WO2023071921A1 - 一种聚酰胺复合材料及其制备方法和应用 - Google Patents
一种聚酰胺复合材料及其制备方法和应用 Download PDFInfo
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- WO2023071921A1 WO2023071921A1 PCT/CN2022/126580 CN2022126580W WO2023071921A1 WO 2023071921 A1 WO2023071921 A1 WO 2023071921A1 CN 2022126580 W CN2022126580 W CN 2022126580W WO 2023071921 A1 WO2023071921 A1 WO 2023071921A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glycidyl
- composite material
- lithium
- parts
- polyamide composite
- Prior art date
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- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 239000004952 Polyamide Substances 0.000 title claims abstract description 33
- 229920002647 polyamide Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 50
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 10
- 230000008439 repair process Effects 0.000 claims description 47
- KBWLNCUTNDKMPN-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) hexanedioate Chemical compound C1OC1COC(=O)CCCCC(=O)OCC1CO1 KBWLNCUTNDKMPN-UHFFFAOYSA-N 0.000 claims description 9
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 9
- -1 glycidyl caproate Chemical compound 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- XNJDQHLXEBQMDE-UHFFFAOYSA-N 2-(cyclohexyloxymethyl)oxirane Chemical compound C1OC1COC1CCCCC1 XNJDQHLXEBQMDE-UHFFFAOYSA-N 0.000 claims description 6
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- FWEHVPCBXKCYHE-FPLPWBNLSA-N oxiran-2-ylmethyl (z)-hexadec-9-enoate Chemical compound CCCCCC\C=C/CCCCCCCC(=O)OCC1CO1 FWEHVPCBXKCYHE-FPLPWBNLSA-N 0.000 claims description 6
- 229920006152 PA1010 Polymers 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- HDDQXUDCEIMISH-UHFFFAOYSA-N 2-[[4-[1,2,2-tris[4-(oxiran-2-ylmethoxy)phenyl]ethyl]phenoxy]methyl]oxirane Chemical compound C1OC1COC(C=C1)=CC=C1C(C=1C=CC(OCC2OC2)=CC=1)C(C=1C=CC(OCC2OC2)=CC=1)C(C=C1)=CC=C1OCC1CO1 HDDQXUDCEIMISH-UHFFFAOYSA-N 0.000 claims description 4
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 4
- 229920006374 copolyamide PA6I/6T Polymers 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000003063 flame retardant Substances 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 150000003951 lactams Chemical class 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- 229920006119 nylon 10T Polymers 0.000 claims description 4
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 claims description 4
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 claims description 4
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 3
- OUQGOXCIUOCDNN-UHFFFAOYSA-N Glycidyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC1CO1 OUQGOXCIUOCDNN-UHFFFAOYSA-N 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- NOQXXYIGRPAZJC-UHFFFAOYSA-N oxiran-2-ylmethyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1OC1 NOQXXYIGRPAZJC-UHFFFAOYSA-N 0.000 claims description 3
- YLNSNVGRSIOCEU-UHFFFAOYSA-N oxiran-2-ylmethyl butanoate Chemical compound CCCC(=O)OCC1CO1 YLNSNVGRSIOCEU-UHFFFAOYSA-N 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- NMTHLPUCSWMDJG-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OCC1CO1 NMTHLPUCSWMDJG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000577 Nylon 6/66 Polymers 0.000 claims description 2
- 229920006153 PA4T Polymers 0.000 claims description 2
- 229920006528 PA66/6 Polymers 0.000 claims description 2
- 229920006883 PAMXD6 Polymers 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000498 cooling water Substances 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 2
- 229960004887 ferric hydroxide Drugs 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- FZBIESPTFIVNEJ-UHFFFAOYSA-N oxiran-2-ylmethyl decanoate Chemical compound CCCCCCCCCC(=O)OCC1CO1 FZBIESPTFIVNEJ-UHFFFAOYSA-N 0.000 claims description 2
- CCNCFYINOYWDOK-UHFFFAOYSA-N oxiran-2-ylmethyl octanoate Chemical compound CCCCCCCC(=O)OCC1CO1 CCNCFYINOYWDOK-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 2
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 claims description 2
- 239000012783 reinforcing fiber Substances 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 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 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 claims 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- GJHIRHGCFZXLSM-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 2-butylbutanedioate Chemical compound C1OC1COC(=O)C(CCCC)CC(=O)OCC1CO1 GJHIRHGCFZXLSM-UHFFFAOYSA-N 0.000 claims 1
- KIKYOFDZBWIHTF-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-3-ene-1,2-dicarboxylate Chemical compound C1CC=CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KIKYOFDZBWIHTF-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 description 19
- 238000006460 hydrolysis reaction Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 230000032683 aging Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000000155 melt Substances 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910000358 iron sulfate Inorganic materials 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 241001312297 Selar Species 0.000 description 1
- 229920003365 Selar® Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229920006020 amorphous polyamide Polymers 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- SXCRXFXUSQYWCD-UHFFFAOYSA-N oxiran-2-ylmethyl phenylmethanesulfonate Chemical compound C1OC1COS(=O)(=O)CC1=CC=CC=C1 SXCRXFXUSQYWCD-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
- C08K2003/3072—Iron sulfates
Definitions
- the invention relates to the technical field of polymer materials, in particular to a polyamide composite material and its preparation method and application.
- the external aid type repair uses the pre-embedded repair agent in the material, stimulates the release of the repair agent and repairs the structure when the material is damaged, and has a high repair efficiency.
- the repair agent is required to be protected, so the coating treatment of the repair agent and the targeted treatment of the damaged position require a higher content, which makes the cost of foreign aid self-repair relatively high, and the effect is obviously affected by the content of the repair agent. limit.
- Intrinsic repair does not need to use complicated coating technology, and can perform multiple repairs by using its own potential repair ability, based on non-covalent bonds and reversible covalent bonds.
- the conditional requirements for intrinsic stimulation of repair behavior may be higher, or the repair efficiency may not be ideal.
- the repair time is required to be longer; through reversible covalent bonds such as disulfide bonds, acylhydrazone bonds, Diels-Alder reactions require or light, or Temperature control for repair.
- the intrinsic repair agent will have some side reactions with the polyamide composite material, which may not only affect the design performance of the material, but also reduce the repairability.
- the repairing agent containing epoxy groups Preferably, 1.5-3 parts of intrinsic repairing agent containing epoxy groups, 0.4-1.2 parts of iron or lithium or copper metal salt; more preferably, 2.1-2.4 parts of intrinsic repairing agent containing epoxy groups , 0.6-0.9 parts of iron or lithium or copper metal salt.
- the intrinsic repair agent containing epoxy groups is selected from glycidyl ethers, glycidyl esters, N,N,N',N'-tetraepoxypropyl-4,4'-diaminobis At least one of phenylmethane, bis[p-(N-methyl-N-2,3-epoxypropylamino)-phenyl]methane;
- the glycidyl ethers are selected from 2,2-bis( At least one of p-hydroxyphenyl) propane diglycidyl ether, 1,1,2,2-tetra(p-hydroxyphenyl) ethane tetraglycidyl ether;
- the glycidyl esters are selected from methyl Glycidyl Acrylate, Glycidyl Butyrate, Glycidyl Succinate, Glycidyl Caproate, Glycidyl Caprylate, Glycidyl Caprate, Glycidyl Stearate, Gly
- the intrinsic repair agent containing epoxy groups is selected from 2,2-di(p-hydroxyphenyl)propane diglycidyl ether, 1,1,2,2-tetrakis(p-hydroxyphenyl) At least one of ethane tetraglycidyl ether, glycidyl palmitoleate, cyclohexyl glycidyl ether, diglycidyl adipate or diglycidyl cyclohexane-1,2-dicarboxylate kind.
- the present invention utilizes the intrinsic repairing agent containing epoxy groups to slowly extend the chain during the long-term use of the polyamide composite material, so that the intrinsic repairing agent containing epoxy groups is subjected to harsh conditions in the composite material. It plays a repairing role when structural damage occurs in working conditions. Furthermore, the presence of metal salts can significantly improve the repairing activity of intrinsic repairing agents containing epoxy groups, prolong the service life of polyamide composites, reduce waste of resources, and improve System security and reliability.
- PA1010 TMNO F PA1010, Arkema;
- Intrinsic restoration agent C cyclohexane-1,2-dicarboxylic acid diglycidyl ester, purchased from Sigma-Aldrich;
- Table 1 Contents (parts by weight) and test results of each component of the polyamide composite material of Examples 1-6
- the iron/lithium/copper metal salt is preferably lithium metal salt, which has the best hydrolysis resistance and xenon lamp aging resistance.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种聚酰胺复合材料，按重量份计，包括以下组分：聚酰胺树脂100份；含有环氧基团的本征型修复剂0.3-5份；铁或锂或铜金属盐0.05-1.5份。本发明通过复配含有环氧基团的本征型修复剂与铁或锂或铜金属盐，上述金属盐的存在能够明显提升含有环氧基团的本征型修复剂在复合材料程遭受恶劣的工况发生结构损伤时起到修复作用，延长聚酰胺复合材料的使用寿命，减少资源浪费，提高系统的安全性和可靠性。
Description
本发明涉及高分子材料技术领域，特别是涉及一种聚酰胺复合材料及其制备方法和应用。
在20世纪80年代中期美国军方提出材料自愈合概念，在1994年美国伊利诺伊大学的Carolyn Dry提出在混凝土中加入缩醛高分子的玻璃纤维，用于修复混凝土裂痕。此后关于材料自修复或自愈合的研究进入快速发展阶段。根据修复剂来源或修复的方式可以划分为外援型和本征型修复，外援型修复是在材料发生破坏后引入外部的修复剂，包括微胶囊型、中空纤维型、微脉管型，通常涉及到修复剂的包覆或保护。本征型修复是利用材料自身的化学结构进行修复，包括共价键型及非共价键型的自修复，即破损得以修复的相互作用方式。
外援型修复通过材料内部预埋修复剂，在材料破损的同时刺激修复剂释放并修复结构，具有较高的修复效率。但正常状态下要求修复剂受保护，因此对修复剂的包覆处理，以及对破损位置的靶向处理需求较高的含量，使得外援型自修复的成本比较高昂，且效果明显受修复剂含量限制。
本征型修复无需采用复杂的包覆技术，利用自身潜在的修复能力，可进行多次修复，基于非共价键和可逆共价键的方式进行修复。但是，一方面，本征型刺激修复行为进行的条件要求可能更高，或者修复的效率并不理想。例如基于配位、氢键、Π键共轭的非共价键作用，修复的时间要求更长；通过可逆的共价键如双硫键、酰腙键、Diels-Alder反应需要或光照、或温度控制进行修复。另一方面，在熔融共混过程中本征型修复剂会与聚酰胺复合材料进行一些副反应，不仅可能会影响材料的设计性能，也可能会降低修复性。
发明内容
本发明的目的在于，提供一种具有良好的自修复性能的聚酰胺复合材料，及其制备方法。
一种聚酰胺复合材料，按重量份计，包括以下组分：
聚酰胺树脂 100份；
含有环氧基团的本征型修复剂 0.3-5份；
铁或锂或铜金属盐 0.05-1.5份。
优选的，含有环氧基团的本征型修复剂1.5-3份，铁或锂或铜金属盐0.4-1.2份；更优选的，含有环氧基团的本征型修复剂2.1-2.4份，铁或锂或铜金属盐0.6-0.9份。
所述的含有环氧基团的本征型修复剂选自缩水甘油醚类、缩水甘油酯类、N,N,N',N'-四 环氧丙基-4,4'-二氨基二苯甲烷、双[对-(N-甲基-N-2,3-环氧丙氨基)-苯基]甲烷中的至少一种；所述的缩水甘油醚类选自2,2-二(对-羟基苯基)丙烷二缩水甘油醚、1,1,2,2-四(对羟基苯基)乙烷四缩水甘油醚中的至少一种；所述的缩水甘油酯类选自甲基丙烯酸缩水甘油酯、丁酸缩水甘油酯、丁二酸缩水甘油酯、己酸缩水甘油酯、辛酸缩水甘油酯、癸酸缩水甘油酯、硬脂酸缩水甘油酯、棕榈油酸缩水甘油酯、环己基缩水甘油酯醚、甲苯磺酸缩水甘油酯、对甲苯磺酸缩水甘油酯、叔碳酸缩水甘油酯、环己烷-1,2-二羧酸二缩水甘油酯、四氢邻苯二甲酸二缩水甘油酯、己二酸二缩水甘油酯或异氰脲酸-三缩水甘油酯中的至少一种。
优选的，所述的含有环氧基团的本征型修复剂选自2,2-二(对-羟基苯基)丙烷二缩水甘油醚、1,1,2,2-四(对羟基苯基)乙烷四缩水甘油醚、棕榈油酸缩水甘油酯、环己基缩水甘油酯醚、己二酸二缩水甘油酯或环己烷-1,2-二羧酸二缩水甘油酯中的至少一种。
更优选的，所述的含有环氧基团的本征型修复剂选自2,2-二(对-羟基苯基)丙烷二缩水甘油醚、己二酸二缩水甘油酯或环己烷-1,2-二羧酸二缩水甘油酯中的至少一种。
所述的铁金属盐选自氯化亚铁、氯化铁、硫酸铁、氧化铁、氧化亚铁或氢氧化铁中的至少一种；所述的锂金属盐选自氯化锂、碳酸锂、硫酸锂或醋酸锂中的至少一种；所述的铜金属盐选自氯化铜、碳酸铜、硫酸铜、醋酸铜、溴化铜或碘化铜中的至少一种；优选的，所述的铁或锂或铜金属盐中选自锂金属盐。
所述的聚酰胺树脂由二元胺和二元酸逐步缩聚而成，或由内酰胺开环聚合而成，或由氨基酸逐步缩聚而成，或由二元胺、二元酸、内酰胺、氨基酸共聚而成；所述的聚酰胺树脂选自PA46、PA66、PA6、PA11、PA12、PA610、PA612、PA1010、PA1012、PA1212、PA4T、PA6T、PA9T、PA10T、PA6I、PAMXD6、PA6I、PA66/6、PA6/66、PA6I/6T或PA6T/66中的一种或几种。
可以根据实际情况选择是否加入0-30份的的抗氧剂、润滑剂、阻燃剂、增强纤维等。
阻燃剂可以是溴系阻燃剂、含锑化合物、金属氢氧化物、硼酸盐等。
抗氧剂可以是单酚和双酚类、亚磷酸酯类、含硫类、胺类、半受阻酚类中的任意一种或多种；润滑剂可以是乙撑双硬脂酰胺、二甲基硅油、硬脂酸酰胺、硬脂酸、硬脂酸丁酯、酯蜡、皂化蜡中的任意一种或多种。
本发明的聚酰胺复合材料的制备方法，包括以下步骤：按照配比将聚酰胺树脂、含有环氧基团的本征型修复剂、铁或锂或铜金属盐混合均匀，后通过双螺杆挤出机挤出造粒，螺杆温度范围是200-320℃、转速范围是200-600rpm，得到聚酰胺复合材料。
本发明的的聚酰胺复合材料的应用，用于制备汽车结构件、散热风扇、护风圈、油底壳、 前端框架、冷却水室、齿轮箱罩盖、发动机罩盖、汽车发动机舱部件、进气管、出气管、电池护套、燃料储罐里衬。
本发明具有如下有益效果
本发明利用了含有环氧基团的本征型修复剂在聚酰胺复合材料在长期的使用过程中进行缓慢的扩链，使含有环氧基团的本征型修复剂在复合材料遭受恶劣的工况发生结构损伤时起到修复作用，进一步的，金属盐的存在能够明显提升含有环氧基团的本征型修复剂的修复活性，延长聚酰胺复合材料的使用寿命，减少资源浪费，提高系统的安全性和可靠性。
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例和对比例所用原材料来源如下：
PA66：EP158，浙江华峰；
PA10T：Vicnyl 700，金发科技；
PA1010：TMNO F PA1010，阿科玛；
PA12：AMNO PA12，阿科玛；
PA6T/66：FE15502，杜邦；
PA6I/6T：Selar PA3426R，杜邦；
本征型修复剂A：2,2-二(对-羟基苯基)丙烷二缩水甘油醚，购自Sigma-Aldrich；
本征型修复剂B：己二酸二缩水甘油酯，购自武汉鑫儒化工有限公司；
本征型修复剂C：环己烷-1,2-二羧酸二缩水甘油酯，购自Sigma-Aldrich；
本征型修复剂D：1,1,2,2-四(对羟基苯基)乙烷四缩水甘油醚，购自Sigma-Aldrich；
本征型修复剂E：棕榈油酸缩水甘油酯，购自Sigma-Aldrich；
本征型修复剂F：环己基缩水甘油酯醚，购自盐城市麦迪科化学品制造有限公司；
本征型修复剂G：丁酸缩水甘油酯，购自Sigma-Aldrich；
本征型修复剂H：N,N,N',N'-四环氧丙基-4,4'-二氨基二苯甲烷，购自Sigma-Aldrich；
本征型修复剂I：甲基丙烯酸缩水甘油酯，购自Sigma-Aldrich；
本征型修复剂J：硬脂酸缩水甘油酯，购自上海阿拉丁生化科技股份有限公司；
本征型修复剂K：异氰脲酸-三缩水甘油酯，购自深圳聚合生化科技有限公司；
氯化铁：市售；
硫酸铁：市售；
氯化锂：市售；
醋酸锂：市售；
硫酸铜：市售；
氯化铜：市售；
硫酸锌：市售；
硫酸镍：市售；
抗氧剂：受阻酚类抗氧剂，Irganox 1098。
实施例和对比例聚酰胺复合材料的制备方法：按照配比将聚酰胺树脂、含有环氧基团的本征型修复剂、铁或锂或铜金属盐混合均匀，后通过双螺杆挤出机挤出造粒，螺杆温度为前后两区180℃-220℃，前后第二区为220℃-260℃，其他230℃-270℃，转速范围是400rpm，得到聚酰胺复合材料。
各项测试方法：
(1)耐水解性评价：根据ISO 527-2/1A，通过模制成型制备的4mm厚测试棒、宽度10mm，测试速度5mm/min，测试23℃在空气中的拉伸强度作为初始性能，然后将其它未测试样条置于乙二醇与水按照1：1混合溶液的水解介质中，将测试拉伸强度样条至于介质中135℃高温存放1000小时，取出除去样条表面多余介质，在23℃测试拉伸样条的拉伸强度作为水解后性能，根据初始性能及水解后的性能计算性能保持率。
(2)耐氙灯老化评价：根据美国汽车协会SAE J2527标准，通过氙灯老化模拟材料接受户外耐候老化的过程，包含光照环境、黑暗环境、喷淋阶段、干燥阶段、加热等环境因素，评价实施例及对照例中的组合物模制成的片材经过2500kJ/m
2的辐照量(约合1900h)之后的表面色差变化(ΔE)，色差变化越大表明材料的耐候性能越差。
(3)熔融指数：根据ISO 1133-1-2001测试水解前后的熔融指数，将待测的颗粒置于不锈钢的网兜或者容器，置于乙二醇与水按照1：1混合溶液中，135℃高温存放1000小时后取出，使用去离子水清洗颗粒表面去除乙二醇溶液，在120℃鼓风干燥箱中烘干4-6小时，作为水解后熔指待测样品。水解前后的待测样品，按照测试温度为熔点Tm+20℃，在2.16kg砝码作用下的熔体流动速率，对于非晶聚酰胺采用300℃，在2.16kg砝码作用下的熔体流动速率。计算水解前后熔体流动速率变化率越低越好。
表1：实施例1-6聚酰胺复合材料各组分含量(重量份)及测试结果
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | |
| PA66 | 100 | |||||
| PA10T | 100 | |||||
| PA1010 | 100 | |||||
| PA12 | 100 | |||||
| PA6T/66 | 100 | |||||
| PA6I/6T | 100 | |||||
| 本征型修复剂A | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| 硫酸铁 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| 抗氧剂 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| 耐水解性，％ | 58 | 67 | 66 | 78 | 59 | 63 |
| ΔE | 2.2 | 3.0 | 1.8 | 1.5 | 3.5 | 3.3 |
| 耐水解测试前熔融指数，g/10min | 15.5 | 14.7 | 28.9 | 25.4 | 13.9 | 15.3 |
| 耐水解测试前后熔融指数变化率，％ | 50 | 24 | 22 | 17 | 44 | 29 |
表2：实施例7-12聚酰胺复合材料各组分含量(重量份)及测试结果
表3：实施例13-16聚酰胺复合材料各组分含量(重量份)及测试结果
| 实施例13 | 实施例14 | 实施例15 | 实施例16 | |
| PA66 | 100 | 100 | 100 | 100 |
| 本征型修复剂H | 0.5 | |||
| 本征型修复剂I | 0.5 | |||
| 本征型修复剂J | 0.5 | |||
| 本征型修复剂K | 0.5 | |||
| 硫酸铁 | 0.2 | 0.2 | 0.2 | 0.2 |
| 抗氧剂 | 0.2 | 0.2 | 0.2 | 0.2 |
| 耐水解性，％ | 47 | 46 | 44 | 48 |
| ΔE | 3.0 | 2.7 | 2.9 | 2.7 |
| 耐水解测试前熔融指数，g/10min | 11.5 | 22.5 | 23.7 | 12.6 |
| 耐水解测试前后熔融指数变化率，％ | 80 | 83 | 86 | 79 |
由实施例1/7-16可知，含有环氧基团的本征型修复剂优选2,2-二(对-羟基苯基)丙烷二缩水甘油醚、1,1,2,2-四(对羟基苯基)乙烷四缩水甘油醚、棕榈油酸缩水甘油酯、环己基缩水甘油酯醚、己二酸二缩水甘油酯或环己烷-1,2-二羧酸二缩水甘油酯中的至少一种。更优选2,2-二(对-羟基苯基)丙烷二缩水甘油醚、己二酸二缩水甘油酯或环己烷-1,2-二羧酸二缩 水甘油酯中的至少一种。。
表4：实施例17-21聚酰胺复合材料各组分含量(重量份)及测试结果
| 实施例17 | 实施例18 | 实施例19 | 实施例20 | 实施例21 | |
| PA66 | 100 | 100 | 100 | 100 | 100 |
| 本征型修复剂A | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| 氯化铁 | 0.2 | ||||
| 氯化锂 | 0.2 | ||||
| 醋酸锂 | 0.2 | ||||
| 硫酸铜 | 0.2 | ||||
| 氯化铜 | 0.2 | ||||
| 抗氧剂 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| 耐水解性，％ | 55 | 61 | 63 | 54 | 52 |
| ΔE | 2.3 | 1.7 | 1.6 | 2.9 | 2.8 |
| 耐水解测试前熔融指数，g/10min | 16.4 | 15.8 | 16.5 | 16.7 | 17.1 |
| 耐水解测试前后熔融指数变化率，％ | 60 | 31 | 28 | 59 | 63 |
由实施例1/17-21可知，铁/锂/铜金属盐优选锂金属盐，耐水解性和耐氙灯老化最好。
表5：实施例22-28聚酰胺复合材料各组分含量(重量份)及测试结果
由实施例1/22-27可知，优选含有环氧基团的本征型修复剂1.5-3份，铁或锂或铜金属盐0.4-1.2份；更优选的，含有环氧基团的本征型修复剂2.1-2.4份，铁或锂或铜金属盐0.6-0.9份。
表6：对比例7-13聚酰胺复合材料各组分含量(重量份)及测试结果
由实施例和对比例可知，本征型修复剂在耐老化测试中不断的修复，使得熔融指数上升 的趋势降缓，结合耐水解和耐氙灯老化性的提高，可知本发明的聚酰胺复合材料具有很好的自修复性。
由对比例1/2可知，本发明的自修复性需要本征型修复剂与铁或锂或铜金属盐的协同，缺一则不能够实现发明目的。
由对比例3/4可知，本征型修复剂含量过低或过多都无法实现良好的自修复性。
由对比例5-6可知，铁或锂或铜金属盐含量过低或过多也无法实现良好的自修复性。
由对比例7-8可知，锌、镍金属盐无法实现本发明的技术效果。
Claims (10)
- 一种聚酰胺复合材料，其特征在于，按重量份计，包括以下组分：聚酰胺树脂 100份；含有环氧基团的本征型修复剂 0.3-5份；铁或锂或铜金属盐 0.05-1.5份。
- 根据权利要求1所述的聚酰胺复合材料，其特征在于，含有环氧基团的本征型修复剂1.5-3份，铁或锂或铜金属盐0.4-1.2份；更优选的，含有环氧基团的本征型修复剂2.1-2.4份，铁或锂或铜金属盐0.6-0.9份。
- 根据权利要求1所述的聚酰胺复合材料，其特征在于，所述的含有环氧基团的本征型修复剂选自缩水甘油醚类、缩水甘油酯类、N,N,N',N'-四环氧丙基-4,4'-二氨基二苯甲烷、双[对-(N-甲基-N-2,3-环氧丙氨基)-苯基]甲烷中的至少一种；所述的缩水甘油醚类选自2,2-二(对-羟基苯基)丙烷二缩水甘油醚、1,1,2,2-四(对羟基苯基)乙烷四缩水甘油醚中的至少一种；所述的缩水甘油酯类选自甲基丙烯酸缩水甘油酯、丁酸缩水甘油酯、丁二酸缩水甘油酯、己酸缩水甘油酯、辛酸缩水甘油酯、癸酸缩水甘油酯、硬脂酸缩水甘油酯、棕榈油酸缩水甘油酯、环己基缩水甘油酯醚、甲苯磺酸缩水甘油酯、对甲苯磺酸缩水甘油酯、叔碳酸缩水甘油酯、环己烷-1,2-二羧酸二缩水甘油酯、四氢邻苯二甲酸二缩水甘油酯、己二酸二缩水甘油酯或异氰脲酸-三缩水甘油酯中的至少一种。
- 根据权利要求3所述的聚酰胺复合材料，其特征在于，所述的含有环氧基团的本征型修复剂选自2,2-二(对-羟基苯基)丙烷二缩水甘油醚、双[对-(N-甲基-N-2,3-环氧丙氨基)-苯基]甲烷、棕榈油酸缩水甘油酯、环己基缩水甘油酯醚、己二酸二缩水甘油酯或环己烷-1,2-二羧酸二缩水甘油酯中的至少一种。
- 根据权利要求4所述的聚酰胺复合材料，其特征在于，所述的含有环氧基团的本征型修复剂选自2,2-二(对-羟基苯基)丙烷二缩水甘油醚、己二酸二缩水甘油酯或环己烷-1,2-二羧酸二缩水甘油酯中的至少一种。
- 根据权利要求1所述的聚酰胺复合材料，其特征在于，所述的铁金属盐选自氯化亚铁、氯化铁、硫酸铁、氧化铁、氧化亚铁或氢氧化铁中的至少一种；所述的锂金属盐选自氯化锂、碳酸锂、硫酸锂或醋酸锂中的至少一种；所述的铜金属盐选自氯化铜、碳酸铜、硫酸铜、醋酸铜、溴化铜或碘化铜中的至少一种；优选的，所述的铁或锂或铜金属盐中选自锂金属盐。
- 根据权利要求1所述的聚酰胺复合材料，其特征在于，所述的聚酰胺树脂由二元胺和二元酸逐步缩聚而成，或由内酰胺开环聚合而成，或由氨基酸逐步缩聚而成，或由二元胺、二元酸、内酰胺、氨基酸共聚而成；所述的聚酰胺树脂选自PA46、PA66、PA6、PA11、PA12、 PA610、PA612、PA1010、PA1012、PA1212、PA4T、PA6T、PA9T、PA10T、PA6I、PAMXD6、PA6I、PA66/6、PA6/66、PA6I/6T或PA6T/66中的一种或几种。
- 根据权利要求1所述的聚酰胺复合材料，其特征在于，还包括0-30份的抗氧剂、润滑剂、阻燃剂、增强纤维中的至少一种。
- 根据权利要求1-8任一项所述的聚酰胺复合材料的制备方法，其特征在于，包括以下步骤：按照配比将聚酰胺树脂、含有环氧基团的本征型修复剂、铁或锂或铜金属盐混合均匀，后通过双螺杆挤出机挤出造粒，螺杆温度范围是200-320℃、转速范围是200-600rpm，得到聚酰胺复合材料。
- 根据权利要求1-8任一项所述的聚酰胺复合材料的应用，其特征在于，用于制备汽车结构件、散热风扇、护风圈、油底壳、前端框架、冷却水室、齿轮箱罩盖、发动机罩盖、汽车发动机舱部件、进气管、出气管、电池护套、燃料储罐里衬。
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