogenizer, part oxidation inhibitor 245 is warming up to 80 ℃, discharging cooling back is to room temperature, this mixture and 22 parts of particulate state SAN resins (MI=2.7g/10min) 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 39MPa
Shock strength 18.1KJ/M
2
82 ℃ of heat-drawn wires
Fire-retardant Ul94-VO
Above technical indicator meets the technical requirements of the fire-retardant SAN/ACS polyblend of HI high impact injection stage.
Embodiment 4:
With 40 parts of ACS (CPE content 40%, MI=0.7g/10min), 4 parts of octa-BDEs, 6 parts of antimonous oxides, 0.7 part of lauric acid toxilic acid dibutyl tin, 0.2 part of processing aids acrylic resin ACR, 0.9 part of antioxidant 1076,0.2 part TNPP, put 90 ℃ in high-speed stirring mixture, discharging is cooled to 45 ℃, this mixture and 32 parts of particulate state SAN resins (MI=0.5g/10min) are put into two weight-loss type feeding machines on forcing machine top respectively, 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 180 185 190 200 210 220 220 210 200 195
The particulate state SAN/ACS polyblend of making physicals after tested is:
Draft temperature 46MPa
Shock strength 10.4KJ/M
2
85 ℃ of heat-drawn wires
Fire-retardant Ul94-VO
This kind polyblend meets the requirement of the fire-retardant SAN/ACS polyblend of high rigidity extrusion grade.
Embodiment 5:
With 72 parts of ACS (CPE content 40%, MI=1.7g/min), 5 part of ten bromic acid phenylate, 2 parts of antimonous oxides, 0.5 part dibutyl tin laurate, 1.5 a part antioxidant 300 places homogenizer to mix and is warming up to 80 ℃, discharging is cooled to 45 ℃, this mixture and 8 parts of particulate state SAN resins (MI=2.7g/10min) 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:
Draft temperature 46MPa
Shock strength 12.7KJ/M
2
83 ℃ of heat-drawn wires
Fire-retardant Ul94-VO
This kind polyblend meets the requirement of the fire-retardant SAN/ACS polyblend of medium resistance to impact shock injection stage.
Embodiment 6:
With 10 parts of poly-triallyl isocyanurate-acrylonitrile-chloride polyethylenes-vinylbenzene quarternary copolymerized resin (CPE content 35%, TAIC content 1.5%, MI=2.6g/mm), 1 part of toxilic acid dibutyl tin, 3 parts of antimonous oxides, 7 parts of decabromodiphenyl oxides, 1.2 part processing aids acrylic resin ACR, put to mix in the homogenizer and be warming up to 85 ℃, discharging cooling back is to room temperature, this mixture and 80 parts of particulate state SAN resins (MI=2.7g/10min) 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 39MPa
Shock strength 17.1KJ/M
2
81 ℃ of heat-drawn wires
Fire-retardant Ul94-VO
Above technical indicator meets the technical requirements of the fire-retardant SAN/ACS polyblend of HI high impact injection stage.
Embodiment 7:
With 22 parts of ACS (CPE content 40%, MI=0.7g/10min), 12 parts of two (tribromophenoxy) ethane, 2.5 parts of antimonous oxides, 1.5 parts of dibutyl tin laurates.1 part of alpha-methyl styrene condenses (model M80), 2 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 70 parts of particulate state SAN resins (MI=0.5g/10min) 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 180 185 190 200 210 220 220 210 200 195
The particulate state SAN/ACS polyblend of making physicals after tested is:
Draft temperature 48MPa
Shock strength 11.4KJ/M
2
89 ℃ of heat-drawn wires
Fire-retardant Ul94-VO
This kind polyblend meets the requirement of the fire-retardant SAN/ACS polyblend of high rigidity extrusion grade.
Embodiment 8:
With 32 parts of ACS (CPE content 40%, MI=1.7g/min), 11 part of ten bromic acid phenylate, 3.5 parts of antimonous oxides, 2 parts of dibutyl tin laurates, 1.5 part toxilic acid dibutyl tin, 0.4 part processing aids acrylic resin ACR, 1.5 parts of antioxidant BHTs place homogenizer to mix and are warming up to 70 ℃, discharging is cooled to 45 ℃, this mixture and 43 parts of particulate state SAN resins (MI=2.7g/10min) 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:
Draft temperature 52MPa
Shock strength 9.7KJ/M
2
82 ℃ of heat-drawn wires
Fire-retardant Ul94-VO
This kind polyblend meets the requirement of the fire-retardant SAN/ACS polyblend of medium resistance to impact shock injection stage.
Embodiment 9:
With 43 parts of poly-triallyl isocyanurate-acrylonitrile-chloride polyethylenes-vinylbenzene quarternary copolymerized resin (CPE content 35%, TAIC content 1.5%, MI=2.6g/mm), 3 parts of toxilic acid dibutyl tins, 4.5 part antimonous oxide, 9 parts of two (tribromophenoxy) ethane, 0.9 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 30 parts of particulate state SAN resins (MI=2.7g/10min) 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 19.1KJ/M
2
82 ℃ of heat-drawn wires
Fire-retardant Ul94-VO
Above technical indicator meets the technical requirements of the fire-retardant SAN/ACS polyblend of HI high impact injection stage.
Claims (6)
1. the manufacture method of fire-retardant acrylonitrile-styrene copolymerized resin/acrylonitrile-chloride polyethylene-styrene copolymerized resin polyblend, it is characterized in that: manufacture method is:
A, getting the total mass umber is the acrylonitrile-styrene copolymerized resin and the acrylonitrile-chloride polyethylene-styrene copolymerized resin of 73-92 part, wherein, the massfraction of acrylonitrile-styrene copolymerized resin is 10-90%, mass fraction is the organo-tin het stabilizer of 0.5-4, mass fraction is the bromide fire retardant of 4-12 part, mass fraction is 2-6 part antimonous oxide, with powdered acrylonitrile-chloride polyethylene-styrene copolymerized resin, organo-tin het stabilizer, bromide fire retardant and antimonous oxide mix
B, with acrylonitrile-chloride polyethylene-styrene copolymerized resin, organo-tin het stabilizer, the mixture of bromide fire retardant and antimonous oxide is put into the stirring of plastics high-speed stirring mixer and is 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: 160-230 ℃, so just obtained fire-retardant acrylonitrile-styrene copolymerized resin/acrylonitrile-chloride polyethylene-styrene copolymerized resin polyblend.
2. the manufacture method of fire-retardant acrylonitrile-styrene copolymerized resin according to claim 1/acrylonitrile-chloride polyethylene-styrene copolymerized resin polyblend, it 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% quality, or adding the quarternary copolymerized resin of the 4th component, the 4th monomer is methyl methacrylate or acrylate or poly-triallyl isocyanurate TAIC or N-phenylmaleimide.
3. the manufacture method of fire-retardant acrylonitrile-styrene copolymerized resin according to claim 1/acrylonitrile-chloride polyethylene-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, lauric acid toxilic acid dibutyl tin, the thio-alcohol trioctylphosphine tin.
4. the manufacture method of fire-retardant acrylonitrile-styrene copolymerized resin according to claim 1/acrylonitrile-chloride polyethylene-styrene copolymerized resin polyblend, it is characterized in that: described bromide fire retardant is meant in tetrabromo-bisphenol epoxy oligomer, decabrominated dipheny base ethane, two (tetrabromo phthalimide) ethane, octa-BDE, decabromodiphenyl oxide, two (tribromophenoxy) ethane, the tetrabromo-bisphenol one or more.
5. the manufacture method of fire-retardant acrylonitrile-styrene copolymerized resin according to claim 1/acrylonitrile-chloride polyethylene-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, plastics oxidation inhibitor refers to amine antioxidants and Hinered phenols antioxidant, it is antioxidant BHT, 425,2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), 1076,245, CA, 300, TNPP, among the DLT.DP one or more.
6. the manufacture method of fire-retardant acrylonitrile-styrene copolymerized resin according to claim 1/acrylonitrile-chloride polyethylene-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 ACR.
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| CNB2006100529650A CN100402603C (en) | 2006-08-15 | 2006-08-15 | Preparation method for flame-proof acrylonitrile-styrene copolymerized resin/acrylonitrile-chlorided polyethylene-styrene copolymerized resinplastic alloy |
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| CN101591463B (en) * | 2009-06-12 | 2011-05-18 | 宁波镇洋化工发展有限公司 | Fire-retardant ACS/PVC plastic alloy and manufacturing method thereof |
| CN101665555B (en) * | 2009-09-01 | 2013-07-03 | 宁波镇洋化工发展有限公司 | Method for preparing continuous bulk of flame retardant and highly impact resistant acrylonitrile-chlorinated polyethylene-styrene resin |
| CN101914260B (en) * | 2010-09-01 | 2012-11-21 | 宁波镇洋新材料股份有限公司 | Flame-retardant ACS resin and manufacturing method thereof |
| CN102443238B (en) * | 2011-10-17 | 2013-07-10 | 陕西省轻工业研究设计院 | Preparation method of high temperature-resistant flame-retardant cable gum material |
| CN102617971A (en) * | 2011-12-09 | 2012-08-01 | 上海锦湖日丽塑料有限公司 | Flame-retardant ABS (acrylonitrile-butadiene-styrene) resin with high weatherability |
| CN103275452A (en) * | 2013-06-07 | 2013-09-04 | 曹广文 | Environmentally-friendly weather and aging resistant flame-retardant resin composition and preparation method thereof |
| CN109233176A (en) * | 2017-07-10 | 2019-01-18 | 合肥杰事杰新材料股份有限公司 | A kind of acrylonitrile-chloride polyethylene-styrene materials of weather-resistance flame-retardant and preparation method thereof |
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| JPH0741623A (en) * | 1993-07-30 | 1995-02-10 | Showa Denko Kk | Resin composition |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0741623A (en) * | 1993-07-30 | 1995-02-10 | Showa Denko Kk | Resin composition |
| 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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Owner name: HANGZHOU KELI CHEMICAL CO., LTD. Free format text: FORMER NAME: KELI CHEMICAL CO., LTD., HANGZHOU |
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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 |