CN103819866A - High-performance permanently-antistatic flame-retardant ABS (acrylonitrile butadiene styrene) material and preparation method and application - Google Patents
High-performance permanently-antistatic flame-retardant ABS (acrylonitrile butadiene styrene) material and preparation method and application Download PDFInfo
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- CN103819866A CN103819866A CN201410054965.9A CN201410054965A CN103819866A CN 103819866 A CN103819866 A CN 103819866A CN 201410054965 A CN201410054965 A CN 201410054965A CN 103819866 A CN103819866 A CN 103819866A
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 135
- 239000003063 flame retardant Substances 0.000 title claims abstract description 66
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 title abstract description 33
- 239000000463 material Substances 0.000 title description 35
- 239000002216 antistatic agent Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
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- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 22
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 18
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 18
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- 238000002156 mixing Methods 0.000 claims description 3
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- 238000007254 oxidation reaction Methods 0.000 claims description 3
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- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 claims description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical group O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 2
- YGYINYOHBXINNO-UHFFFAOYSA-N 4-(2,3,4-tribromophenyl)triazine Chemical compound BrC1=C(Br)C(Br)=CC=C1C1=CC=NN=N1 YGYINYOHBXINNO-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 2
- -1 antimony peroxide Chemical class 0.000 claims description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 2
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
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- 230000000694 effects Effects 0.000 abstract description 14
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000003292 glue Substances 0.000 description 20
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- 238000012360 testing method Methods 0.000 description 6
- 150000003384 small molecules Chemical class 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the technical field of ABS (acrylonitrile butadiene styrene) resin, and discloses high-performance permanently-antistatic flame-retardant ABS (acrylonitrile butadiene styrene) resin and a preparation method and application. The resin comprises the following components by mass: 60-75% of styrene resin; 7-20% of a permanently-antistatic agent; 11-23% of a flame retardant, 3-10% of a compatibilizer and 3-10% of a toughening agent. The high-performance permanently-antistatic flame-retardant ABS (acrylonitrile butadiene styrene) resin can maintain a stable permanently-antistatic effect, and at the same time, the use amount of the permanently-antistatic agent is reduced by 50%, the high-performance permanently-antistatic flame-retardant ABS (acrylonitrile butadiene styrene) resin can maintain a stable permanently-antistatic effect has a better antistatic property both in a dry or humid environment; with a low use amount of the flame retardant, the high-performance permanently-antistatic flame-retardant ABS (acrylonitrile butadiene styrene) resin has a good flame retardant performance, processing performance and good physical mechanical property, and compared with a substrate, the retention rate of the main mechanical properties is 90%. The machining process is free of small molecular substance precipitation and extraneous odour, and does not affect the appearance of prepared parts. The prepared products can be recyclable for use, the recovered products still have better antistatic properties.
Description
Technical field
The invention belongs to ABS resin technical field, particularly a kind of high-performance permanent anti-static flame-proof ABS resin and its preparation method and application.
Background technology
The terpolymer that ABS resin is made up of vinylbenzene, divinyl, vinyl cyanide, it has concentrated the high tenacity of cinnamic high workability, divinyl and the chemicals-resistant characteristic of vinyl cyanide, there is good processing characteristics, electrical insulation capability, resistance to chemical corrosion and high gloss and excellent plating performance, there is the excellent characteristics such as creep resistant is good, dimensional stability is high, molding shrinkage is little simultaneously, very extensive in field application such as automobile, electronic apparatus and household electrical appliance industries.But the oxygen index of ABS resin is low, belongs to inflammable material, and there is higher smoke density, while therefore use as electric equipment products, need to carry out ABS resin flame-retardant modified, to reach the service requirements of fire safety.In some special use occasions, such as the field that mine operation etc. easily produces static, ABS resin not only should meet certain fire-retardant requirement, also should have certain anti-static function.
The antistatic technology and the product that on market, are using at present, mainly by adding tensio-active agent, coated with conductive coating and adding the methods such as conductive filler material and realize, but all there are some familiar lacunas in these methods, cannot meet the field of some uses.The antistatic material that interpolation tensio-active agent makes can cause product surface atomization due to the migration of tensio-active agent, and the antistatic effect of material can greatly be subject to the impact of atmospheric moisture.The method that realizes antistatic effect by coating antistatic coating is more complicated, and cost is high, and the production cycle is long, and antistatic coating easily comes off, and affects product outward appearance.The method of adding the conductive filler materials such as carbon black, carbon fiber, prepared material color is single, and physical and mechanical properties is poor.
In Chinese patent CN 102020825 A, contriver makes the ABS matrix material with permanent anti-static effect by add permanent anti-static agent in ABS resin, there is lasting antistatic property, but the consistency of static inhibitor and ABS is poor, the made antistatic ABS mechanical property of materials is poor.In CN 101759974A, contriver has prepared a kind of low smell, antistatic, and the PC/ABS alloy material of high tenacity, has good mechanical property, but the addition of static inhibitor is more, and cost is higher.CN 101709126A discloses in ABS resin and has reached antistatic effect by the static inhibitor that adds small molecules type, but the static inhibitor of small molecules type is easily along with the prolongation antistatic effect of time progressively disappears, and antistatic effect is very large to the dependency of ambient moisture, affect the practical application of material.
Summary of the invention
In order to overcome the poor shortcoming of static inhibitor and ABS material compatibility in above-mentioned prior art and the deficiency that static inhibitor consumption is large, lasting effect is poor, primary and foremost purpose of the present invention is to provide a kind of high-performance permanent anti-static flame-proof ABS resin, this resin has stable permanent anti-static effect, good flame-retardance energy and processing characteristics, and separate out without small-molecule substance, free from extraneous odour, can not affect the outward appearance of product, material recoverable, still has good antistatic property after recovery.
Another object of the present invention is to provide a kind of preparation method of above-mentioned high-performance permanent anti-static flame-proof ABS resin.
Still a further object of the present invention is to provide the application of above-mentioned high-performance permanent anti-static flame-proof ABS resin in automobile, electronic apparatus, household electrical appliances.
Object of the present invention realizes by following proposal:
A kind of high-performance permanent anti-static flame-proof ABS resin, the component that comprises following massfraction:
Described styrene resin is at least one in acrylonitrile-butadiene-phenylethene grafted copolymer (ABS), acrylonitrile-styrene-acrylic copolymer (ASA) and MBS graft copolymer (MBS).
Preferably, described ABS resinoid refers to the ABS resin that substance law is synthetic.
Described permanent anti-static agent refers to for the segmented copolymer containing polyamide segment or polyethers.
Preferably, described permanent anti-static agent has as shown in the formula structure shown in ():
More preferably, selecting the density of the permanent anti-static agent of the structure shown in () that has formula is 1.14g/cm
3, fusing point is 204 ℃, surface resistivity is 10
7omh/sq, specific refractory power is 1.508.The present invention's permanent anti-static agent used is a kind of thermoplastic elastomer, can reduce material surface resistance, gives material permanent antistatic property.
Described permanent anti-static agent content is low to moderate 11wt%, and the surface resistivity of ABS resin material can reach 10
8Ω.
Described fire retardant is the mixture of bromine flame retardant and Sb system fire retardant.Wherein the weight ratio of bromide fire retardant and Sb system fire retardant is 3:1～5:1.
Described bromine flame retardant is at least one in TDE, decabromodiphynly oxide, brominated epoxy resin, brominated Polystyrene, tetrabromo-bisphenol and three (tribromo phenyl) triazine.In ABS resin, flame retardant agent content is preferably 11～15wt%, can realize the burning grade of V-0.
Described Sb system fire retardant refers at least one in sb oxide and antimonic salt.
More preferably, described Sb system fire retardant is at least one in antimonous oxide, antimony peroxide, butter of antimony and antimony pentachloride.
Described compatilizer is preferably styrene-maleic anhydride copolymer, and wherein the weight percent of maleic anhydride is 60wt%.The compatilizer that the present invention uses can improve the consistency of fluoropolymer resin and static inhibitor, and minimizing static inhibitor is deteriorated to material mechanical performance, improves the toughness of material.
Described toughner is preferably the ABS of rubber content at 50～70wt%.
More preferably, described toughner is that rubber content is 55～60wt%, and the number-average molecular weight Mn of SAN is the ABS of 10000g/mol left and right.
The toughner using in the present invention is mainly the shock strength for improving material, gives good toughness, and itself and ABS resin should have good consistency.
In ABS resin of the present invention, can also include at least one in 1～3wt% flow ability modifying agent, 0～2wt% processing aid, 0～2wt% anti-dripping agent and 0～2wt% oxidation inhibitor.
The present invention's flow ability modifying agent used is at least one in N-ethylene bis stearamide, fatty acid mixture, silicone oil, white mineral oil and silicone mixture.
The present invention also provides a kind of preparation method of above-mentioned high-performance permanent anti-static flame-proof ABS resin, comprises the following steps:
Styrene resin 60～75wt%, permanent anti-static agent 7～20wt%, fire retardant 11～23wt%, compatilizer 3～10wt% and toughner 3～10wt% are mixed, through screw extrusion press melting mixing, extruding pelletization, obtain high-performance permanent anti-static flame-proof ABS resin.
High-performance permanent anti-static flame-proof ABS resin of the present invention has stable permanent anti-static effect and good material mechanical property, can be widely used in automobile, electronic apparatus, household electric appliances, can prevent that accumulation of static electricity from causing the electric discharge phenomena of device, reduce micronic dust absorption.
Mechanism of the present invention is:
The present invention selects the segmented copolymer with polyethers or polymeric amide as permanent anti-static agent and utilizes bromine flame retardant to be mated use, use Sb system fire retardant as synergistic flame retardant simultaneously, reach under identical flame retardant rating prerequisite guaranteeing, not only reduced the consumption of fire retardant and static inhibitor and improved the antistatic property of material.And the present invention does not add inorganics etc., in the gained ABS resin course of processing without small molecules separate out, free from extraneous odour, do not affect products appearance, processing characteristics excellence.
The present invention, with respect to prior art, has following advantage and beneficial effect:
(1) TDE flame-retardant system has certain synergy to the effect performance of this permanent anti-static agent, is reaching in other situation of identical antistatic-level, can reduce the usage quantity of static inhibitor.
(2) high-performance permanent anti-static flame-proof ABS resin of the present invention has better physical and mechanical properties, stable permanent anti-static effect, good flame-retardance energy and processing characteristics, and Main Mechanical compares with base material, and its conservation rate is in 90% left and right.
(3) the required permanent anti-static agent of high-performance permanent anti-static flame-proof ABS resin of the present invention, amount of flame-retardant agent are few, antistatic property excellence.
(4) high-performance permanent anti-static flame-proof ABS resin of the present invention is separated out, free from extraneous odour, can not be affected the outward appearance of product without small-molecule substance in the course of processing.
(5) high-performance permanent anti-static flame-proof ABS resin of the present invention all has good antistatic property in very dry or moist environment.
(6) the goods recoverable of high-performance permanent anti-static flame-proof ABS resin of the present invention, still has good antistatic property after recovery.
Accompanying drawing explanation
Fig. 1 is the change curve of ABS resin electrical resistance storage period and humidity.
Fig. 2 is the water tolerance performance curve of ABS resin.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
ABS resin: ABS8391, ABS DG-MG29, Sinopec; High glue powder: ABS60p, Korea S Jin Hu; Permanent anti-static agent: MH2030, French Acker agate; Compatilizer: SMA700, Guangzhou Teng is along chemical industry; Bromine flame retardant: SAYTEX4010, Ya Bao company of the U.S.; Antimony based flame retardant: S-05N, Shanghai Mai Ruier chemistry; Oxidation inhibitor: 1010 and 168, Ciba company limited; Processing aid: amides Lubricate EBS B50 and stearic acid lubricant BS3818, the sky, Sichuan chemistry.
In the following example, preparation method's step of high-performance permanent anti-static anti-flaming ABS material is as follows:
A, each component raw material is fully mixed 10～60 minutes at high-speed mixer by proportioning;
B, said mixture is transported in twin screw extruder through the pay-off of delicate metering, each section of extruder temperature of forcing machine is controlled between 170～230 ℃, the length-to-diameter ratio of twin screw extruder is 20～35, screw speed is 200～800 revs/min, the shearing of screw rod, mixing and carry under, material is able to abundant fusing, compound, then through extruding pelletization, the dry permanent anti-static flame-proof ABS particle that obtains;
C, permanent anti-static flame-proof ABS particle is joined and in injection moulding machine, is processed into required test bars; Described injecting condition: 180～220 ℃ of barrel temperatures, 50～70 ℃ of die temperatures, injection pressure 45～85MPa.
Embodiment 1: the preparation of high-performance permanent anti-static flame-proof ABS resin
83wt%ABS resin, 3.6wt% high glue powder, the agent of 7wt% permanent anti-static, 5.8wt% compatilizer, 0.2wt% antioxidant 1010,0.2wt% irgasfos 168 and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 2: the preparation of high-performance permanent anti-static flame-proof ABS resin
80wt%ABS resin, 3.6wt% high glue powder, the agent of 10wt% permanent anti-static, 5.8wt% compatilizer, 0.2wt% antioxidant 1010,0.2wt% irgasfos 168 and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 3: the preparation of high-performance permanent anti-static flame-proof ABS resin
78wt%ABS resin, 3.6wt% high glue powder, the agent of 12wt% permanent anti-static, 5.8wt% compatilizer, 0.2wt% antioxidant 1010,0.2wt% irgasfos 168 and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 4: the preparation of high-performance permanent anti-static flame-proof ABS resin
76wt%ABS resin, 3.6wt% high glue powder, the agent of 14wt% permanent anti-static, 5.8wt% compatilizer, 0.2wt% antioxidant 1010,0.2wt% irgasfos 168 and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 5: the preparation of high-performance permanent anti-static flame-proof ABS resin
74wt%ABS resin, 3.6wt% high glue powder, the agent of 16wt% permanent anti-static, 5.8wt% compatilizer, 0.2wt% antioxidant 1010,0.2wt% irgasfos 168 and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 6: the preparation of high-performance permanent anti-static flame-proof ABS resin
72wt%ABS resin, 3.6wt% high glue powder, the agent of 18wt% permanent anti-static, 5.8wt% compatilizer, 0.2wt% antioxidant 1010,0.2wt% irgasfos 168 and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 7: the preparation of high-performance permanent anti-static flame-proof ABS resin
70wt%ABS resin, 3.6wt% high glue powder, the agent of 20wt% permanent anti-static, 5.8wt% compatilizer, 0.2wt% antioxidant 1010,0.2wt% irgasfos 168 and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 8: the preparation of high-performance permanent anti-static flame-proof ABS resin
67.2wt%ABS resin, 3.6wt% high glue powder, the agent of 7wt% permanent anti-static, 5.8wt% compatilizer, 12wt% bromine flame retardant, 4wt% Sb system fire retardant, 0.2wt% anti-dripping agent and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 9: the preparation of high-performance permanent anti-static flame-proof ABS resin
65.2wt%ABS resin, 4.6wt% high glue powder, the agent of 8wt% permanent anti-static, 5.8wt% compatilizer, 12wt% bromine flame retardant, 4wt% Sb system fire retardant, 0.2wt% anti-dripping agent and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 10: the preparation of high-performance permanent anti-static flame-proof ABS resin
63.2wt%ABS resin, 5.6wt% high glue powder, the agent of 9wt% permanent anti-static, 5.8wt% compatilizer, 12wt% bromine flame retardant, 4wt% Sb system fire retardant, 0.2wt% anti-dripping agent and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 11: the preparation of high-performance permanent anti-static flame-proof ABS resin
61.2wt%ABS resin, 6.6wt% high glue powder, the agent of 10wt% permanent anti-static, 5.8wt% compatilizer, 12wt% bromine flame retardant, 4wt% Sb system fire retardant, 0.2wt% anti-dripping agent and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 12: the preparation of high-performance permanent anti-static flame-proof ABS resin
59.2wt%ABS resin, 7.6wt% high glue powder, the agent of 11wt% permanent anti-static, 5.8wt% compatilizer, 12wt% bromine flame retardant, 4wt% Sb system fire retardant, 0.2wt% anti-dripping agent and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 13: the preparation of high-performance permanent anti-static flame-proof ABS resin
56.2wt%ABS resin, 9.6wt% high glue powder, the agent of 12wt% permanent anti-static, 5.8wt% compatilizer, 12wt% bromine flame retardant, 4wt% Sb system fire retardant, 0.2wt% anti-dripping agent and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 14: the preparation of high-performance permanent anti-static flame-proof ABS resin
61wt%ABS8391,5.4wt% high glue powder, the agent of 11wt% permanent anti-static, 5.8wt% compatilizer, 13wt% ten bromine flame retardants, 3wt% Sb system fire retardant, 0.2wt% antioxidant 1010,0.2wt% irgasfos 168,0.2wt% anti-dripping agent and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 15: the preparation of high-performance permanent anti-static flame-proof ABS resin
30.5wt%ABS8391,30.5wt%ABS DG-MG29,5.4wt% high glue powder, the agent of 11wt% permanent anti-static, 5.8wt% compatilizer, 13wt% ten bromine flame retardants, 3wt% Sb system fire retardant, 0.2wt% antioxidant 1010,0.2wt% irgasfos 168,0.2wt% anti-dripping agent and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 16: the preparation of high-performance permanent anti-static flame-proof ABS resin
43.6wt%ABS8391,17.4wt%ABS DG-MG29,5.4wt% high glue powder, the agent of 11wt% permanent anti-static, 5.8wt% compatilizer, 13wt% ten bromine flame retardants, 3wt% Sb system fire retardant, 0.2wt% antioxidant 1010,0.2wt% irgasfos 168,0.2wt% anti-dripping agent and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 17: the preparation of high-performance permanent anti-static flame-proof ABS resin
45.7wt%ABS8391,15.3wt%ABS DG-MG29,5.4wt% high glue powder, the agent of 11wt% permanent anti-static, 5.8wt% compatilizer, 13wt% ten bromine flame retardants, 3wt% Sb system fire retardant, 0.2wt% antioxidant 1010,0.2wt% irgasfos 168,0.2wt% anti-dripping agent and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 18: the preparation of high-performance permanent anti-static flame-proof ABS resin
50.7wt%ABS8391,15.3wt%ABS DG-MG29,5.4wt% high glue powder, the agent of 11wt% permanent anti-static, 5.8wt% compatilizer, 8wt% ten bromine flame retardants, 3wt% Sb system fire retardant, 0.2wt% antioxidant 1010,0.2wt% irgasfos 168,0.2wt% anti-dripping agent and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 19: the preparation of high-performance permanent anti-static flame-proof ABS resin
38.7wt%ABS8391,15.3wt%ABS DG-MG29,5.4wt% high glue powder, the agent of 11wt% permanent anti-static, 5.8wt% compatilizer, 20wt% ten bromine flame retardants, 3wt% Sb system fire retardant, 0.2wt% antioxidant 1010,0.2wt% irgasfos 168,0.2wt% anti-dripping agent and 0.2wt% processing aid are mixed in high-speed mixer, claim to drop in twin screw extruder through delicate metering again, squeeze out ﹑ through overmulling refining ﹑ and draw bar ﹑ water cooling, pelletizing, obtain high-performance permanent anti-static flame-proof ABS resin.
Embodiment 20: the performance index of high-performance permanent anti-static flame-proof ABS resin
The ABS resin that embodiment 1～17 is prepared is carried out performance test, and test event and standard are in table 1, and test result is in table 2～4.
Table 1 performance test project and standard
| Test item | Unit | Operative norm |
| Density | g/cm 3 | ISO1183-87 |
| Molten refer to (200 ℃/5kg) | g/10min | ISO1133-91 |
| Tensile strength | MPa | ISO527/2-93 |
| Elongation at break | % | ISO527/2-93 |
| Modulus in flexure | MPa | ISO178-93 |
| Flexural strength | MPa | ISO178-93 |
| Socle girder notched Izod impact strength | KJ/m 2 | ISO180-93 |
| Surface resistivity | Ω | IEC60093 |
The performance index of the ABS resin of table 2 embodiment 1～7
Can be seen by table 2, in embodiment 1～7, while not adding fire retardant, the consumption of permanent anti-static agent is in the time of 10wt% left and right, and ABS resin has up to 10
10the surface resistivity of Ω, the consumption of permanent anti-static agent is in the time of 12～14wt%, and surface resistivity is still 10
9Ω left and right, just can be reduced to 10 when the consumption of permanent anti-static agent is greater than 16wt%
8Ω.
The performance index of the ABS resin of table 3 embodiment 8～13
The performance index of the ABS resin of table 4 embodiment 14～17
| Test item | Embodiment 14 | Embodiment 15 | Embodiment 16 | Embodiment 17 |
| Tensile strength (MPa) | 39.63 | 35.7 | 37.5 | 36.8 |
| Elongation at break (MPa) | 8.12 | 11.7 | 7.93 | 9.1 |
| Socle girder notched Izod impact strength (KJ/m 2） | 6.0 | 9.64 | 7.58 | 7.43 |
| Flexural strength (MPa) | 58.8 | 53.5 | 55.6 | 55.1 |
| Modulus in flexure (MPa) | 1960 | 1766 | 1835 | 1828 |
| Melt index (g/10min) | 4.5 | 3.2 | 3.6 | 3.5 |
| Density (g/cm 3） | 1.185 | 1.180 | 1.184 | 1.183 |
| Flame retardant rating (2.0mm) | V-0 | V-0 | V-0 | V-0 |
| Surface resistivity (Ω) | 10 8 | 10 8 | 10 8 | 10 8 |
From table 3,4, the interpolation of fire retardant, makes ABS material have the antistatic property significantly improving, and when permanent anti-static agent consumption is only 11wt%, surface resistivity can be reduced to 10
8Ω, and material has the flame retardant properties of V-0, good impact property and rigidity, ABS resin of the present invention is guaranteeing under flame retardant effect and antistatic property, the permanent anti-static agent of 50wt% capable of reducing using, the consumption that greatly reduces expensive permanent anti-static agent, significantly reduces costs.Contrasted from embodiment 3 and embodiment 13, TDE flame-retardant system has certain synergy to the effect performance of this permanent anti-static agent, is reaching in other situation of identical antistatic-level, can reduce the usage quantity of static inhibitor.
Embodiment 21: the static resistance stabilizability of high-performance permanent anti-static flame-proof ABS resin
(1) for the impact of the different atmospheric moistures of research on ABS resin antistatic property of the present invention, embodiment 15 resulting materials are placed in after the environment 24h of different atmospheric moistures, the surface resistivity of material is characterized, result is as Fig. 1.As seen from Figure 1, along with the increase of atmospheric moisture, the surface resistivity of material decreases slightly, but antistatic property is all in the same order of magnitude (10
8Ω), illustrate that the antistatic property of this material is not subject to the impact of ambient moisture, has stable antistatic property.Material is at room temperature placed more than 3 years, and the surface resistivity of material increases slightly to some extent, but still has excellent antistatic property, and illustrative material has permanent antistatic performance.
(2) for whether exosyndrome material has static inhibitor separate out, the batten of embodiment 15 gained permanent anti-static anti-flaming ABS materials is boiled to the different time in boiling water, batten being placed in to 75 ℃ of oven drying 2h, then carry out the variation of test material surface resistivity, result is as shown in Figure 2.As seen from Figure 2, after poach certain hour, there is not too large variation in the surface resistivity of material, all in the same order of magnitude (10
8Ω), illustrate that static inhibitor and ABS have good consistency, be difficult for moving from matrix, and then show, ABS resin antistatic property of the present invention is not to play a role by separating out, but transmits electric charge by forming conductive network, plays antistatic property.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a high-performance permanent anti-static flame-proof ABS resin, is characterized in that the component that comprises following massfraction:
2. high-performance permanent anti-static flame-proof ABS resin according to claim 1, is characterized in that: described styrene resin is at least one in acrylonitrile-butadiene-phenylethene grafted copolymer, acrylonitrile-styrene-acrylic copolymer and MBS graft copolymer.
3. high-performance permanent anti-static flame-proof ABS resin according to claim 1, is characterized in that: described permanent anti-static agent refers to the segmented copolymer containing polyamide segment or polyethers.
4. high-performance permanent anti-static flame-proof ABS resin according to claim 1, is characterized in that: described fire retardant is the mixture of bromine flame retardant and Sb system fire retardant.
5. high-performance permanent anti-static flame-proof ABS resin according to claim 4, is characterized in that: in described fire retardant, the weight ratio of bromide fire retardant and Sb system fire retardant is 3:1～5:1.
6. high-performance permanent anti-static flame-proof ABS resin according to claim 4, is characterized in that: described bromine flame retardant is at least one in TDE, decabromodiphynly oxide, brominated epoxy resin, brominated Polystyrene, tetrabromo-bisphenol and three (tribromo phenyl) triazine; Described Sb system fire retardant is at least one in antimonous oxide, antimony peroxide, butter of antimony and antimony pentachloride.
7. high-performance permanent anti-static flame-proof ABS resin according to claim 1, is characterized in that: described compatilizer is styrene-maleic anhydride copolymer; Described toughner is the ABS of rubber content at 50～70wt%.
8. high-performance permanent anti-static flame-proof ABS resin according to claim 1, is characterized in that: include at least one in 1～3wt% flow ability modifying agent, 0～2wt% processing aid, 0～2wt% anti-dripping agent and 0～2wt% oxidation inhibitor.
9. according to a preparation method for the high-performance permanent anti-static flame-proof ABS resin described in claim 1～8 any one, it is characterized in that comprising the following steps:
Styrene resin 60～75wt%, permanent anti-static agent 7～20wt%, fire retardant 11～23wt%, compatilizer 3～10wt% and toughner 3～10wt% are mixed, through screw extrusion press melting mixing, extruding pelletization, obtain high-performance permanent anti-static flame-proof ABS resin.
10. the application in automobile, electronic apparatus, household electrical appliances according to the high-performance permanent anti-static flame-proof ABS resin described in claim 1～8 any one.
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| CN105086334A (en) * | 2015-08-28 | 2015-11-25 | 烟台顺隆化工科技有限公司 | Composite environment friendly flame retardant for ABS |
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