CN101914260B - Flame-retardant ACS resin and manufacturing method thereof - Google Patents

Flame-retardant ACS resin and manufacturing method thereof Download PDF

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Publication number
CN101914260B
CN101914260B CN2010102734834A CN201010273483A CN101914260B CN 101914260 B CN101914260 B CN 101914260B CN 2010102734834 A CN2010102734834 A CN 2010102734834A CN 201010273483 A CN201010273483 A CN 201010273483A CN 101914260 B CN101914260 B CN 101914260B
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parts
retardant
fire
flame
resin
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CN101914260A (en
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周文斌
谢滨
王国兵
邱琪浩
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Zhejiang zhe Gang Chuangxin Chemical Technology Co., Ltd.
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NINGBO OCEANKING NEW MATERIAL CO Ltd
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Abstract

The invention relates to a flame-retardant ACS resin, which is characterized by comprising the following components. Compared with the prior art, the flame-retardant ACS resin has excellent flame retardancy, can achieve an FV-0 class, has the tensile strength of 35 to 42 MPa, the bending strength of 55 to 65 MPa and the impact strength of a cantilever beam gap of 90to 250 J/m, has high weatherability, mechanical property and machinability, and can be widely applied in the fields of electronics, electrical appliances, communications, instruments, illuminations, auto parts and the like.

Description

A kind of flame-retardant ACS resin and method of manufacture thereof
Technical field
The present invention relates to the modified-high polymer field, specifically refer to a kind of flame-retardant ACS resin and method of manufacture thereof.
Background technology
The ACS resin is meant vinyl cyanide/chlorinatedpolyethylene/cinnamic terpolymer, promptly is grafted on the main chain of chlorinatedpolyethylene (CPE) and the graftomer that forms by vinyl cyanide (AN) and vinylbenzene (St).Owing to adopt ageing-resistant CPE to replace the photothermy that receives in the ABS resin to be prone to the polyhutadiene component of deterioration by oxidation, so its weathering resistance, flame retardant resistance, antistatic property are excellent than ABS resin.Though the introducing of halogen has improved the flame retardant resistance of ACS resin, the oxygen index of universal ACS resin also is merely 20～23, belongs to non-flame-retardant materials, has limited its application in fields such as electric, automobile component, communication, office equipment.
Blending and modifying is one of measure that improves ACS resin flame retardant properties.
For example publication number is that the one Chinese patent application of CN101591463 discloses a kind of fire-retardant ACS/PVC polyblend and method of manufacture thereof.It utilizes SE (PVC) to have HS, oil resistant, chemical-resistant resistance, characteristics that flame retardant resistance is good, adds in the ACS resin, in the hope of improving the flame retardant resistance of ACS.But owing to add a large amount of polyvinyl chloride resins, make that the heat-drawn wire of fire-retardant ACS/PVC alloy is lower, and the machine-shaping TR is narrower, Application Areas is significantly limited.
Notification number is the method for manufacture that the one Chinese patent application of CN1908060 then proposes a kind of fire-retardant acrylonitrile-styrene copolymerized resin/acrylonitrile-chloride polyethylene-styrene copolymerized resin polyblend.The polyblend over-all properties that this method is made is good, but owing to adopt rigid acrylonitrile-styrene copolymerized resin (SAN) modification ACS resin, cause alloy to extrude processing temperature higher, wayward, and production cost is higher.
People such as He Song rolled up 44～46 pages of 3 phases in 2006 34 in " plastics industry " and have reported Sb 2O 3The preparation method of modification ACS matrix material and to Effect on Performance.Adopt Sb 2O 3Modification ACS resin can improve the flame retardant properties of matrix material, but has Sb 2O 3Addition is big, and the ACS resin over-all properties range of decrease is bigger, and the flame retardant properties raising receives certain restriction.
Summary of the invention
Technical problem to be solved by this invention is that the present situation that is directed against prior art provides a kind of flame-retardant ACS resin that has good weather resistance, mechanical property and processing characteristics at the same time.
Another technical problem to be solved by this invention is the method for manufacture that a kind of flame-retardant ACS resin is provided to the present situation of prior art.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: this flame-retardant ACS resin is characterized in that comprising following component:
100 parts of ACS resins
10～20 parts of bromide fire retardants
3～8 parts of Antimony Trioxide: 99.5Mins
1～4 part of stablizer
5～15 parts of toughner
0.5～2 part of lubricant
0.5～1.5 part in oxidation inhibitor
Wherein said bromide fire retardant is selected from least a in tetrabromo-bisphenol, TDE, low molecular weight brominated epoxy resin, the brominated polycarbonate oligopolymer.Described stablizer is selected from least a in calcium/zinc composite stabilizer, hydrotalcite, epoxy soybean oil, the phosphorous acid ester.Described toughner is selected from least a among SBS (styrene-butadiene-styrene block copolymer), the MBS (methacrylate butadi ene styrene copolymer).Described lubricant is selected from least a in pentaerythritol ester, ethylene bis stearic acid amide, the calcium stearate.Described oxidation inhibitor is selected from least a among antioxidant 1010,1076,168, the TNPP.The umber of above-mentioned each component is weight part.
The method of manufacture of above-mentioned flame-retardant ACS resin; It is characterized in that ACS resin, stablizer, bromide fire retardant, Antimony Trioxide: 99.5Min, toughner, lubricant and oxidation inhibitor once join by proportioning is warming up to 60～90 ℃ in the high-speed mixer; Mixed 5～15 minutes, and obtained compound; Above-mentioned compound is joined extruding pelletization in the forcing machine, and the temperature of forcing machine is provided with 150～190 ℃, and screw speed 100～400rpm obtains flame-retardant ACS resin.
Both cooperative flame retardant effects have been brought into play in the use of bromide fire retardant and Antimony Trioxide: 99.5Min compositional flame-retardant system, have reduced the usage quantity of fire retardant, and the decline of flame-retardant ACS resin physical strength obtains control to a certain degree.Because fire retardant and ACS resin compatible are relatively poor, under flame retardant properties prerequisite up to standard, should reduce its consumption as far as possible.Add an amount of toughner and can further improve the defective that the interpolation because of fire retardant causes the flame-retardant ACS resin shock strength to decline to a great extent,, can obtain the flame-retardant ACS resin of rigidity, middle anti-impact, high-impact different size and purposes through the consumption of adjustment toughner.Owing to added compound heat stabilizer; Utilize the synergistic effect between multiple thermo-stabilizer; Guarantee that the hydrogen halide that ACS resin and bromide fire retardant produce because of degraded in the high temperature process process is in time absorbed, color of resin variation, the physical strength avoiding causing because of dehydrohalogenation reduce and the mould corrosion.The interpolation of lubricant further improves the processing forming of flame-retardant ACS resin, has improved the surface smoothness of flame-retardant ACS resin.The adding of oxidation inhibitor then improves the hot workability and the thermo oxidative aging stability of flame-retardant ACS resin, has guaranteed the work-ing life of goods, makes flame-retardant ACS resin life-time service out of doors.
Owing to the best mixture temperature and the time that draw through TE, extrude processing temperature and screw speed; The good distribution of fire retardant, the plasticizing fully of resin have been guaranteed; Avoid because of excessive temperature and cross strong shearing force and cause the resin degraded, guaranteed the mechanical property and the good surface appearance smooth finish of resin.
Compared with prior art; Flame-retardant ACS resin flame retardant properties provided by the present invention is excellent, can reach the FV-0 grade, and tensile strength can reach 35～42MPa; Flexural strength is 55～65MPa; Socle girder breach resistance to impact shock can reach 90～250J/m, and weather resistance, mechanical property and processing characteristics are all good, can be widely used in fields such as electronics, electrical equipment, communication, instrument, illumination and automobile component.The method of manufacture of flame-retardant ACS resin provided by the present invention is simple, and practicality is good.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 4.0 parts of calcium/zinc composite stabilizer (Zhejiang Hai Pudun Chemical Manufacture; Trade mark HCZ 1086L), 15 parts of tetrabromo-bisphenols, 5 parts of Antimony Trioxide: 99.5Mins, 5 parts of SBS (Yanshan Petrochemical productions; The trade mark 4452), 0.5 part of antioxidant 1010,0.5 part of ethylene bis stearic acid amide join to stir in the high-speed mixer and are warming up to 60 ℃, mixed at high speed 5 minutes, discharging; Above-mentioned compound is added twin screw extruder carry out extruding pelletization, obtain flame-retardant ACS resin.Wherein the screw speed of forcing machine is 150rpm, and the temperature in 10 districts of forcing machine is provided with as shown in table 1.
Table 1
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 182 182 182 182 180 180 175 175
Flame-retardant ACS resin to obtaining carries out performance test, and test result is as shown in table 2.
Table 2
Performance Testing method Condition Unit Numerical value
Izod breach resistance to impact shock ASTM?D256 3.2mm，23℃ J/m 100
Tensile strength ASTM?D638 3.2mm，50mm/min MPa 38
Flexural strength ASTM?D790 3.2mm，2mm/min MPa 58
Heat-drawn wire ASTM?D648 6.4mm，1.82MPa ℃ 77.5
Mass flow rate ASTM?D1238 200℃，5kg g/10min 8.0
Flame retardant rating GB/T?2408-2008 1.6mm —— FV-0
Embodiment 2:
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 3.0 parts of calcium/zinc composite stabilizer (Zhejiang Hai Pudun Chemical Manufacture; Trade mark HCZ 1086L), 10 parts of TDEs, 3 parts of Antimony Trioxide: 99.5Mins, 5 parts of SBS (Yanshan Petrochemical productions; The trade mark 4452), 0.5 part of antioxidant 1010,1.0 parts of ethylene bis stearic acid amides join to stir in the high-speed mixer and are warming up to 80 ℃, mixed at high speed 5 minutes, discharging; Above-mentioned compound is added twin screw extruder carry out extruding pelletization, obtain flame-retardant ACS resin.Wherein the screw speed of forcing machine is 250rpm, and the temperature in 10 districts of forcing machine is provided with as shown in table 3.
Table 3
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 190 190 190 190 185 185 182 182
The The performance test results that obtains the ACS flame-retarded resin is as shown in table 4.
Table 4
Performance Testing method Condition Unit Numerical value
Izod breach resistance to impact shock ASTM?D256 3.2mm，23℃ ?J/m 85
Tensile strength ASTM?D638 3.2mm，50mm/min ?MPa 40
Flexural strength ASTM?D790 3.2mm，2mm/min ?MPa 64
Heat-drawn wire ASTM?D648 6.4mm，1.82MPa ?℃ 84.4
Mass flow rate ASTM?D1238 200℃，5kg ?g/10min 3.5
Flame retardant rating GB/T?2408-2008 1.6mm ?—— FV-0
Embodiment 3:
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 3.0 parts of calcium/zinc composite stabilizer (Zhejiang Hai Pudun Chemical Manufacture; Trade mark HCZ 1086L), 14 parts of brominated epoxy resins (the permanent Dehua worker in Weifang produces trade mark EC-2000), 4 parts of Antimony Trioxide: 99.5Mins, ((Yanshan Petrochemical production, the trade mark 4452), 0.6 part of antioxidant 1010,1.0 parts of ethylene bis stearic acid amides join to stir in the high-speed mixer and are warming up to 60 ℃ 5 parts of SBS; Mixed at high speed 5 minutes; Discharging adds twin screw extruder with above-mentioned compound and carries out extruding pelletization, obtains flame-retardant ACS resin.Wherein the screw speed of forcing machine is 150rpm, and the temperature in 10 districts of forcing machine is provided with as shown in table 5.
Table 5
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 185 185 185 185 182 182 180 180
The The performance test results that obtains the ACS flame-retarded resin is as shown in table 6.
Table 6
Figure BSA00000258471700051
Embodiment 4:
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 3.0 parts of calcium/zinc composite stabilizer (Zhejiang Hai Pudun Chemical Manufacture; Trade mark HCZ 1086L), 14 parts of brominated epoxy resins (the permanent Dehua worker in Weifang produces trade mark EC-4000), 4 parts of Antimony Trioxide: 99.5Mins, 5 parts of SBS (Yanshan Petrochemical production, the trade mark 4452), 0.6 part of antioxidant 1010,1.0 parts of ethylene bis stearic acid amides join to stir in the high-speed mixer and are warming up to 60 ℃; Mixed at high speed 5 minutes; Discharging adds twin screw extruder with above-mentioned compound and carries out extruding pelletization, obtains flame-retardant ACS resin.Wherein the screw speed of forcing machine is 150rpm, and the temperature in 10 districts of forcing machine is provided with as shown in table 7.
Table 7
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 185 185 185 185 182 182 180 180
The The performance test results that obtains the ACS flame-retarded resin is as shown in table 8.
Table 8
Figure BSA00000258471700052
Embodiment 5:
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 3.0 parts of calcium/zinc composite stabilizer (Zhejiang Hai Pudun Chemical Manufacture; Trade mark HCZ 1086L), 18 parts of tetrabromobisphenol a polycarbonate oligopolymers (trade mark BC-52 is produced in the plasticizing of Zhenyang, Weifang), 5 parts of Antimony Trioxide: 99.5Mins, 5 parts of SBS (Yanshan Petrochemical production, the trade mark 4452), 0.6 part of antioxidant 1076,1.0 parts of ethylene bis stearic acid amides join to stir in the high-speed mixer and are warming up to 60 ℃; Mixed at high speed 5 minutes; Discharging adds twin screw extruder with above-mentioned compound and carries out extruding pelletization, obtains flame-retardant ACS resin.Wherein the screw speed of forcing machine is 150rpm, and the temperature in 10 districts of forcing machine is provided with as shown in table 9.
Table 9
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 188 188 188 188 185 185 182 182
The The performance test results that obtains the ACS flame-retarded resin is as shown in table 10.
Table 10
Performance Testing method Condition Unit Numerical value
Izod breach resistance to impact shock ASTM?D256 3.2mm，23℃ J/m 118
Tensile strength ASTM?D638 3.2mm，50mm/min MPa 42
Flexural strength ASTM?D790 3.2mm，2mm/min MPa 64
Heat-drawn wire ASTM?D648 6.4mm，1.82MPa ℃ 83.4
Mass flow rate ASTM?D1238 200℃，5kg g/10min 5.5
Flame retardant rating GB/T?2408-2008 1.6mm —— FV-0
Embodiment 6:
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 4.0 parts of hydrotalcite (Shanghai beam allusion quotation chemical prodn; Trade mark NA-500), 14 parts of brominated epoxy resins (the permanent Dehua worker in Weifang produces trade mark EC-4000), 4 parts of Antimony Trioxide: 99.5Mins, 5 parts of SBS (Yanshan Petrochemical production, the trade mark 4452), 0.6 part of antioxidant 1076,1.0 parts of pentaerythritol esters join to stir in the high-speed mixer and are warming up to 60 ℃; Mixed at high speed 5 minutes; Discharging adds twin screw extruder with above-mentioned compound and carries out extruding pelletization, obtains flame-retardant ACS resin.Wherein the screw speed of forcing machine is 150rpm, and the temperature in 10 districts of forcing machine is provided with as shown in table 11.
Table 11
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 185 185 185 185 182 182 180 180
The The performance test results that obtains the ACS flame-retarded resin is as shown in table 12.
Table 12
Figure BSA00000258471700071
Embodiment 7:
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 4.0 parts of epoxy soybean oils, 14 parts of brominated epoxy resins (permanent Dehua worker productions in Weifang; Trade mark EC-4000), 4 parts of Antimony Trioxide: 99.5Mins, 5 parts of SBS (Yanshan Petrochemical productions; The trade mark 4452), 0.6 part of antioxidant 1076,1.0 parts of ethylene bis stearic acid amides join to stir in the high-speed mixer and are warming up to 60 ℃, mixed at high speed 5 minutes, discharging; Above-mentioned compound is added twin screw extruder carry out extruding pelletization, obtain flame-retardant ACS resin.Wherein the screw speed of forcing machine is 150rpm, and the temperature in 10 districts of forcing machine is provided with as shown in table 13.
Table 13
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 185 185 185 185 182 182 180 180
The The performance test results that obtains the ACS flame-retarded resin is as shown in table 14.
Table 14
Figure BSA00000258471700072
Embodiment 8:
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 4.0 parts of phosphorous acid ester (good great productions in Wuxi; Trade mark JH-1500), 14 parts of brominated epoxy resins (the permanent Dehua worker in Weifang produces trade mark EC-4000), 4 parts of Antimony Trioxide: 99.5Mins, 5 parts of SBS (Yanshan Petrochemical production, the trade mark 4452), 0.6 part of antioxidant 1076,1.0 parts of ethylene bis stearic acid amides join to stir in the high-speed mixer and are warming up to 60 ℃; Mixed at high speed 5 minutes; Discharging adds twin screw extruder with above-mentioned compound and carries out extruding pelletization, obtains flame-retardant ACS resin.Wherein the screw speed of forcing machine is 150rpm, and the temperature in 10 districts of forcing machine is provided with as shown in Tble 15.
Table 15
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 185 185 185 185 182 182 180 180
The The performance test results that obtains the ACS flame-retarded resin is shown in table 16.
Table 16
Figure BSA00000258471700081
Embodiment 9:
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 2.5 parts of calcium/zinc composite stabilizer (Zhejiang Hai Pudun Chemical Manufacture; Trade mark HCZ 1086L), 0.3 part of hydrotalcite (Shanghai beam allusion quotation chemical prodn; Trade mark NA-500), 0.3 part of epoxy soybean oil, 14 parts of brominated epoxy resins (the permanent Dehua worker in Weifang produces trade mark EC-4000), 4 parts of Antimony Trioxide: 99.5Mins, 5 parts of MBS (ROHM AND HAAS production, trade mark EXL 2691A), 0.2 part of antioxidant 1076,168,1.0 parts of ethylene bis stearic acid amides of 0.4 part of oxidation inhibitor, 1.0 parts of calcium stearates join to stir in the high-speed mixer and are warming up to 60 ℃; Mixed at high speed 5 minutes; Discharging adds twin screw extruder with above-mentioned compound and carries out extruding pelletization, obtains flame-retardant ACS resin.Wherein the screw speed of forcing machine is 250rpm, and the temperature in 10 districts of forcing machine is provided with shown in table 17.
Table 17
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 185 185 185 185 182 182 180 180
The The performance test results that obtains the ACS flame-retarded resin is shown in table 18.
Table 18
Figure BSA00000258471700091
Embodiment 10:
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 2.5 parts of calcium/zinc composite stabilizer (Zhejiang Hai Pudun Chemical Manufacture; Trade mark HCZ 1086L), 0.5 part of hydrotalcite (Shanghai beam allusion quotation chemical prodn; Trade mark NA-500), 0.5 part of epoxy soybean oil, 14 parts of brominated epoxy resins (the permanent Dehua worker in Weifang produces trade mark EC-4000), 4 parts of Antimony Trioxide: 99.5Mins, 10 parts of MBS (ROHM AND HAAS production, trade mark EXL 2691A), 0.4 part of antioxidant 1076,0.6 part of oxidation inhibitor TNPP, 1.0 parts of ethylene bis stearic acid amides join to stir in the high-speed mixer and are warming up to 80 ℃; Mixed at high speed 8 minutes; Discharging adds twin screw extruder with above-mentioned compound and carries out extruding pelletization, obtains flame-retardant ACS resin.Wherein the screw speed of forcing machine is 250rpm, and the temperature in 10 districts of forcing machine is provided with shown in table 19.
Table 19
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 188 188 188 188 185 185 180 180
The The performance test results that obtains the ACS flame-retarded resin is shown in table 20.
Table 20
Figure BSA00000258471700092
Embodiment 11:
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 2.5 parts of calcium/zinc composite stabilizer (Zhejiang Hai Pudun Chemical Manufacture; Trade mark HCZ 1086L), 0.5 part of hydrotalcite (Shanghai beam allusion quotation chemical prodn; Trade mark NA-500), 0.5 part of epoxy soybean oil, 18 parts of brominated epoxy resins (the permanent Dehua worker in Weifang produces trade mark EC-4000), 4 parts of Antimony Trioxide: 99.5Mins, ((ROHM AND HAAS production, trade mark EXL2691A), 0.5 part of antioxidant 1076,1.0 parts of oxidation inhibitor TNPP, 1.0 parts of ethylene bis stearic acid amides, 0.5 part of calcium stearate join to stir in the high-speed mixer and are warming up to 90 ℃ 15 parts of MBS; Mixed at high speed 15 minutes; Discharging adds twin screw extruder with above-mentioned compound and carries out extruding pelletization, obtains flame-retardant ACS resin.Wherein the screw speed of forcing machine is 300rpm, and the temperature in 10 districts of forcing machine is provided with shown in table 21.
Table 21
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 190 190 190 190 185 185 183 183
The The performance test results that obtains the ACS flame-retarded resin is shown in table 22.
Table 22
Figure BSA00000258471700101
Embodiment 12:
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 2.5 parts of calcium/zinc composite stabilizer (Zhejiang Hai Pudun Chemical Manufacture; Trade mark HCZ 1086L), 0.5 part of hydrotalcite (Shanghai beam allusion quotation chemical prodn; Trade mark NA-500), 0.5 part of epoxy soybean oil, 20 parts of brominated epoxy resins (the permanent Dehua worker in Weifang produces trade mark EC-4000), 8 parts of Antimony Trioxide: 99.5Mins, 15 parts of MBS (ROHM AND HAAS production, trade mark EXL 2691A), 0.5 part of antioxidant 1076,1.0 parts of oxidation inhibitor TNPP, 0.5 part of calcium stearate join to stir in the high-speed mixer and are warming up to 90 ℃; Mixed at high speed 15 minutes; Discharging adds twin screw extruder with above-mentioned compound and carries out extruding pelletization, obtains flame-retardant ACS resin.Wherein the screw speed of forcing machine is 300rpm, and the temperature in 10 districts of forcing machine is provided with shown in table 23.
Table 23
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 190 190 190 190 185 185 183 183
The The performance test results that obtains the ACS flame-retarded resin is shown in table 24.
Table 24
Figure BSA00000258471700111
Embodiment 13:
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark HI101), 1.5 parts of calcium/zinc composite stabilizer (Zhejiang Hai Pudun Chemical Manufacture; Trade mark HCZ 1086L), 0.5 part of hydrotalcite (Shanghai beam allusion quotation chemical prodn; Trade mark NA-500), 0.5 part of epoxy soybean oil, 18 parts of brominated epoxy resins (the permanent Dehua worker in Weifang produces trade mark EC-4000), 4 parts of Antimony Trioxide: 99.5Mins, 15 parts of MBS (ROHM AND HAAS production, trade mark EXL 2691A), 0.5 part of antioxidant 1076,1.0 parts of oxidation inhibitor TNPP, 4.0 parts of calcium stearates join to stir in the high-speed mixer and are warming up to 90 ℃; Mixed at high speed 15 minutes; Discharging adds twin screw extruder with above-mentioned compound and carries out extruding pelletization, obtains flame-retardant ACS resin.Wherein the screw speed of forcing machine is 300rpm, and the temperature in 10 districts of forcing machine is provided with as shown in Tble 25.
Table 25
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 190 190 190 190 185 185 185 185
The The performance test results that obtains the ACS flame-retarded resin is shown in table 26.
Table 26
Embodiment 14:
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 2.5 parts of calcium/zinc composite stabilizer (Zhejiang Hai Pudun Chemical Manufacture; Trade mark HCZ 1086L), 0.5 part of hydrotalcite (Shanghai beam allusion quotation chemical prodn; Trade mark NA-500), 0.5 part of epoxy soybean oil, 20 parts of brominated epoxy resins (the permanent Dehua worker in Weifang produces trade mark EC-4000), 8 parts of Antimony Trioxide: 99.5Mins, 15 parts of MBS (ROHM AND HAAS production, trade mark EXL 2691A), 0.5 part of antioxidant 1076,1.0 parts of oxidation inhibitor TNPP, 0.5 part of calcium stearate join to stir in the high-speed mixer and are warming up to 90 ℃; Mixed at high speed 15 minutes; Discharging adds twin screw extruder with above-mentioned compound and carries out extruding pelletization, obtains flame-retardant ACS resin.Wherein the screw speed of forcing machine is 100rpm, and the temperature in 10 districts of forcing machine is provided with shown in table 27.
Table 27
The extruder temperature section 1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) 150 150 190 190 190 190 185 185 183 183
The The performance test results that obtains the ACS flame-retarded resin is shown in table 28.
Table 28
Figure BSA00000258471700122
Embodiment 15:
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 2.5 parts of calcium/zinc composite stabilizer (Zhejiang Hai Pudun Chemical Manufacture; Trade mark HCZ 1086L), 0.5 part of hydrotalcite (Shanghai beam allusion quotation chemical prodn; Trade mark NA-500), 0.5 part of epoxy soybean oil, 10 parts of TDEs, 10 parts of brominated epoxy resins (the permanent Dehua worker in Weifang produces trade mark EC-4000), 8 parts of Antimony Trioxide: 99.5Mins, 15 parts of MBS (ROHM AND HAAS production, trade mark EXL 2691A), 0.5 part of antioxidant 1076,1.0 parts of oxidation inhibitor TNPP, 0.5 part of calcium stearate join to stir in the high-speed mixer and are warming up to 90 ℃; Mixed at high speed 15 minutes; Discharging adds twin screw extruder with above-mentioned compound and carries out extruding pelletization, obtains flame-retardant ACS resin.Wherein the screw speed of forcing machine is 400rpm, and the temperature in 10 districts of forcing machine is provided with shown in table 29.
Table 29
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 190 190 190 190 185 185 183 183
The The performance test results that obtains the ACS flame-retarded resin is shown in table 30.
Table 30
Figure BSA00000258471700131
Comparative Examples 1
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 5.0 parts of calcium/zinc composite stabilizer (Zhejiang Hai Pudun Chemical Manufacture; Trade mark HCZ 1086L), 14 parts of brominated epoxy resins (the permanent Dehua worker in Weifang produces trade mark EC-4000), 4 parts of Antimony Trioxide: 99.5Mins, 5 parts of SBS (Yanshan Petrochemical production, the trade mark 4452), 0.6 part of antioxidant 1010,1.0 parts of ethylene bis stearic acid amides join to stir in the high-speed mixer and are warming up to 60 ℃; Mixed at high speed 5 minutes; Discharging adds twin screw extruder with above-mentioned compound and carries out extruding pelletization, obtains flame-retardant ACS resin.Wherein the screw speed of forcing machine is 150rpm, and the temperature in 10 districts of forcing machine is provided with shown in table 31.
Table 31
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 185 185 185 185 182 182 180 180
The The performance test results that obtains the ACS flame-retarded resin is shown in table 32.
Table 32
Figure BSA00000258471700141
Comparative Examples 2
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 3.0 parts of calcium/zinc composite stabilizer (Zhejiang Hai Pudun Chemical Manufacture; Trade mark HCZ 1086L), 14 parts of brominated epoxy resins (the permanent Dehua worker in Weifang produces trade mark EC-4000), 4 parts of Antimony Trioxide: 99.5Mins, 20 parts of SBS (Yanshan Petrochemical production, the trade mark 4452), 0.6 part of antioxidant 1010,1.0 parts of ethylene bis stearic acid amides join to stir in the high-speed mixer and are warming up to 60 ℃; Mixed at high speed 5 minutes; Discharging adds twin screw extruder with above-mentioned compound and carries out extruding pelletization, obtains flame-retardant ACS resin.Wherein the screw speed of forcing machine is 200rpm, and the temperature in 10 districts of forcing machine is provided with shown in table 33.
Table 33
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 185 185 185 185 182 182 180 180
The The performance test results that obtains the ACS flame-retarded resin is shown in table 34.
Table 34
Figure BSA00000258471700142
Comparative Examples 3
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 3.0 parts of calcium/zinc composite stabilizer (Zhejiang Hai Pudun Chemical Manufacture; Trade mark HCZ 1086L), 25 parts of brominated epoxy resins (the permanent Dehua worker in Weifang produces trade mark EC-4000), 10 parts of Antimony Trioxide: 99.5Mins, 5 parts of SBS (Yanshan Petrochemical production, the trade mark 4452), 0.6 part of antioxidant 1010,1.0 parts of ethylene bis stearic acid amides join to stir in the high-speed mixer and are warming up to 60 ℃; Mixed at high speed 5 minutes; Discharging adds twin screw extruder with above-mentioned compound and carries out extruding pelletization, obtains flame-retardant ACS resin.Wherein the screw speed of forcing machine is 200rpm, and the temperature in 10 districts of forcing machine is provided with shown in table 35.
Table 35
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 185 185 185 185 182 182 180 180
The The performance test results that obtains the ACS flame-retarded resin is shown in table 36.
Table 36
Figure BSA00000258471700151
Comparative Examples 4
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 3.0 parts of calcium/zinc composite stabilizer (Zhejiang Hai Pudun Chemical Manufacture; Trade mark HCZ 1086L), 14 parts of brominated epoxy resins (the permanent Dehua worker in Weifang produces trade mark EC-4000), 4 parts of Antimony Trioxide: 99.5Mins, 5 parts of SBS (Yanshan Petrochemical production, the trade mark 4452), 0.4 part of antioxidant 1010,168,4.0 parts of ethylene bis stearic acid amides of 0.8 part of oxidation inhibitor join to stir in the high-speed mixer and are warming up to 60 ℃; Mixed at high speed 5 minutes; Discharging adds twin screw extruder with above-mentioned compound and carries out extruding pelletization, obtains flame-retardant ACS resin.Wherein the screw speed of forcing machine is 200rpm, and the temperature in 10 districts of forcing machine is provided with shown in table 37.
Table 37
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 185 185 185 185 182 182 180 180
The The performance test results that obtains the ACS flame-retarded resin is shown in table 38.
Table 38
Figure BSA00000258471700161
Comparative Examples 5
(worker's production is foreignized in the Ningbo town with 100 parts of ACS resins; Trade mark GE101), 3.0 parts of calcium/zinc composite stabilizer (Zhejiang Hai Pudun Chemical Manufacture; Trade mark HCZ 1086L), 14 parts of brominated epoxy resins (the permanent Dehua worker in Weifang produces trade mark EC-4000), 4 parts of Antimony Trioxide: 99.5Mins, 5 parts of SBS (Yanshan Petrochemical production, the trade mark 4452), 1.0 parts of antioxidant 1010s, 168,1.0 parts of ethylene bis stearic acid amides of 2.0 parts of oxidation inhibitor join to stir in the high-speed mixer and are warming up to 60 ℃; Mixed at high speed 5 minutes; Discharging adds twin screw extruder with above-mentioned compound and carries out extruding pelletization, obtains flame-retardant ACS resin.Wherein the screw speed of forcing machine is 50rpm, and the temperature in 10 districts of forcing machine is provided with shown in table 39.
Table 39
The extruder temperature section ?1 2 3 4 5 6 7 8 9 10
The temperature setting (℃) ?150 150 185 185 185 185 182 182 180 180
The The performance test results that obtains the ACS flame-retarded resin is shown in table 40.
Table 40
Figure BSA00000258471700162

Claims (8)

1. fire-retardant acrylonitrile-chlorinatedpolyethylene-styrene copolymer resin is characterized in that being made up of following material:
Figure FSB00000826398400011
Wherein said bromide fire retardant is selected from least a in tetrabromo-bisphenol, TDE, low molecular weight brominated epoxy resin or the brominated polycarbonate oligopolymer; Described stablizer is selected from least a in calcium/zinc composite stabilizer, hydrotalcite, epoxy soybean oil or the phosphorous acid ester; Described toughner is selected from least a among styrene-butadiene-styrene block copolymer SBS or the methacrylate butadi ene styrene copolymer MBS; Described lubricant is selected from least a in pentaerythritol ester, ethylene bis stearic acid amide or the calcium stearate; Described oxidation inhibitor be selected from antioxidant 1010,1076,168 or TNPP at least a; The umber of above-mentioned each component is weight part.
2. fire-retardant acrylonitrile-chlorinatedpolyethylene according to claim 1-styrene copolymer resin is characterized in that said bromide fire retardant is the mixture of TDE and low molecular weight brominated epoxy resin.
3. fire-retardant acrylonitrile-chlorinatedpolyethylene according to claim 2-styrene copolymer resin, the molecular weight that it is characterized in that said low molecular weight brominated epoxy resin is 2000～4000.
4. fire-retardant acrylonitrile-chlorinatedpolyethylene according to claim 1-styrene copolymer resin is characterized in that said stablizer is the mixture of calcium/zinc composite stabilizer, hydrotalcite and epoxy soybean oil.
5. fire-retardant acrylonitrile-chlorinatedpolyethylene according to claim 1-styrene copolymer resin is characterized in that said toughner is methacrylate butadi ene styrene copolymer.
6. fire-retardant acrylonitrile-chlorinatedpolyethylene according to claim 1-styrene copolymer resin is characterized in that described lubricant is an ethylene bis stearic acid amide.
7. fire-retardant acrylonitrile-chlorinatedpolyethylene according to claim 1-styrene copolymer resin is characterized in that said oxidation inhibitor is the mixture in antioxidant 1010 and the oxidation inhibitor 168.
8. the method for manufacture of fire-retardant acrylonitrile-chlorinatedpolyethylene as claimed in claim 1-styrene copolymer resin; It is characterized in that acrylonitrile-chloride polyethylene-styrene copolymer resin, stablizer, bromide fire retardant, Antimony Trioxide: 99.5Min, toughner, lubricant and oxidation inhibitor once join in the high-speed mixer by proportioning; Be warming up to 60～90 ℃; Mixed 5～15 minutes, and obtained compound; Above-mentioned compound is joined extruding pelletization in the forcing machine, and the temperature of forcing machine is provided with 150～190 ℃, and screw speed 100～400rpm obtains fire-retardant acrylonitrile-chlorinatedpolyethylene-vinylbenzene.
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