CN115895246A - Expandable graphite modified polyamide elastomer material and preparation method and application thereof - Google Patents
Expandable graphite modified polyamide elastomer material and preparation method and application thereof Download PDFInfo
- Publication number
- CN115895246A CN115895246A CN202211512991.2A CN202211512991A CN115895246A CN 115895246 A CN115895246 A CN 115895246A CN 202211512991 A CN202211512991 A CN 202211512991A CN 115895246 A CN115895246 A CN 115895246A
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- CN
- China
- Prior art keywords
- parts
- expandable graphite
- polyamide elastomer
- antioxidant
- flame retardant
- Prior art date
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- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229920001971 elastomer Polymers 0.000 title claims abstract description 76
- 239000000806 elastomer Substances 0.000 title claims abstract description 75
- 239000004952 Polyamide Substances 0.000 title claims abstract description 72
- 229920002647 polyamide Polymers 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 67
- 239000010439 graphite Substances 0.000 title claims abstract description 66
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003063 flame retardant Substances 0.000 claims abstract description 96
- 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 claims abstract description 93
- 239000007822 coupling agent Substances 0.000 claims abstract description 28
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 27
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 24
- 230000002195 synergetic effect Effects 0.000 claims abstract description 20
- 239000002250 absorbent Substances 0.000 claims abstract description 17
- 230000002745 absorbent Effects 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims description 33
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 26
- 229920000570 polyether Polymers 0.000 claims description 26
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229920002292 Nylon 6 Polymers 0.000 claims description 15
- 238000005469 granulation Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- 229920000728 polyester Polymers 0.000 claims description 14
- 229920002614 Polyether block amide Polymers 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 8
- 239000004677 Nylon Substances 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 229920001778 nylon Polymers 0.000 claims description 7
- -1 polyhexamethylene Polymers 0.000 claims description 7
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 5
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 claims description 5
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 4
- 239000000391 magnesium silicate Substances 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 235000019792 magnesium silicate Nutrition 0.000 claims description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 3
- 239000012803 melt mixture Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229960002684 aminocaproic acid Drugs 0.000 claims description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 229940057995 liquid paraffin Drugs 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 claims description 2
- 229940100530 zinc ricinoleate Drugs 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims 2
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 claims 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 claims 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims 1
- 235000019341 magnesium sulphate Nutrition 0.000 claims 1
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229920003225 polyurethane elastomer Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 244000178289 Verbascum thapsus Species 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 235000012243 magnesium silicates Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an expandable graphite modified polyamide elastomer material, and a preparation method and application thereof. The expandable graphite modified polyamide elastomer material comprises the following components in parts by weight based on 100 parts of total weight: 45-74 parts of polyamide elastomer, 15-40 parts of expandable graphite flame retardant, 8-25 parts of synergistic flame retardant, 0.3-3 parts of coupling agent, 0.5-3 parts of dispersing agent, 0.1-2 parts of antioxidant and 0.1-2 parts of absorbent. The flame retardant property of the expandable graphite modified polyamide elastomer flame retardant material can reach UL94-V0 level, the tensile strength is 27-43MPa, and the impact strength is 20KJ/m 2 The method is suitable for preparing the automobile parts.
Description
Technical Field
The invention belongs to the field of elastomer composite materials, and particularly relates to an expandable graphite modified polyamide elastomer material as well as a preparation method and application thereof.
Background
The trend of light weight of automobiles and the popularization of new energy automobiles put forward higher requirements on mechanical and flame retardant properties for preparing flame retardant materials of automobile parts such as spherical couplings, dust caps, shockproof parts, mud guards, anti-skid chains and the like.
Most of halogen-free flame retardant materials in the market are prepared by adding or blending organic and inorganic flame retardants into base materials, but the mechanical properties (such as tensile strength and impact property) of the materials are greatly reduced while the flame retardant property is realized. In addition, the base materials with poor performance, such as most of the rubbers and some elastomer materials used in the prior art, have the problems of poor flexibility, high hardness, difficult recovery, poor compatibility with flame retardants and the like due to the fact that the base materials cannot be recovered or have poor mechanical and aging resistance, and are difficult to meet the use requirements of certain specific environments. For example, currently, the polyurethane elastomers (TPU) which are researched more are difficult to be used for preparing the automobile parts due to insufficient mechanical properties.
Polyamide elastomers (TPAE), also known as thermoplastic polyamide elastomers, are block copolymers containing polyamide hard segments and aliphatic polyester or polyether soft segments. TPAE can be classified into two types according to hardness, i.e., polyether block amide (PEBA) in which a hard segment is an aliphatic polyamide, and other TPAEs in which a hard segment is a semi-aromatic polyamide, such as polyether ester amide (PEEA), polyester amide (PEA), and polycarbonate amide (PCEA). Although TPAE has the characteristics of low hardness, good flexibility, high tensile strength, good elastic recovery, high low-temperature impact strength, excellent low-temperature resistance and the like, the existing polyamide elastomer still has the defects of low oxygen index, easy combustion and poor mechanical property when being used as a flame retardant material, and the application of the TPAE in the field of automobiles is limited.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and the expanded flame-retardant elastomer material prepared by performing expandable graphite flame-retardant modification on the polyamide elastomer (TPAE) has the advantages of high-efficiency flame retardance, excellent mechanical property, environmental friendliness, low cost and recyclability, and can be used for preparing parts such as automobile spherical couplings, dust caps, shockproof parts, mud guards and the like.
In view of the above objects, a first aspect of the present invention provides an expandable graphite-modified polyamide elastomer material comprising, based on 100 parts by total weight: 45-74 parts of polyamide elastomer, 15-40 parts of expandable graphite flame retardant, 8-25 parts of synergistic flame retardant, 0.3-3 parts of coupling agent, 0.5-3 parts of dispersing agent, 0.1-2 parts of antioxidant and 0.1-2 parts of absorbent.
Preferably, the expandable graphite-modified polyamide elastomeric material comprises, based on 100 parts by total weight: 50-70 parts of polyamide elastomer, 15-30 parts of expandable graphite flame retardant, 10-20 parts of synergistic flame retardant, 0.4-1 part of coupling agent, 0.6-1.5 parts of dispersing agent, 0.1-1 part of antioxidant and 0.1-0.6 part of absorbent; more preferably, it comprises, based on 100 parts by total weight: 60-68 parts of polyamide elastomer, 20-25 parts of expandable graphite flame retardant, 10-15 parts of synergistic flame retardant, 0.4-0.8 part of coupling agent, 0.8-1.2 parts of dispersing agent, 0.3-0.8 part of antioxidant and 0.2-0.5 part of absorbent.
In some embodiments, the polyamide elastomer is one or more selected from long or short chain polyether block amide (PEBA), polyether ester amide (PEEA), polyester amide (PEA), and polycarbonate amide (PCEA) block copolymers; preferably short chain polyether block polyamide elastomers; more preferably nylon 6 type polyether block polyamide elastomer (i.e. polyamide 6 type thermoplastic elastomer, TPAE-6).
In the invention, the long-chain polyether block amide refers to polyether block amide synthesized by long-carbon-chain nylon, such as nylon 10, nylon 1010, nylon 11, nylon 12 and the like, of hard-segment polyamide. The short-chain polyether block amide refers to polyether block amide synthesized by nylon with short carbon chains, such as nylon 6 and the like, of hard-segment polyamide compared with long-chain nylon Long Lai.
In some embodiments, the polyamide elastomer has a relative viscosity value of 1.5 to 3.0, preferably 2.0 to 2.8 (measured using GB/T12006.1 (ISO 307) standard method and formic acid solution as solvent) and a hardness value of 25D to 60D (measured using GB/T2411-2008 standard method) to facilitate a compromise between processing flow and mechanical properties of the composite.
In some embodiments, the nylon 6-type polyether block polyamide elastomer is a polyamide 6 thermoplastic elastomer resin prepared by the process of patent CN104327266B, comprising the steps of:
adding polyether/polyester, caprolactam, deionized water, a catalyst and diacid into a reactor, heating to 200-240 ℃ under the protection of nitrogen, and reacting for 0.5-2 hours under mechanical stirring; then, continuously mechanically stirring and reacting for 0.5 to 3 hours at the temperature of between 250 and 280 ℃ and under the condition of vacuumizing to between 20 and 500 Pa; then extracting by boiling water, and drying to obtain the polyamide 6 thermoplastic elastomer resin, wherein the diacid is oxalic acid, malonic acid, succinic acid or adipic acid, and the catalyst is phosphoric acid, sulfuric acid or aminocaproic acid.
Preferably, in the preparation method of the nylon 6 type thermoplastic elastomer resin as described above, the polyester/polyether is one or more selected from Polytetrahydrofuran (PTMEG), polyethylene glycol (PEG), polypropylene glycol (PPG) or polyhexamethylene glycol. Preferably, the number average molecular weight of the polyester/polyether is 300-8000, preferably 500-6000. Preferably, the polyester/polyether soft block is used in an amount of 10 to 60wt%, based on the total weight of polyether/polyester and caprolactam. Preferably, the caprolactam is used in an amount of 40 to 90wt%, based on the total weight of polyether/polyester and caprolactam; and/or the amount of the diacid is 1 to 10 weight percent; and/or the amount of the catalyst is 0.1-4 wt%, preferably 1-3 wt%; and/or the deionized water is used in an amount of 0.5 to 4wt%, preferably 1 to 3wt%. Preferably, the mechanical stirring speed is 100-800 rpm.
The relative viscosity of the nylon 6 type thermoplastic elastomer resin prepared by the method is between 1.5 and 3.0 (measured by taking a GB/T12006.1 (ISO 307) standard method and a formic acid solution as a solvent), and the stable viscosity is obtained by adjusting the reaction temperature and the reaction time more accurately.
In particular, the structure of the nylon 6 type polyether block polyamide elastomer is as follows:
{[CO-(CH 2 ) 5 -HN] m -CO-(CH 2 ) 4 -COO-PE} n
wherein, PE represents soft segment polyester or polyether, such as polyethylene glycol (PEG), tetrahydrofuran Polyether (PTMG), propylene oxide polyether (PPG), polycaprolactone (PCL) and the like, and the number average molecular weight is 300-8000, preferably 500-6000;
m＝6-100，n＝2-15。
preferably, in the nylon 6 type thermoplastic elastomer resin as described above, the content of the nylon 6 hard segment is 40 to 90wt% of the total amount of the polymer hard segment and soft segment; the content of the polyether/polyester soft segment accounts for 1 to 60 weight percent of the total content of the hard segment and the soft segment of the polymer.
The nylon 6 type polyether block polyamide elastomer is short in carbon chain, relatively high in N content and more excellent in flame retardant property, contains a large amount of amino-terminated groups and carboxyl-terminated groups, is relatively strong in polarity, is well compatible with an expanded graphite flame retardant and a synergistic flame retardant in the presence of a coupling agent, forms relatively strong hydrogen bonds, and can greatly improve the mechanical property and flame retardant property of the composite flame retardant material.
In some embodiments, the expandable graphite is selected from a medium onset expansion temperature graphite or a high onset temperature expanded graphite, preferably a medium onset expansion temperature expanded graphite, having an expansion temperature of not less than 250 ℃. In this preferred case, there is not only a cost advantage but also superior performance to the high onset temperature expanded graphite.
In the present invention, the medium initial expansion temperature graphite generally refers to expanded graphite having an initial expansion temperature of 150 ℃ to 290 ℃; high onset temperature expanded graphite generally refers to expanded graphite having an onset expansion temperature greater than 290 ℃.
In some embodiments, the expandable graphite has a particle size of 30 to 100 mesh, preferably 80 mesh, and an expandable ratio of not less than 200 times, preferably not less than 230 times.
In some embodiments, the synergistic flame retardant is one or more selected from magnesium hydroxide (MDH), aluminum hydroxide (ATH), red Phosphorus (RP), ammonium polyphosphate (APP), triphenyl phosphate (TPP), magnesium hydroxide whiskers, silica whiskers. The synergistic flame retardant can increase the residual carbon quantity and improve the carbon layer quality so as to improve the flame retardant efficiency and reduce the cost as much as possible.
Preferably, the synergistic flame retardant is aluminum hydroxide (ATH). The aluminum hydroxide is decomposed by heating, so that heat is absorbed, the temperature rise and the degradation speed of the material are inhibited, and water vapor generated by decomposition can dilute combustible gas; meanwhile, the decomposition product is not combustible, and the residual carbon quantity can be increased, the strength of the expanded carbon layer can be enhanced, and the candle wick effect is avoided.
In some embodiments, the mass ratio of the synergistic flame retardant to expandable graphite flame retardant is 1:1 to 1:3, in the ratio range, more efficient flame retardance is realized by high carbon forming property and expanded network skeleton.
In some embodiments, the coupling agent is one or more selected from silane coupling agents, titanate coupling agents.
Preferably, the silane coupling agent is selected from KH560, KH550, KH570, KH792 and DL602, and the titanate coupling agent is 201, 101, 105, 311, TTS; more preferably, the coupling agent is a silane coupling agent KH560. The epoxy group in the alkyl coupling agent KH560 reacts with TPAE6 terminal amino group and terminal carboxyl group for coupling, and the methoxy group thereof is hydrolyzed to generate Si-OH group, so as to react with inorganic materials such as expandable graphite, ATH, siO 2 And the like.
In some embodiments, the amount of the coupling agent is 0.5 to 3.5 percent of the total mass of the flame retardant; within the proportion range, the improvement of the adhesion between the flame retardant and the polyamide elastomer is facilitated, so that the comprehensive performances of the product, such as mechanical performance, ageing resistance and the like, are improved.
In some embodiments, the dispersant is selected from Ethylene Bis Stearamide (EBS), glyceryl monostearate, glyceryl tristearate, polyethylene wax, liquid paraffin, metal salts of higher fatty acids such as barium stearate, calcium stearate, zinc stearate, and the like, pentaerythritol stearate, preferably Ethylene Bis Stearamide (EBS).
In some embodiments, the antioxidant is selected from hindered phenolic, hindered amine and phosphite antioxidants, preferably one or more of antioxidant 168, antioxidant 608, antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 3114, antioxidant 164, antioxidant 264, antioxidant BHT, antioxidant T501, antioxidant B215, antioxidant B225, more preferably antioxidant 1098 and antioxidant 168 or a combination thereof.
In some embodiments, the absorbent is one or more selected from the group consisting of nano titanium dioxide, porous silicate, diatomite, zinc ricinoleate, zinc sulfate, nano zinc oxide; preferably a porous silicate; the porous silicates include natural porous silicates such as natural zeolites, kaolinite, and artificial porous silicates such as artificial zeolites, ceramics, magnesium silicates, and the like.
The expandable graphite generates a small amount of SO during the expansion process 2 And the invention adds a small amount of absorbent to absorb SO while retarding flame 2 The influence of the flame-retardant material on the environment is avoided, and the effects of no halogen, no toxicity, green and environmental protection are achieved.
In some embodiments, the mass ratio of the absorbent to expandable graphite is: 10:1000 to 25:1000, and the preferred mass ratio is: 15:1000 to 20:1000, in the proportion range, the absorption of acid gas, combustion decomposition activity and harmful gas of the expandable graphite is facilitated, and the flame retardant efficiency and the environmental protection effect are improved.
In a second aspect of the present invention, a preparation method of the expandable graphite modified polyamide elastomer material is provided, wherein the preparation method is selected from processing modes of banburying single-screw extrusion granulation, conical twin-screw granulation, side feeding type parallel twin-screw granulation, planetary extrusion granulation and reciprocating screw extrusion granulation, and preferably, the banburying single-screw extrusion granulation is adopted.
In some embodiments, the method for preparing the expandable graphite-modified polyamide elastomer material comprises the following steps:
s1: mixing expandable graphite, a synergistic flame retardant, a coupling agent and a compatilizer, heating to a certain temperature, and stopping mixing to ensure that the coupling agent and the flame retardant fully react;
s2: adding polyamide elastomer resin, a dispersing agent, an antioxidant and an absorbent, and continuously mixing for a period of time to obtain a material;
s3: placing the mixed materials into an internal mixer for internal mixing to obtain a melt-shaped mixture of the polyamide elastomer material modified by the expandable graphite;
s4: and extruding and granulating the melt mixture in an extruder to obtain the expandable graphite modified polyamide elastomer material.
In some embodiments, in step S1, the mixing is stopped at a temperature of 60 to 80 ℃ based on the temperature of the mixed material.
In some embodiments, in step S1, the temperature is raised while mixing in a high-speed mixing friction heating manner, wherein the high-speed mixing rotation speed is 850 to 1440r/min; alternatively, the temperature is raised while mixing by heating and high-speed mixing, and the mixing time until the predetermined temperature is reached is controlled within a range of 5 to 15min, preferably 10 to 12min.
In some embodiments, the mixing time in step S2 is 3-10min, preferably 3-5min. In some embodiments, in step S3, the banburying temperature is 150 to 180 ℃.
In some embodiments, the temperature of extrusion granulation in step S4 is 160 to 210 ℃.
The processing temperature provided in the preparation method of the invention is not too high and cannot exceed the decomposition temperature of the expandable graphite.
In a third aspect of the present invention, there is provided a use of the expandable graphite-modified polyamide elastomer material for producing automobile parts.
Preferably, the automobile parts comprise a spherical coupling, a dust cover, a shockproof part, a mudguard and a tyre chain.
Advantageous effects
1. The polyamide elastomer flame-retardant material is prepared by adopting a polyamide elastomer, particularly a nylon 6 type polyether block polyamide elastomer as a base material, expandable graphite and aluminum hydroxide (ATH) as a flame retardant system and adding a proper coupling agent and a proper dispersing agent. The expansion flame-retardant material has the advantages of large expansion rate of the heating surface, thick carbon layer, high flame-retardant efficiency, no halogen, low smoke, no toxicity, environmental protection and excellent mechanical property.
2. The flame retardant property of the expandable graphite modified polyamide elastomer flame retardant material can reach UL94-V0 level, the tensile strength is 27-43MPa, and the impact strength is 20KJ/m 2 The method is suitable for preparing the automobile parts.
3. The preparation method has simple and convenient process and low production cost, and is convenient for large-scale production.
Detailed Description
The invention will be understood by reference to the following examples, which are intended to illustrate the invention and should not be construed as limiting the scope of the invention in any way.
The flame retardant material is an intumescent flame retardant system consisting of expandable graphite and a synergistic flame retardant. The expandable graphite is a novel flame retardant in the utilization of the halogen-free flame retardant technology at the present stage, and the intercalation agent (such as acid, alkali metal, salt and other chemical substances) is inserted into the carbon hexagonal network plane structure between graphite layers by mainly utilizing a chemical and physical method, so that a crystal compound is formed. In practical use, the principle of the flame retardant is as follows: when the crystal compound is heated, the interlaminar inserted substance can be decomposed or gasified due to heating, so that a large amount of expansion heat is generated, because the expansion heat is far greater than the Van der Waals force of a graphite space, the sheet layer can be expanded by air flow, the distance between the graphite layers is further enlarged, so that the worm-shaped expanded graphite is formed, a thick porous carbon layer is formed and covers the surface of the base material, the carbon layer has enough heat stability to separate the flame-retardant main body from a heat source, so that the decomposition of the polymer is delayed and terminated, meanwhile, acid radicals in the interlayer are released during expansion, the carbonization of the base material is promoted, so that a good effect is achieved through various flame-retardant modes, the material is non-toxic, no toxic or corrosive gas container is generated during heating, and the smoke generation amount can be greatly reduced. Meanwhile, the synergistic flame retardant aluminum hydroxide is decomposed by heating, absorbs heat in the environment, inhibits the temperature rise and degradation speed of the material, and can dilute combustible gas by water vapor generated by decomposition; meanwhile, the decomposition product is not combustible, and the residual carbon quantity can be increased, the strength of the expanded carbon layer can be enhanced, and the candle wick effect is avoided.
Reagent:
self-made TPAE6: the self-made polyamide elastomer resin TPAE-6 (relative viscosity is about 2.0) is prepared by a preparation method of patent CN104327266B example 2, and the preparation method comprises the following specific steps:
adding 20g of polyethylene glycol with the number average molecular weight of 2000, 80g of caprolactam, 3g of deionized water, 3g of sulfuric acid and 1g of adipic acid into a reactor, heating to 240 ℃ under the protection of nitrogen, and reacting for 1.5 hours under the condition of mechanical stirring at 800 rpm; then the mixture is vacuumized to 40Pa at 260 ℃ and continuously stirred mechanically at 800rpm for reaction for 2.5 hours, and then the mixture is extracted by boiling water and dried.
Expandable graphite: EG-X200 with the grain diameter of 80 meshes, the expansion ratio of more than or equal to 230, the initial expansion temperature of more than 250 ℃, qingdao rock-sea graphite Limited company.
Aluminum hydroxide (ATH): FR-3801, whiteness not less than 97, particle size D 50 1.5-2.0 μm, and is available from combined fertilizer, zhongke antiflaming New Material Co.
Ethylene Bis Stearamide (EBS): EB-FF, a plastication Co., ltd, shang guan city.
Polyurethane elastomer (TPU): WHT-8254 Wanhua chemical.
Other TPAEs 6 were purchased from: akoma PEBAX HD5513.
Coupling agent KH560: FT-560 of Nanjing Feiteng New Material science and technology Co.
Antioxidant 1098/168: basf 1098 and 168 of Dinghai plastics chemical Co., ltd.
Absorbent porous silicate: magnesium silicate MS10E from the company Tianjin Italon auxiliaries.
Equipment:
high-speed mixer: HSM-50 Jiangsu Bell machines;
single-screw all-in-one machine of internal mixer: yongfeng CF-10L, yongfeng mechanical science and technology, inc., dongguan City.
An injection molding machine: UN120SM Mi precision machines, inc. of Guandongyi;
electronic universal material testing machine: zwick/Roell Z020 Shanghai Z Wei Ke mechanical Equipment, inc.;
horizontal vertical burning apparatus: CZF-5 Beijing Zhonghang times instruments and equipments, inc.;
pendulum impact tester: zwick/RoellHIT50P Shanghai Z Wei Ke mechanical devices, inc.;
an incision instrument: b1120.26.10 Shanghai Zxft Wei Ke mechanical devices, inc.
Example 1
The embodiment provides a preparation method for preparing an expandable graphite modified polyamide elastomer material, which comprises the following steps:
(1) Adding 15 parts by weight of expandable graphite, 15 parts by weight of ATH and 0.4 part by weight of silane coupling agent KH560 (which can be diluted by 95 vol% ethanol when added, the content represents the content before dilution, and the dilution volume ratio KH560:95% ethanol = 1:5) into a high-speed mixer in a spray form, heating while mixing in a high-speed mixing friction heating manner, wherein the high-speed mixing rotation speed is 1250r/min, and stopping mixing after the temperature reaches 70 ℃ to obtain a flame retardant mixture subjected to surface treatment;
(2) Adding 68.2 parts by weight of self-made TPAE6, 0.6 part by weight of EBS, 0.5 part by weight of antioxidant mixture (0.2 part by weight of 1098 and 0.3 part by weight of 168 parts by weight) and 0.3 part by weight of absorbent magnesium silicate into the flame retardant mixture subjected to surface treatment, continuously and fully blending for 3-5 minutes in a high-speed mixer, and discharging to obtain the expanded flame-retardant polyamide elastomer raw material mixture.
(3) And adding the expanded flame-retardant polyamide elastomer raw material mixture into an internal mixer, and carrying out melt mixing at the temperature of 150-180 ℃ to obtain an expanded flame-retardant polyamide elastomer melt mixture.
(4) And adding the expanded flame-retardant polyamide elastomer molten mixture into a single-screw extruder, and extruding and granulating at the temperature of 160-210 ℃ to obtain the expanded flame-retardant polyamide elastomer material.
Examples 2 to 6
A polyamide elastomer material was prepared by the method of example 1, except that the amounts of the components were varied, as specified in Table 1.
Table 1 examples 1-6 raw material components for preparing polyamide elastomer materials
| Examples | Self-made TPAE6 | Expandable graphite | ATH | KH560 | EBS | Antioxidant agent | Absorbent agent | Total amount of |
| 1 | 68.2 | 15 | 15 | 0.4 | 0.6 | 0.5 | 0.3 | 100 |
| 2 | 57.6 | 20 | 20 | 0.5 | 1 | 0.5 | 0.4 | 100 |
| 3 | 62.6 | 25 | 10 | 0.5 | 1 | 0.5 | 0.4 | 100 |
| 4 | 49.2 | 30 | 18 | 0.6 | 1.2 | 0.5 | 0.5 | 100 |
| 5 | 65.7 | 20 | 12 | 0.5 | 1 | 0.5 | 0.3 | 100 |
| 6 | 46.6 | 35 | 15 | 0.8 | 1.5 | 0.5 | 0.6 | 100 |
Comparative examples 1 to 2: :
an intumescent flame retardant material was prepared by the method of example 1 except that the home-made TPAE6 substrate was replaced with the commercial TPAE6 polyamide elastomer PEBAX HD5513 or the commercial polyurethane elastomer TPU (WHT-8254), and the remaining components and amounts are shown in table 2.
Table 2 comparative examples 1 to 8 raw material components for preparing intumescent flame retardant materials
Comparative examples 3 to 8
Comparative examples 3-8 a polyamide elastomer flame retardant material was prepared by the method of example 1, except that the expandable graphite, ATH or KH560 was not included in the components or the expandable graphite, ATH or KH560 were out of the range claimed in the present invention, as shown in table 2.
Experimental example 1 testing of mechanical properties and flame retardancy:
the flame retardant performance and the mechanical property of the composite materials of the examples 1 to 6 and the comparative examples 1 to 8 are tested, and the performance evaluation method and the test standard are as follows:
the extruded, pelletized composite was dried at 90 ℃ for 1-2 hours and then test specimens (each set of specimens comprised 5 tensile, impact test specimens and 10 flame retardant test specimens) were molded using an injection molding machine equipped with a standard test specimen mold.
And (3) testing mechanical properties: the tensile properties of the composite were tested using a universal tensile tester according to the ASTM D638-2003 Standard for tensile Properties of plastics, american society for testing materials. Tensile testing was performed on at least 5 replicates per group and the results averaged. The composite was tested according to the standard for plastic cantilever beam impact in ISO180-2001, with at least 5 parallel samples per group being guaranteed for impact testing, and the results averaged (pendulum impact tester, notch gauge).
And (3) testing the flame retardant property: the flame retardant performance of the flame retardant is tested according to the UL94-2006 standard, and the standard of a spline is 125x13x1.6mm (horizontal and vertical combustion tester).
The test results are shown in Table 3.
TABLE 3 flame retardancy of intumescent flame retardant materials and mechanical test results
As shown in Table 3, it can be seen from examples 1-6 that 15-40% by weight of expandable graphite is added to a flame retardant polyamide elastomer system of ATH synergistic expandable graphite to achieve the flame retardant effect of UL94-V0, and the flame retardant polyamide elastomer is low in smoke, halogen-free, environment-friendly and excellent in mechanical properties, and is an ideal flame retardant elastomer material for preparing automobile parts.
In comparative examples 1 and 2, TPAE6 PEBAX HD5513 and polyurethane elastomer WHT-8254 which are commonly used in the market are adopted for preparing the intumescent flame retardant material, and under the condition that the elastomers have the same addition and proportion, the flame retardant property of the intumescent flame retardant material is equivalent to that of self-made TPAE6, but the tensile strength of the intumescent flame retardant material is inferior to that of a flame retardant composite material of a polyamide elastomer base material, so that the self-made TPAE6 has good mechanical property advantages.
In comparative examples 3, 4 and 7, the flame retardant effect and mechanical property of the system are not ideal under the condition that the intumescent flame retardant system respectively lacks the main flame retardant expandable graphite, the synergist ATH and the coupling agent KH560. Similarly, in comparative examples 5, 6 and 8, when the mixture ratio of the expanded flame-retardant system substrate polyamide 6 elastomer, the main flame retardant expandable graphite, the synergist ATH and the coupling agent KH560 is not within the range claimed by the invention, the flame-retardant effect or mechanical property of the system is not ideal.
Therefore, through selection of the resin base material, the expandable graphite flame retardant and the ATH synergistic flame retardant, and addition of the coupling agent and the dispersing agent with proper types and dosage, the expandable graphite modified polyamide elastomer material can show excellent balance of flame retardant property and mechanical property, and is environment-friendly and low in cost.
Although the present application has been described with reference to preferred embodiments, it is not intended to limit the scope of the claims, and many possible variations and modifications may be made by one skilled in the art without departing from the spirit of the application.
Claims (10)
1. An expandable graphite-modified polyamide elastomer material, characterized in that it comprises, based on 100 parts by total weight: 45-74 parts of polyamide elastomer, 15-40 parts of expandable graphite flame retardant, 8-25 parts of synergistic flame retardant, 0.3-3 parts of coupling agent, 0.5-3 parts of dispersing agent, 0.1-2 parts of antioxidant and 0.1-2 parts of absorbent.
2. The expandable graphite-modified polyamide elastomer material according to claim 1, wherein the expandable graphite-modified polyamide elastomer material comprises, based on 100 parts by total weight: 50-70 parts of polyamide elastomer, 15-30 parts of expandable graphite flame retardant, 10-20 parts of synergistic flame retardant, 0.4-1 part of coupling agent, 0.6-1.5 parts of dispersing agent, 0.1-1 part of antioxidant and 0.1-0.6 part of absorbent; preferably, based on 100 parts of total weight, comprises: 60-68 parts of polyamide elastomer, 20-25 parts of expandable graphite flame retardant, 10-15 parts of synergistic flame retardant, 0.4-0.8 part of coupling agent, 0.8-1.2 parts of dispersing agent, 0.3-0.8 part of antioxidant and 0.2-0.5 part of absorbent.
3. Expandable graphite modified polyamide elastomer material according to claim 1 or 2, characterized in that the polyamide elastomer is one or more selected from long or short chain polyether block amides, polyether ester amides, polyester amides and polycarbonate amide block copolymers; preferably short chain polyether block polyamide elastomers; more preferably nylon 6 type polyether block polyamide elastomer;
preferably, the polyamide elastomer has a relative viscosity value of 1.5 to 3.0, preferably 2.0 to 2.8, and a hardness value of 25D to 60D.
4. The expandable graphite-modified polyamide elastomer material as claimed in claim 3, wherein the preparation process of the nylon 6-type polyether block polyamide elastomer comprises the following steps:
adding polyether/polyester, caprolactam, deionized water, a catalyst and diacid into a reactor, heating to 200-240 ℃ under the protection of nitrogen, and reacting for 0.5-2 hours under mechanical stirring; then, continuously mechanically stirring and reacting for 0.5 to 3 hours at the temperature of between 250 and 280 ℃ and under the condition of vacuumizing to between 20 and 500 Pa; then extracting with boiling water, and drying to obtain polyamide 6 thermoplastic elastomer resin, wherein the diacid is oxalic acid, malonic acid, succinic acid or adipic acid, and the catalyst is phosphoric acid, sulfuric acid or aminocaproic acid;
preferably, the polyester/polyether is one or more selected from polytetrahydrofuran, polyethylene glycol, polypropylene glycol or polyhexamethylene glycol;
preferably, the number average molecular weight of the polyester/polyether is 300-8000;
preferably, the polyester/polyether soft block is used in an amount of 10 to 60wt%, based on the total weight of polyether/polyester and caprolactam;
preferably, the caprolactam is used in an amount of 40 to 90wt%, based on the total weight of polyether/polyester and caprolactam; and/or the use amount of the diacid is 1 to 10 weight percent; and/or the dosage of the catalyst is 0.1 to 4 weight percent; and/or the dosage of the deionized water is 0.5 to 4 weight percent; preferably, the mechanical stirring speed is 100-800 rpm.
5. Expandable graphite-modified polyamide elastomer material according to claim 1 or 2, characterised in that the expandable graphite is selected from the group consisting of medium or high initial expansion temperature expanded graphite, preferably medium initial expansion temperature expanded graphite, the expansion temperature being not lower than 250 ℃;
preferably, the particle size of the expandable graphite is 30-100 meshes, preferably 80 meshes, and the expandable ratio is not less than 200 times, preferably not less than 230 times;
and/or the synergistic flame retardant is one or more selected from magnesium hydroxide, aluminum hydroxide, red phosphorus, ammonium polyphosphate, triphenyl phosphate, basic magnesium sulfate whisker and silicon dioxide whisker, and is preferably aluminum hydroxide;
preferably, the mass ratio of the synergistic flame retardant to the expandable graphite flame retardant is 1: 1-1: 3.
6. The expandable graphite-modified polyamide elastomer material as claimed in claim 1 or 2, wherein the coupling agent is one or more selected from silane coupling agents, titanate coupling agents;
preferably, the silane coupling agent is selected from KH560, KH550, KH570, KH792 and DL602, and the titanate coupling agent is 201, 101, 105, 311 and TTS; more preferably, the coupling agent is a silane coupling agent KH560;
preferably, the using amount of the coupling agent is 0.5-3.5% of the total mass of the flame retardant;
and/or the dispersing agent is selected from ethylene bis stearamide, glycerol monostearate, glycerol tristearate, polyethylene wax, liquid paraffin, metal salts of higher fatty acid, pentaerythritol stearate, preferably, the metal salts of higher fatty acid comprise barium stearate, calcium stearate, zinc stearate; the dispersant is preferably ethylene bis stearamide.
7. The expandable graphite-modified polyamide elastomer material according to claim 1 or 2, wherein the antioxidant is selected from hindered phenolic, hindered amine and phosphite antioxidants, preferably from antioxidant 168, antioxidant 608, antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 3114, antioxidant 164, antioxidant 264, antioxidant BHT, antioxidant T501, antioxidant B215 and antioxidant B225, more preferably from antioxidant 1098 and antioxidant 168 or a combination thereof;
and/or the absorbent is one or more of nano titanium dioxide, porous silicate, diatomite, zinc ricinoleate, zinc sulfate and nano zinc oxide; preferably a porous silicate; the porous silicate includes natural porous silicate and artificial porous silicate; preferably, the natural porous silicate is selected from natural zeolites, kaolinite, and the artificial porous silicate is selected from artificial zeolites, ceramics, magnesium silicate;
preferably, the mass ratio of the absorbent to the expandable graphite is: 10: 1000-25: 1000, and the preferred mass ratio is: 15: 1000-20: 1000.
8. The process for the preparation of expandable graphite-modified polyamide elastomer material as claimed in any of claims 1 to 7, characterized in that the preparation process is selected from the group of processing modes consisting of internal mixing single-screw extrusion granulation, conical twin-screw granulation, side-fed parallel twin-screw granulation, planetary extrusion granulation, reciprocating screw extrusion granulation, preferably internal mixing single-screw extrusion granulation.
9. The method of claim 8, comprising the steps of:
s1: mixing expandable graphite, a synergistic flame retardant, a coupling agent and a compatilizer, heating to a certain temperature, and stopping mixing to ensure that the coupling agent and the flame retardant fully react;
s2: adding polyamide elastomer resin, a dispersing agent, an antioxidant and an absorbent, and continuously mixing for a period of time to obtain a material;
s3: placing the mixed materials into an internal mixer for internal mixing to obtain a melt-shaped mixture of the polyamide elastomer material modified by the expandable graphite;
s4: extruding and granulating the melt mixture in an extruder to obtain the expandable graphite modified polyamide elastomer material;
preferably, in the step S1, the mixture is mixed by taking the temperature as a standard, and the mixing is stopped when the temperature reaches 60-80 ℃;
preferably, in step S1, the temperature is raised while mixing in a high-speed mixing friction heating manner, wherein the high-speed mixing rotation speed is 850 to 1440r/min; or, the temperature is raised while mixing in a heating high-speed mixing mode, and the mixing time for reaching the specified temperature is controlled within the range of 5-15 min, preferably 10-12 min;
preferably, in step S2, the mixing time is 3-10min, preferably 3-5min;
preferably, in the step S3, the banburying temperature is 150-180 ℃;
preferably, in step S4, the temperature for extrusion granulation is 160 to 210 ℃.
10. Use of an expandable graphite-modified polyamide elastomer material according to any one of claims 1 to 7 or prepared by the preparation process according to claim 8 or 9 for the preparation of automotive parts;
preferably, the automobile parts comprise a ball coupling, a dust cover, a shockproof part, a mudguard and a tyre chain.
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