CN116041823A - Halogen-free intumescent flame-retardant antistatic thermoplastic elastomer composite foaming material and preparation method thereof - Google Patents
Halogen-free intumescent flame-retardant antistatic thermoplastic elastomer composite foaming material and preparation method thereof Download PDFInfo
- Publication number
- CN116041823A CN116041823A CN202211713143.8A CN202211713143A CN116041823A CN 116041823 A CN116041823 A CN 116041823A CN 202211713143 A CN202211713143 A CN 202211713143A CN 116041823 A CN116041823 A CN 116041823A
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- China
- Prior art keywords
- flame retardant
- thermoplastic elastomer
- component
- composite
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000002131 composite material Substances 0.000 title claims abstract description 93
- 239000003063 flame retardant Substances 0.000 title claims abstract description 84
- 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 83
- 238000005187 foaming Methods 0.000 title claims abstract description 59
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 20
- 239000011256 inorganic filler Substances 0.000 claims abstract description 20
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 20
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 19
- 239000002216 antistatic agent Substances 0.000 claims abstract description 19
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010439 graphite Substances 0.000 claims abstract description 18
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 18
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004088 foaming agent Substances 0.000 claims abstract description 15
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 14
- 229920000388 Polyphosphate Polymers 0.000 claims abstract description 14
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 14
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 14
- 239000001205 polyphosphate Substances 0.000 claims abstract description 14
- 235000011176 polyphosphates Nutrition 0.000 claims abstract description 14
- 239000012756 surface treatment agent Substances 0.000 claims abstract description 13
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008117 stearic acid Substances 0.000 claims abstract description 8
- 239000011787 zinc oxide Substances 0.000 claims abstract description 8
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229920001903 high density polyethylene Polymers 0.000 claims description 23
- 239000004700 high-density polyethylene Substances 0.000 claims description 23
- 229920001684 low density polyethylene Polymers 0.000 claims description 20
- 239000004702 low-density polyethylene Substances 0.000 claims description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 19
- 239000006261 foam material Substances 0.000 claims description 19
- 239000008187 granular material Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- 239000004156 Azodicarbonamide Substances 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 5
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 4
- 238000004073 vulcanization Methods 0.000 claims description 4
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 229910017059 organic montmorillonite Inorganic materials 0.000 claims description 2
- 125000005456 glyceride group Chemical group 0.000 claims 1
- 230000003068 static effect Effects 0.000 abstract description 4
- 230000005611 electricity Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 239000005038 ethylene vinyl acetate Substances 0.000 description 11
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 11
- 239000007789 gas Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- -1 but not limited to Chemical compound 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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Abstract
The invention relates to the technical field of high polymer materials, in particular to a halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foaming material and a preparation method thereof. The composite foaming material comprises a component A and a component B; the component A comprises a thermoplastic elastomer resin mixture, an antistatic agent, a composite foaming agent, a cross-linking agent, a compatibilizer, an inorganic filler and a processing aid; the component B comprises a composite flame retardant, a flame retardant synergist and a surface treatment agent; the components of the thermoplastic elastomer resin mixture include EVA, PE and POE; the composite flame retardant comprises expandable graphite, ammonium polyphosphate and melamine polyphosphate; the processing aid includes zinc oxide, stearic acid and zinc stearate. The composite foaming material has good mechanical properties and simultaneously has the functions of green flame retardance and static electricity resistance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foaming material and a preparation method thereof.
Background
Thermoplastic elastomers are a class of polymeric materials that have rubbery properties at room temperature and are plasticizable and shaped at high temperatures. The thermoplastic elastomer composite foaming material has various excellent performances such as ageing resistance, oil resistance, impact resistance and the like of rubber, and simultaneously has the characteristics of multiple common plastic processing modes, simplicity and convenience, and is widely applied to the fields of shoe materials, packaging industry, automobile industry and the like.
However, it has the following disadvantages:
(1) The flame retardant property is poor, the smoke generation amount is large, the heat release amount is large, and the limiting oxygen index is relatively low;
(2) High resistivity, and is likely to accumulate static electricity to cause a risk.
These two drawbacks, however, have limited the wider use of thermoplastic elastomer composite foam materials.
Disclosure of Invention
To solve the problems of the prior art mentioned in the background art: the existing thermoplastic elastomer composite foaming material has the problems of easy combustion, low flame retardant efficiency, high resistivity and the like; the invention provides a halogen-free intumescent flame-retardant antistatic thermoplastic elastomer composite foaming material, which has the following technical scheme:
the halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foaming material comprises a component A and a component B; the component A comprises a thermoplastic elastomer resin mixture, an antistatic agent, a composite foaming agent, a cross-linking agent, a compatibilizer, an inorganic filler and a processing aid; the component B comprises a composite flame retardant, a flame retardant synergist and a surface treatment agent; the components of the thermoplastic elastomer resin mixture comprise EVA, PE and POE; the composite flame retardant comprises expandable graphite, ammonium polyphosphate and melamine polyphosphate; the processing aid includes zinc oxide, stearic acid, and zinc stearate.
In one embodiment, the component A comprises, by weight, 40-60 parts of a thermoplastic elastomer resin mixture, 5-15 parts of an antistatic agent, 2.5-3.0 parts of a composite foaming agent, 0.9-1.1 parts of a cross-linking agent, 10-15 parts of a compatibilizer, 3.0-5.5 parts of an inorganic filler and 0.9-1.2 parts of a processing aid; the component B comprises 15 to 30 parts of composite flame retardant, 1.0 to 3.5 parts of flame retardant synergist and 0.3 to 0.4 part of surface treatment agent; the weight ratio of the component A to the component B is (70-82): (18-30).
In one embodiment, the thermoplastic elastomer resin mixture is composed of EVA, HDPE/LDPE and POE, wherein the weight ratio of the EVA, the HDPE/LDPE and the POE is (10-15): (1-3): (2-5); in the HDPE/LDPE, the weight ratio of HDPE to LDPE is 1:1; the composite flame retardant comprises 4-7 parts of expandable graphite, 16-20 parts of ammonium polyphosphate and 0.5-3 parts of melamine polyphosphate according to parts by weight; the processing aid comprises 0.6-0.7 part of zinc oxide, 0.1-0.2 part of stearic acid and 0.2-0.3 part of zinc stearate.
In one embodiment, the expandable graphite has an expansion degree of 60m l/g to 250m l/g, a particle size of 80 mesh to 150 mesh, and a pH of (6.5 to 7.5).
In one embodiment, the melamine polyphosphate is prepared by the steps of: the melamine phosphate is synthesized by taking melamine and phosphoric acid as raw materials and reacting for 2-3 hours at the temperature of 80-120 ℃, and then the melamine phosphate is obtained by drying and dehydrating reaction at the temperature of 250-300 ℃.
In one embodiment, the antistatic agent is conductive carbon black; the cross-linking agent is dicumyl peroxide; the compound foaming agent is at least one of azodicarbonamide, sodium bicarbonate, p-toluenesulfonyl hydrazide, azodiisobutyronitrile and dinitroso pentamethylene tetramine.
In one embodiment, the compatibilizer is at least one of ethylene-acrylate, maleic anhydride grafted high density polyethylene, butyl acrylate, methyl methacrylate, and fatty acid glycerides; the inorganic filler is at least one of talcum powder, nano calcium carbonate, kaolin and bentonite.
In one embodiment, the flame retardant synergist is at least one of zinc borate, organic montmorillonite and antimony trioxide; the surface treatment agent is at least one of a silane coupling agent, a phosphate coupling agent and an aluminum-titanium composite coupling agent.
The invention provides a preparation method of the halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foaming material, which comprises the following steps:
preparing a component A: uniformly mixing a thermoplastic elastomer resin compound, an antistatic agent, a composite foaming agent, a cross-linking agent, a compatibilizer, an inorganic filler and a processing aid according to the formula proportion to obtain a component A;
and (3) preparing a component B: uniformly mixing the composite flame retardant, the flame retardant synergist and the surface treatment agent according to the formula proportion to obtain a component B;
preparing foaming granules: according to the formula proportion, putting the component A and the component B into a double-screw extruder for melt extrusion, cooling and granulating to obtain foaming granules;
and (3) composite foaming: and (3) vulcanizing and foaming the foaming granules to obtain the halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foaming material.
In one embodiment, the inorganic filler is dried in an oven at 60-80 ℃ for 8-10 hours before preparing the A component;
in the preparation process of the component A, according to the formula proportion, a thermoplastic elastomer resin compound, an antistatic agent, a compound foaming agent, a crosslinking agent, a compatibilizer, an inorganic filler and a processing aid are put into a high-speed mixer, and are mixed at a high speed at normal temperature for 1 min-2 min to be uniformly mixed to obtain the component A;
during the preparation of the component B: according to the formula proportion, putting the composite flame retardant, the flame retardant synergist and the surface treating agent into a high-speed mixer, mixing at normal temperature and high speed for 2 min-4 min to uniformly mix, and then drying at the temperature of (50-70) ℃ for 2-3 h to obtain a component B;
and (3) placing the foaming granules into a preheated plate vulcanizing machine die, and performing vulcanization foaming under the conditions of (160-175) DEG C and (13-17) MPa and maintaining pressure for 8 min-10 min to obtain the halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foaming material.
Compared with the prior art, the halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foaming material provided by the invention has the following technical effects:
the halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foaming material provided by the invention has excellent flame retardant property, does not contain halogen, polybrominated diphenyl, mercury, lead, cadmium and other harmful substances, does not generate harmful gas during processing, does not pollute the environment by harmful hydrogen halide gas during combustion, and the adopted composite flame retardant belongs to a green halogen-free intumescent flame retardant, so that the prepared composite foaming material has the characteristic of environmental friendliness. In addition, the composite foaming material has good mechanical properties and simultaneously has the functions of green flame retardance and static electricity resistance.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure and/or components pointed out in the written description and claims.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the following description will be made in connection with the technical solutions in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foaming material, which comprises the following steps:
step (1), placing the inorganic filler in an oven at 60-80 ℃ for drying for 8-10 h;
step (2) preparing a component A: according to the formula proportion, putting the thermoplastic elastomer resin compound, the antistatic agent, the composite foaming agent, the cross-linking agent, the compatibilizer, the inorganic filler and the processing aid into a high-speed mixer, and mixing at a high speed at normal temperature for 1 min-2 min to obtain a component A;
and (3) preparing a component B: according to the formula proportion, putting the composite flame retardant, the flame retardant synergist and the surface treating agent into a high-speed mixer, mixing at normal temperature and high speed for 2 min-4 min to uniformly mix, and then drying at the temperature of (50-70) ℃ for 2-3 h to obtain a component B;
preparing foaming granules: according to the formula proportion, putting the component A and the component B into a double-screw extruder for melt extrusion, cooling and granulating to obtain foaming granules; wherein the melting temperature of the twin-screw extruder is (110-150) DEG C, and the rotating speed is (350-450) rpm.
In the composite foaming process, the foaming granules are placed in a preheated press vulcanizer die, and the pressure is maintained for 8 min-10 min under the conditions of (160-175) DEG C and (13-17) MPa for vulcanization foaming, thus obtaining the halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foaming material
The formula of the raw material components comprises the following steps:
the formula of the halogen-free intumescent flame-retardant antistatic thermoplastic elastomer composite foaming material is as follows: the composite material comprises a component A and a component B; the component A comprises, by weight, 40-60 parts of a thermoplastic elastomer resin mixture, 5-15 parts of an antistatic agent, 2.5-3.0 parts of a composite foaming agent, 0.9-1.1 parts of a cross-linking agent, 10-15 parts of a compatibilizer, 3.0-5.5 parts of an inorganic filler and 0.9-1.2 parts of a processing aid; the component B comprises 15 to 30 parts of composite flame retardant, 1.0 to 3.5 parts of flame retardant synergist and 0.3 to 0.4 part of surface treatment agent; the weight ratio of the component A to the component B is (70-82): (18-30).
Wherein the thermoplastic elastomer resin mixture consists of EVA, HDPE/LDPE and POE, and the weight ratio of the EVA, the HDPE/LDPE and the POE is (10-15): (1-3): (2-5); in the HDPE/LDPE, the weight ratio of HDPE to LDPE is 1:1;
the composite flame retardant comprises 4-7 parts of expandable graphite, 16-20 parts of ammonium polyphosphate and 0.5-3 parts of melamine polyphosphate according to parts by weight; the processing aid comprises 0.6-0.7 part of zinc oxide, 0.1-0.2 part of stearic acid and 0.2-0.3 part of zinc stearate.
In addition, the invention also provides a preferred embodiment of the preparation process of the melamine polyphosphate: the melamine phosphate is synthesized by taking melamine and phosphoric acid as raw materials and reacting for 2-3 hours at the temperature of 80-120 ℃, and then the melamine phosphate is obtained by drying and dehydrating reaction at the temperature of 250-300 ℃.
The invention also provides examples and comparative examples shown in the following table:
the formulations (unit: parts by weight) of examples and comparative examples provided by the present invention are shown in table 1 below:
TABLE 1
In Table 1, the raw materials are as follows:
the thermoplastic elastomer resin mixtures of examples 1-3, comparative examples 2-5 consisted of EVA, HDPE/LDPE and POE in a weight ratio of 10:1:2; the weight ratio of HDPE to LDPE in HDPE/LDPE is 1:1; the thermoplastic elastomer resin mixture of comparative example 1 consisted of EVA and HDPE/LDPE with a composition of 10:1. Wherein, EVA is 460 of DuPont in U.S., HDPE is R444L of Qilu petrochemical industry, LDPE is 8320 of Daqing petrochemical industry, POE is 875L of Korean SK;
the composite flame retardant of examples 1-3 and comparative example 1 is prepared from expandable graphite, ammonium polyphosphate and melamine polyphosphate in a weight ratio of 6:18:1, the composition is as follows; the composite flame retardant in comparative example 3 consists of ammonium polyphosphate and melamine polyphosphate in a weight ratio of 18: 1. The composite flame retardant in comparative example 4 consists of expanded graphite and melamine polyphosphate according to the weight ratio of 6: 1. In the example 5, the composite flame retardant consists of expanded graphite and ammonium polyphosphate according to the weight ratio of 1: 3.
The remaining raw material components of the examples and comparative examples were selected in agreement with each other except for the above raw material components: the antistatic agent is conductive carbon black; the composite foaming agent consists of azodicarbonamide and azodiisobutyronitrile, and the weight ratio of the azodicarbonamide to the azodiisobutyronitrile is 1:1, a step of; the cross-linking agent is dicumyl peroxide; the compatibilizer is ethylene-acrylic ester; the inorganic filler is talcum powder; the processing aid consists of zinc oxide, stearic acid and zinc stearate, and comprises 0.6 weight percent of zinc oxide, 0.1 weight percent of stearic acid and 0.2 weight percent of zinc stearate; the expandable graphite had an expansion degree of 250m l/g, a particle diameter of 106 mesh and a pH of 7. The flame retardant synergist is zinc borate.
The ammonium polyphosphate is industrial grade ammonium polyphosphate produced by Shandong Shian chemical industry; the melamine polyphosphate is prepared by a laboratory, and the synthesis process comprises the following steps: the melamine phosphate is synthesized by taking melamine and phosphoric acid as raw materials and reacting for 2 hours at the temperature of 100 ℃, and then the melamine phosphate is obtained by drying and dehydrating reaction at the temperature of 250 ℃, wherein the weight ratio of the melamine to the phosphoric acid is 19:5.
according to the formulation of table 1, the raw material components in the examples and the comparative examples are prepared into halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foam materials according to the following preparation method, and the preparation steps are as follows:
step one, preparing a component A: placing the inorganic filler in a baking oven at 60 ℃ for drying for 8 hours; and then placing the thermoplastic elastomer resin compound, the antistatic agent, the compound foaming agent, the cross-linking agent, the compatibilizer, the inorganic filler and the processing aid into a high-speed mixer according to the formula requirement, mixing at high speed for 1min at normal temperature, and taking out for later use.
Step two, preparing a component B: putting the composite flame retardant, the flame retardant synergist and the surface treatment agent into a high-speed mixer, stirring at a high speed for 2min, and then drying in an oven at about 60 ℃ for 2h for later use.
Step three, preparing foaming granules: and (3) adding the component A and the component B into a double-screw extruder together according to the formula requirement, heating and extruding the mixture into strips, and cooling and granulating the strips to obtain the foaming granules.
Specifically, the twin-screw extruder is provided with 9 barrels, namely the twin-screw extruder is uniformly divided into 9 areas, the temperatures of the areas of the twin-screw extruder are 110 ℃, 120 ℃, 130 ℃, 150 ℃, 140 ℃, 130 ℃, 120 ℃, 125 ℃, 130 ℃, the head temperature is 145 ℃, the length-diameter ratio of the screw of the twin-screw extruder is 35:1, and the screw rotating speed is 400rpm.
Step four, compound foaming: weighing a proper amount of foaming granules, placing the foaming granules into a preheated plate vulcanizing machine die, and performing vulcanization foaming under the conditions of 170 ℃ and 15MPa and pressure maintaining for 9 min.
The composite foam materials prepared in examples and comparative examples were subjected to the test for the relevant index, and the test results are shown in Table 2 below
TABLE 2
Wherein, the test standard of the oxygen index is GBT 2406.1-2008; tensile strength test standard I S0527,0527; the volume resistance standard is GBT 1410-2006; the flame retardant performance test standard is UL94, and the flame retardant grades are V0, V1, V2 and NV in sequence from good to poor; the rebound resilience test standard is GB/T1681-2009; the tearing strength standard is GB/T529-2008;
from the test results in table 2, it can be seen that:
the halogen-free intumescent flame-retardant antistatic thermoplastic elastomer composite foaming material provided by the embodiment of the invention has excellent flame retardant property, does not contain halogen, polybrominated diphenyl, mercury, lead, cadmium and other harmful substances, does not generate harmful gas during processing, does not pollute the environment by harmful hydrogen halide gas during combustion, has good mechanical property and low volume resistance, and has the functions of green flame retardance and antistatic property.
Comparative example 1 differs from example 2 in that: the thermoplastic elastomer resin mixture used in comparative example 1 consisted of EVA with HDPE/LDPE, as can be seen from the data in Table 2: the tensile strength of comparative example 1 was decreased and the volume resistance was increased relative to example 2.
Comparative example 2 differs from example 2 in that: comparative example 2 the composite flame retardant in the example was replaced with a thermoplastic elastomer resin mixture, as can be seen from the data in table 2: the UL-94 rating of comparative example 2 was NV and its oxygen index was lowered, and its flame retardant properties were significantly deteriorated, as compared with example 2.
Comparative examples 3 to 5 differ from example 2 in that: the composite flame retardants of comparative examples 3-5 are a combination of two of expandable graphite, ammonium polyphosphate, melamine polyphosphate, as can be seen from the data of table 2: the UL-94 rating of comparative examples 3 to 5 was deteriorated, the oxygen index was lowered, and the flame retardant property was remarkably deteriorated, as compared with example 2.
The invention provides the polyolefin composite foaming material to achieve the required beneficial effects through the following conception or action mechanism:
the thermoplastic elastomer resin mixture selected by the invention is a mixture composed of ethylene-vinyl acetate copolymer (EVA), high-density polyethylene/low-density polyethylene polymer (HDPE/LDPE) and ethylene-octene copolymer (POE) with good compatibility, and a compatibilizer is also added, so that the compatibility of an organic phase and an inorganic phase is improved, and the physical and mechanical properties of the prepared composite foaming material are improved.
The composite foaming material provided by the invention is added with the composite flame retardant, and the expandable graphite in the composite flame retardant has good compatibility with the thermoplastic elastomer resin mixture, so that the melt viscosity is low, the material has good processability, the thermoplastic elastomer resin mixture is a good conductive material, and the volume resistance of the material can be effectively reduced by adding the antistatic agent; the expandable graphite, ammonium polyphosphate and phosphate in the composite flame retardant have respective characteristics, so that the composite foaming material prepared by the invention has the environment-friendly characteristic;
the processing aid is added into the composite foaming material, so that the particle accumulation phenomenon in the extrusion process can be reduced, and the uniform extrusion of a melt is ensured, so that the tensile property of the composite foaming material is ensured;
the halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foaming material prepared by the invention has the advantages of good physical and mechanical properties, impact resistance, oil resistance and the like, and simultaneously has flame retardant and antistatic properties.
In conclusion, the invention does not contain halogen, polybrominated diphenyl, mercury, lead, cadmium and other harmful substances, no harmful gas is generated in the processing process, and no toxic hydrogen halide gas causes environmental pollution in the combustion process. The expandable graphite, ammonium polyphosphate and phosphate in the composite flame retardant have respective characteristics, so that the composite foaming material prepared by the invention has the environment-friendly characteristic; the expandable graphite is a conductive material, and the antistatic agent is added, so that the volume resistance of the composite foaming material can be reduced, and the composite foaming material has the functions of green flame retardance and static resistance.
It should be noted that:
in addition to the practical choices embodied in the above embodiments, the expandable graphite may preferably have an expansion degree of 60m l/g to 250m l/g, a particle size of 80 mesh to 150 mesh, and a pH of (6.5 to 7.5), including but not limited to the practical choices embodied in the above embodiments;
in addition to the actual choices presented in the above embodiments, the antistatic agent may be selected from existing antistatic agents, such as, preferably, conductive carbon black, including, but not limited to, the actual choices presented in the above embodiments;
in addition to the actual choices presented in the above embodiments, the crosslinking agent may be selected from existing crosslinking agents, such as preferably dicumyl peroxide, including but not limited to the actual choices presented in the above embodiments;
in addition to the actual choices embodied in the specific examples above, the composite blowing agent may preferably be at least one of azodicarbonamide, sodium bicarbonate, p-toluenesulfonyl hydrazide, azodiisobutyronitrile, dinitroso pentamethylene tetramine, including but not limited to the actual choices embodied in the examples above;
in addition to the actual choices presented in the specific examples above, the compatibilizer may preferably be at least one of ethylene-acrylate, maleic anhydride grafted high density polyethylene, butyl acrylate, methyl methacrylate, fatty acid glycerides, including, but not limited to, the actual choices presented in the examples above;
in addition to the actual choices presented in the above specific examples, the inorganic filler may preferably be at least one of talc, nano calcium carbonate, kaolin, bentonite, including but not limited to the actual choices presented in the above examples;
in addition to the actual choices embodied in the specific examples above, the flame retardant synergist may preferably be at least one of zinc borate, organo montmorillonite, antimony trioxide, including but not limited to the actual choices embodied in the examples above;
in addition to the actual choices presented in the above specific examples, the surface treatment agent may preferably be at least one of a silane-based coupling agent, a phosphate coupling agent, an aluminum titanium composite coupling agent, including but not limited to the actual choices presented in the above examples.
In summary, the specific parameters or some common reagents or raw materials in the above embodiments are specific embodiments or preferred embodiments under the concept of the present invention, and are not limiting; and can be adaptively adjusted by those skilled in the art within the concept and the protection scope of the invention.
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 same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foaming material is characterized by comprising a component A and a component B;
the component A comprises a thermoplastic elastomer resin mixture, an antistatic agent, a composite foaming agent, a cross-linking agent, a compatibilizer, an inorganic filler and a processing aid; the component B comprises a composite flame retardant, a flame retardant synergist and a surface treatment agent;
the components of the thermoplastic elastomer resin mixture comprise EVA, PE and POE; the composite flame retardant comprises expandable graphite, ammonium polyphosphate and melamine polyphosphate; the processing aid includes zinc oxide, stearic acid, and zinc stearate.
2. The halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foam material according to claim 1, wherein the foam material is characterized by: the component A comprises, by weight, 40-60 parts of a thermoplastic elastomer resin mixture, 5-15 parts of an antistatic agent, 2.5-3.0 parts of a composite foaming agent, 0.9-1.1 parts of a cross-linking agent, 10-15 parts of a compatibilizer, 3.0-5.5 parts of an inorganic filler and 0.9-1.2 parts of a processing aid;
the component B comprises 15 to 30 parts of composite flame retardant, 1.0 to 3.5 parts of flame retardant synergist and 0.3 to 0.4 part of surface treatment agent;
the weight ratio of the component A to the component B is (70-82): (18-30).
3. The halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foam material according to claim 1, wherein the foam material is characterized by: the thermoplastic elastomer resin mixture consists of EVA, HDPE/LDPE and POE, wherein the weight ratio of the EVA, the HDPE/LDPE and the POE is (10-15): (1-3): (2-5); in the HDPE/LDPE, the weight ratio of HDPE to LDPE is 1:1;
the composite flame retardant comprises 4-7 parts of expandable graphite, 16-20 parts of ammonium polyphosphate and 0.5-3 parts of melamine polyphosphate according to parts by weight; the processing aid comprises 0.6-0.7 part of zinc oxide, 0.1-0.2 part of stearic acid and 0.2-0.3 part of zinc stearate.
4. The halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foam material according to claim 1, wherein the foam material is characterized by: the expandable graphite has an expansion degree of 60ml/g to 250ml/g, a particle diameter of 80 to 150 meshes, and a pH of 6.5 to 7.5.
5. The halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foam material according to claim 1, wherein the foam material is characterized by: the preparation process of the melamine polyphosphate comprises the following steps: the melamine phosphate is synthesized by taking melamine and phosphoric acid as raw materials and reacting for 2-3 hours at the temperature of 80-120 ℃, and then the melamine phosphate is obtained by drying and dehydrating reaction at the temperature of 250-300 ℃.
6. The halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foam material according to claim 1, wherein the foam material is characterized by: the antistatic agent is conductive carbon black; the cross-linking agent is dicumyl peroxide; the compound foaming agent is at least one of azodicarbonamide, sodium bicarbonate, p-toluenesulfonyl hydrazide, azodiisobutyronitrile and dinitroso pentamethylene tetramine.
7. The halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foam material according to claim 1, wherein the foam material is characterized by: the compatibilizer is at least one of ethylene-acrylic ester, maleic anhydride grafted high-density polyethylene, butyl acrylate, methyl methacrylate and fatty glyceride;
the inorganic filler is at least one of talcum powder, nano calcium carbonate, kaolin and bentonite.
8. The halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foam material according to claim 1, wherein the foam material is characterized by: the flame retardant synergist is at least one of zinc borate, organic montmorillonite and antimony trioxide;
the surface treatment agent is at least one of a silane coupling agent, a phosphate coupling agent and an aluminum-titanium composite coupling agent.
9. A method for preparing the halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foam material as claimed in any one of claims 1-8, which comprises the following steps:
preparing a component A: uniformly mixing a thermoplastic elastomer resin compound, an antistatic agent, a composite foaming agent, a cross-linking agent, a compatibilizer, an inorganic filler and a processing aid according to the formula proportion to obtain a component A;
and (3) preparing a component B: uniformly mixing the composite flame retardant, the flame retardant synergist and the surface treatment agent according to the formula proportion to obtain a component B;
preparing foaming granules: according to the formula proportion, putting the component A and the component B into a double-screw extruder for melt extrusion, cooling and granulating to obtain foaming granules;
and (3) composite foaming: and (3) vulcanizing and foaming the foaming granules to obtain the halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foaming material.
10. The method for preparing the halogen-free intumescent flame retardant antistatic thermoplastic elastomer composite foam material according to claim 9, which is characterized in that: before the component A is prepared, the inorganic filler is placed in an oven at 60-80 ℃ to be dried for 8-10 hours;
in the preparation process of the component A, according to the formula proportion, the thermoplastic elastomer resin compound, the antistatic agent, the compound foaming agent, the cross-linking agent, the compatibilizer, the inorganic filler and the processing aid are put into a high-speed mixer and mixed at normal temperature for 1 to 2 minutes at high speed to be uniformly mixed to obtain the component A;
during the preparation of the component B: according to the formula proportion, putting the composite flame retardant, the flame retardant synergist and the surface treatment agent into a high-speed mixer, mixing at normal temperature for 2-4 min at high speed to uniformly mix, and then drying at (50-70) ℃ for 2-3 h to obtain a component B;
and (3) placing the foaming granules into a preheated press vulcanizer die, and maintaining the pressure for 8-10 min at the temperature of (160-175) DEG C and the pressure of (13-17) MPa for vulcanization foaming to obtain the halogen-free intumescent flame-retardant antistatic thermoplastic elastomer composite foaming material.
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