CN115403896B - A kind of ABS composite material and its preparation method and application - Google Patents
A kind of ABS composite material and its preparation method and application Download PDFInfo
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- CN115403896B CN115403896B CN202211219419.7A CN202211219419A CN115403896B CN 115403896 B CN115403896 B CN 115403896B CN 202211219419 A CN202211219419 A CN 202211219419A CN 115403896 B CN115403896 B CN 115403896B
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- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000003063 flame retardant Substances 0.000 claims abstract description 97
- 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 class 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 claims abstract description 93
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 61
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 6
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 3
- VXHYVVAUHMGCEX-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)phenol Chemical group OC1=CC=CC=C1OC1=CC=CC=C1O VXHYVVAUHMGCEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 150000003918 triazines Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 229920000089 Cyclic olefin copolymer Polymers 0.000 abstract description 3
- 229920006351 engineering plastic Polymers 0.000 abstract description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 42
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 41
- 230000000052 comparative effect Effects 0.000 description 9
- -1 phosphate compound Chemical class 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CTMFECUQKLSOGJ-UHFFFAOYSA-N 4-bromotriazine Chemical compound BrC1=CC=NN=N1 CTMFECUQKLSOGJ-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 201000007694 Athabaskan brainstem dysgenesis syndrome Diseases 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 208000020006 human HOXA1 syndromes Diseases 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical group [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an ABS composite material, a preparation method and application thereof, and relates to the technical field of engineering plastics. The invention provides an ABS composite material, which comprises the following components in parts by weight: 80-82 parts of ABS resin, 10-13 parts of brominated flame retardant, 1-3 parts of antimony flame retardant, 4-10 parts of flame retardant synergist and 0.5-1.5 parts of processing aid; the flame-retardant synergist comprises a flame-retardant synergist A and a flame-retardant synergist B, wherein the flame-retardant synergist A is silicon dioxide, and the flame-retardant synergist B is a tetrafluoroethylene-olefin copolymer. The invention provides an ABS composite material, which is characterized in that a flame retardant synergist A and a flame retardant synergist B are creatively matched together, so that the flame retardant effect is effectively and synergistically improved, and meanwhile, the addition amount of high-price brominated flame retardants and antimony flame retardants in the ABS composite material is reduced, and the excellent flame retardant performance is still maintained on the premise of greatly reducing the cost.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to an ABS composite material and a preparation method and application thereof.
Background
ABS is one of the most widely used engineering plastics, and consists of three units of acrylonitrile, butadiene and styrene, so that excellent performance is given to the ABS; acrylonitrile imparts chemical stability, oil resistance, certain rigidity and hardness to ABS resin; butadiene can improve toughness, impact resistance and cold resistance; styrene has good dielectric properties and good processability; therefore, ABS has excellent comprehensive physical and mechanical properties, excellent low-temperature impact resistance, dimensional stability and good mechanical processing. However, ABS is a flammable material, and cannot be applied to industries and fields with high safety regulations, and flame retardant modification of ABS is required.
At present, ABS flame-retardant modification mainly comprises two types of technologies, namely halogen-antimony compound flame retardant, flame-retardant modification is carried out by bromine and chlorine in combination with antimony oxide, the technology is mature at present, the market share is highest, but the technology is limited by halogen compounds and antimony compounds, the price is high at present, and meanwhile, the material performance is affected to a certain extent due to the need of filling a large amount of flame retardants; the other type is halogen-free flame retardant, the flame retardant system is mainly phosphate compound, but the current commercialization is mainly V-2 and other low flame retardant grades due to limited flame retardant efficiency, and the application of the product is limited. At present, research interest in reducing the content of flame retardant ABS (Acrylonitrile butadiene styrene) flame retardant is concentrated at home and abroad, and patent CN113429734A shows that triazine or triamine derivatives can replace part of conventional brominated flame retardant under certain addition part, but the total content of flame retardant components is not effectively reduced due to higher addition part of substitutes, so that the material cost is reduced limitedly, and meanwhile, the material performance is not effectively improved.
Disclosure of Invention
Based on the above, the present invention aims to overcome the defects of the prior art and provide an ABS composite material, and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: an ABS composite material comprises the following components in parts by weight: 80-82 parts of ABS resin, 10-13 parts of brominated flame retardant, 1-3 parts of antimony flame retardant, 4-10 parts of flame retardant synergist and 0.5-1.5 parts of processing aid; the flame-retardant synergist comprises a flame-retardant synergist A and a flame-retardant synergist B, wherein the flame-retardant synergist A is silicon dioxide, and the flame-retardant synergist B is a tetrafluoroethylene-olefin copolymer.
The invention provides an ABS composite material, which is characterized in that a flame retardant synergist A and a flame retardant synergist B are creatively matched together, so that the flame retardant effect is effectively and synergistically improved, and meanwhile, the addition amount of high-price brominated flame retardants and antimony flame retardants in the ABS composite material is reduced, and the excellent flame retardant performance is still maintained on the premise of greatly reducing the cost and maintaining the mechanical performance.
According to the invention, the flame retardant synergist A is silicon dioxide, and can be cooperated with a halogen-antimony system in the combustion process to improve the strength of carbide, so that the blocking effect on combustible gas is enhanced; the flame retardant synergist B is a copolymer of tetrafluoroethylene and olefin, hydrogen fluoride generated by combustion reacts with silicon dioxide to generate water, and has a flame retardant effect, so that the addition amount of the halogen flame retardant can be reduced.
Preferably, the weight ratio of the flame retardant synergist A to the flame retardant synergist B is: flame retardant synergist A: flame retardant synergist b= (3-5): (1-2).
The inventor of the application discovers through a great deal of experiments that when the weight ratio of the flame retardant synergist A to the flame retardant synergist B is the specific weight ratio, the prepared ABS composite material has the best flame retardant effect, and the mechanical property of the ABS composite material is further improved.
Preferably, the flame retardant synergist B is at least one of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP) and tetrafluoroethylene-ethylene copolymer (ETFE).
Preferably, the silica has a particle size D50 of 5-12 μm.
According to the invention, the flame retardant synergist A is silicon dioxide with the particle size D50 of 5-12 mu m, so that the mechanical property of the ABS composite material is further improved.
Preferably, the processing aid is at least one of an anti-dripping agent, an antioxidant and a lubricant. Further preferably, the anti-dripping agent is at least one of SAN coated polytetrafluoroethylene micro powder, acrylate coated polytetrafluoroethylene micro powder and siloxane coated polytetrafluoroethylene micro powder; the antioxidant is hindered phenol antioxidant and/or phosphite antioxidant; the lubricant is at least one of amides, stearates, esters and silicone.
Preferably, the ABS composite material comprises at least one of the following (a) - (c):
(a) The weight percentage of butadiene in the ABS resin is 22-29%;
(b) The brominated flame retardant is at least one of bromotriazine, brominated epoxy and tetrabromobisphenol A;
(c) The antimony flame retardant is at least one of antimony oxide and antimonate.
In addition, the invention provides a preparation method of the ABS composite material, which comprises the following steps:
(1) Weighing various raw materials according to the proportion;
(2) Adding the various raw materials in the step (1) into a mixer to be mixed uniformly, so as to obtain a mixed material;
(3) And (3) adding the mixed material obtained in the step (2) into a double-screw extruder for melt extrusion granulation to obtain the ABS composite material.
Preferably, in the step (2), the mixing time is 2-10min, and the mixing rotating speed is 800-1200r/min; in the step (3), the temperature of each section of the double-screw extruder is 160-210 ℃, and the screw rotating speed of the double-screw extruder is 400-600r/min.
Further, the invention provides application of the ABS composite material in the field of electric appliances.
Preferably, the invention provides application of the ABS composite material in the fields of household appliances, electronic appliances and the like.
Compared with the prior art, the invention has the beneficial effects that: the invention provides an ABS composite material, which is characterized in that a flame retardant synergist A and a flame retardant synergist B are creatively matched together, so that the flame retardant effect is effectively and synergistically improved, and meanwhile, the addition amount of high-price brominated flame retardants and antimony flame retardants in the ABS composite material is reduced, and the excellent flame retardant performance is still maintained on the premise of greatly reducing the cost. According to the invention, the mechanical properties of the ABS composite material are further improved under the condition that the flame retardant effect of the prepared ABS composite material is kept to be optimal by selecting the specific proportion of the flame retardant synergist A and the flame retardant synergist B and the specific particle size D50 of the flame retardant synergist A.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used, unless otherwise specified, are commercially available. The anti-dripping agent, the antioxidant and the lubricant used in all the examples and the comparative examples are identical;
The following description of the raw materials used in the examples and comparative examples is provided, but is not limited to these materials:
ABS resin-1: the weight percentage of butadiene is 29%, ABS PA-747S, taiwan Qimei;
ABS resin-2: the weight percentage of butadiene is 22%, ABSD-120A, qiao in Taiwan China;
ABS resin-3: the weight percentage of butadiene is 16%, ABS GP-22, the Yingli benzene collar;
Brominated flame retardant-1: tetrabromobisphenol A, FR-1524, commercially available;
brominated flame retardant-2: bromotriazine, FR-245, commercially available;
antimony-based flame retardant-1: antimony trioxide, commercially available;
antimony-based flame retardant-2: sodium antimonate, commercially available;
Flame retardant synergist a-silica:
silica-1, hs-3386 (particle size D50 of 5 microns), a company of the weifang scintillant nanomaterials limited;
Silica-2, H-102 (particle size D50 7 microns), new Material Co., ltd;
Silica-3, H-103, (particle size D50 of 12 microns), new Material Co., ltd;
silica-4, TS-720 (particle size D50 of 4.3 microns), carbot, U.S.;
Silica-5, HS-3325 (particle size D50 of 45 microns), weifang constant scintillation nanomaterial Co., ltd;
flame retardant synergist B-tetrafluoroethylene and olefin copolymer:
Tetrafluoroethylene and olefin copolymer-1: tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), AP-202, company Jin Fuhua, china, inc;
tetrafluoroethylene and olefin copolymer-2: tetrafluoroethylene-hexafluoropropylene copolymer (FEP), NP-3180, da Jin Fuhua (China) Co., ltd;
Tetrafluoroethylene and olefin copolymer-3: tetrafluoroethylene-ethylene copolymer (ETFE), EP-506, inc. (China) Inc. of Jin Fuhua;
Polytetrafluoroethylene-4: polytetrafluoroethylene (PTFE), F-106, inc. of Jin Fuhua, china;
processing aid:
anti-drip agent: coating polytetrafluoroethylene micropowder with acrylic ester, and selling in the market;
An antioxidant: antioxidant 1-THANOX 1010 (pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) and antioxidant 2-THANOX168 (tris (2, 4-di-tert-butylphenyl) phosphite), commercially available;
and (3) a lubricant: pentaerythritol stearate lubricants, commercially available;
Examples 1 to 12 and comparative examples 1 to 6
The components and parts by weight of the ABS composites of examples and comparative examples are shown in table 1, wherein,
The preparation method of the ABS composite materials of examples 1-12 and comparative examples 1-6 comprises the following steps:
(1) Weighing various raw materials according to the proportion;
(2) Adding the various raw materials in the step (1) into a mixer to be mixed uniformly, so as to obtain a mixed material; the mixing time is 5min, and the mixing rotating speed is 1000r/min;
(3) And (3) adding the mixed material obtained in the step (2) into a double-screw extruder for melt extrusion granulation, wherein the temperature of each section of the double-screw extruder is 160-210 ℃, and the screw speed of the double-screw extruder is 400-600r/min, so as to obtain the ABS composite material.
Wherein, the processing aid consists of an anti-dripping agent, pentaerythritol stearate lubricant and an antioxidant according to the following weight percentage of 2:1:1, wherein the antioxidant consists of a main antioxidant THANOX and an auxiliary antioxidant THANOX168 according to the mass ratio of 3:2;
TABLE 1
TABLE 2
Performance testing
Drying the ABS composite materials prepared in the examples and the comparative examples in a blast oven at 80 ℃ for 4 hours, and then injecting the ABS composite materials into standard sample bars by a plastic injection molding machine, wherein the injection molding temperature is 200-210 ℃; the molded bars were subjected to performance testing after being placed at 23 ℃ for at least 24 hours at 50% relative humidity.
(1) Flame retardant rating of 1.6mm standard bars were tested according to UL94-2009 standard;
(2) Notched Izod impact Strength: injection molding a bar-shaped spline (notch Type A) meeting the requirements of ISO 180-2019 cantilever notch impact strength test, and performing the cantilever notch impact strength test at 25 ℃;
(3) Flexural strength: according to the ISO 178-2019 method, the test speed is 2mm/min;
The test results are shown in tables 3 and 4;
TABLE 3 Table 3
TABLE 4 Table 4
The invention provides an ABS composite material, which is characterized in that a flame retardant synergist A and a flame retardant synergist B are creatively matched together, so that the flame retardant effect is effectively and synergistically improved, and meanwhile, the addition amount of high-price brominated flame retardants and antimony flame retardants in the ABS composite material is reduced, and the excellent flame retardant performance is still maintained on the premise of greatly reducing the cost and maintaining the mechanical performance.
As shown in the table, the ABS composite material prepared by the embodiment of the invention has the flame retardant property (1.6 mm) of V-0, the notch impact strength of the cantilever beam is more than or equal to 15KJ/m 2, and the bending strength is more than or equal to 60MPa.
As can be seen from the comparison of examples 3-6 and example 1, the mechanical properties of the ABS composite material are further improved by selecting the flame retardant synergist A as silicon dioxide with the particle size D50 of 5-12 mu m.
As is clear from the comparison of examples 7 to 8, example 1 and comparative example 1, the flame retardant property and mechanical property are better when the flame retardant synergist B is a copolymer of tetrafluoroethylene and olefin.
As can be seen from comparison of example 1 and comparative examples 2-3, when the flame retardant synergist is 4-10 parts, the ABS composite material prepared by the method has better flame retardant property and mechanical property.
As can be seen from the comparison of examples 9-12 and example 1, the weight ratio of the flame retardant synergist A to the flame retardant synergist B is: flame retardant synergist A: flame retardant synergist b= (3-5): and (1-2), the ABS composite material prepared by the method has better flame retardant property and mechanical property.
As can be seen from the comparison of the example 1 and the comparative examples 4-6, the flame retardant synergist of the invention has a synergistic effect, lacks any one, has poor flame retardant effect, and has obvious reduction of the notch impact strength of the cantilever beam.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
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