CN117327392A - Halogen-free flame-retardant polyamide composition and preparation method and application thereof - Google Patents
Halogen-free flame-retardant polyamide composition and preparation method and application thereof Download PDFInfo
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- CN117327392A CN117327392A CN202311148349.5A CN202311148349A CN117327392A CN 117327392 A CN117327392 A CN 117327392A CN 202311148349 A CN202311148349 A CN 202311148349A CN 117327392 A CN117327392 A CN 117327392A
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- halogen
- zinc
- free flame
- flame retardant
- polyamide composition
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 66
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 239000004952 Polyamide Substances 0.000 title claims abstract description 49
- 229920002647 polyamide Polymers 0.000 title claims abstract description 49
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 6
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 55
- 239000011701 zinc Substances 0.000 claims abstract description 32
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 238000002844 melting Methods 0.000 claims abstract description 24
- 230000008018 melting Effects 0.000 claims abstract description 24
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 23
- 239000003365 glass fiber Substances 0.000 claims abstract description 11
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 22
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- -1 zinc carboxylate Chemical class 0.000 claims description 9
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 8
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 4
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 238000004146 energy storage Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 229940102001 zinc bromide Drugs 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 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
- HHIMNFJHTNVXBJ-UHFFFAOYSA-L zinc;dinitrite Chemical compound [Zn+2].[O-]N=O.[O-]N=O HHIMNFJHTNVXBJ-UHFFFAOYSA-L 0.000 claims description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims 1
- HFVKYLPSHXAMME-UHFFFAOYSA-J diethylphosphinate;titanium(4+) Chemical compound [Ti+4].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC HFVKYLPSHXAMME-UHFFFAOYSA-J 0.000 claims 1
- GTOWTBKGCUDSNY-UHFFFAOYSA-K tris[[ethyl(methyl)phosphoryl]oxy]alumane Chemical compound [Al+3].CCP(C)([O-])=O.CCP(C)([O-])=O.CCP(C)([O-])=O GTOWTBKGCUDSNY-UHFFFAOYSA-K 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000155 melt Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 229920006119 nylon 10T Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 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 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 2
- DMHHYBUEZRZGDK-UHFFFAOYSA-N 2-(3,5-ditert-butyl-4-hydroxyphenyl)propanamide Chemical compound NC(=O)C(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 DMHHYBUEZRZGDK-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- FLZYQMOKBVFXJS-UHFFFAOYSA-N 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoic acid Chemical compound CC1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O FLZYQMOKBVFXJS-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- GYOZZWNPRKAISG-UHFFFAOYSA-N P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(O)(C(CO)(CO)CO)C1=CC(=C(C(=C1)C(C)(C)C)C)C(C)(C)C)C(C)(C)C)C Chemical compound P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(O)(C(CO)(CO)CO)C1=CC(=C(C(=C1)C(C)(C)C)C)C(C)(C)C)C(C)(C)C)C GYOZZWNPRKAISG-UHFFFAOYSA-N 0.000 description 1
- 229920006152 PA1010 Polymers 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 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 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- BSQWCPPAKRSDNZ-UHFFFAOYSA-N [PH2](O)=O.C(C)[Zn]CC Chemical compound [PH2](O)=O.C(C)[Zn]CC BSQWCPPAKRSDNZ-UHFFFAOYSA-N 0.000 description 1
- JMJWMGLCPXGAFU-UHFFFAOYSA-M [PH2]([O-])=O.C[Al+]CC Chemical compound [PH2]([O-])=O.C[Al+]CC JMJWMGLCPXGAFU-UHFFFAOYSA-M 0.000 description 1
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QYVZEPLDLPYECM-XUTLUUPISA-N octadecyl (e)-3-(3,4-dihydroxyphenyl)prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)\C=C\C1=CC=C(O)C(O)=C1 QYVZEPLDLPYECM-XUTLUUPISA-N 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 229920006115 poly(dodecamethylene terephthalamide) Polymers 0.000 description 1
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920006396 polyamide 1012 Polymers 0.000 description 1
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- PCHQDTOLHOFHHK-UHFFFAOYSA-L zinc;hydrogen carbonate Chemical compound [Zn+2].OC([O-])=O.OC([O-])=O PCHQDTOLHOFHHK-UHFFFAOYSA-L 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C08K2003/168—Zinc halides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- 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
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a halogen-free flame-retardant polyamide composition, and a preparation method and application thereof. The halogen-free flame retardant polyamide composition comprises the following components in parts by weight: 30-80 parts of polyamide resin; 10-40 parts of glass fiber; 10-30 parts of halogen-free flame retardant; 0.1 to 3 parts of zinc-containing compound; the melting point of the zinc-containing compound is less than or equal to 600 ℃; the halogen-free flame retardant is dialkyl hypophosphite. According to the invention, the inorganic zinc-containing compound with a specific melting point is added, ionization can occur at the flame temperature to generate zinc ions, so that coordination with the polyamide resin and the halogen-free flame retardant occurs, the phenomenon of molten drop in the combustion process is avoided, and the fluidity of the polyamide composition is not affected.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a halogen-free flame-retardant polyamide composition, and a preparation method and application thereof.
Background
The polyamide material is a material widely applied in engineering plastics, has excellent heat resistance, solvent resistance, mechanics and processing performance, and is widely applied to the fields of electronics and electrics, rail transit, electric tools, household appliances, sports equipment and the like. Currently, halogen-free flame retardants applied to glass fiber reinforcement mainly comprise two main types of basic systems: one is red phosphorus; one type is a phosphorus-nitrogen flame retardant system. However, when the glass fiber reinforced halogen-free flame retardant polyamide material is subjected to flame retardant test, the problem of flame retardant failure caused by dripping is often caused. To solve this problem, it is common in the prior art to add an anti-dripping agent such as polytetrafluoroethylene to improve the anti-dripping effect of the material, but this method reduces the fluidity of the system, resulting in the composition having a phenomenon of lack of glue during injection molding and being expensive.
Therefore, there is a need in the art to develop a halogen-free flame retardant polyamide composition having both good anti-drip effect and good flowability.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a halogen-free flame retardant polyamide composition which has good anti-dripping performance and flowability.
It is another object of the present invention to provide a method for preparing the halogen-free flame retardant polyamide composition.
The invention further aims to provide application of the halogen-free flame retardant polyamide composition in a new energy connector and an energy storage connector.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the halogen-free flame retardant polyamide composition comprises the following components in parts by weight:
the melting point of the zinc-containing compound is less than or equal to 600 ℃; the halogen-free flame retardant is dialkyl hypophosphite.
The invention provides a halogen-free flame retardant polyamide composition, which is prepared by adding a zinc-containing compound with the melting point not exceeding 600 ℃. The flame temperature is usually 500-600 ℃, the melting point of the zinc-containing compound can be ionized below the flame temperature, generated metal ions can coordinate with polyamide resin and dialkyl hypophosphite, so that dripping during combustion is slowed down, the dripping resistance effect is achieved, the flowability of the polyamide composition cannot be affected by the addition of the zinc-containing compound, and the zinc-containing compound can be well molded in the subsequent processing process.
In the present invention, the zinc-containing compound has a melting point of not more than 600℃and specifically 550℃at 500℃at 450℃at 400℃at 350℃at 300℃at 250℃at 200℃at 150℃at 100 ℃. In the present invention, anions of the zinc-containing compound are not particularly limited, such as, but not limited to, bromide, chloride, iodide, sulfate, acetate, carbonate, basic carbonate, octoate, nitrite, carboxylate. Zinc-containing compounds having a melting point of not more than 600 c are all within the skill of the art for practicing the present invention. Zinc compounds having a melting point of no more than 600 ℃ include, but are not limited to, one or more of zinc bromide, zinc chloride, zinc iodide, zinc sulfate, zinc acetate, zinc carbonate, basic zinc carbonate, zinc octoate, zinc nitrite, zinc carboxylate.
Further, the melting point of the zinc-containing compound is 200-400 ℃.
Further, the zinc-containing compound has a melting point of 220 to 300 ℃.
Further, the zinc-containing compound accounts for 0.09 to 7.5wt% based on the sum of the polyamide resin and the dialkylhypophosphite. Such as, but not limited to, 0.1wt%, 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 3.5wt%, 4.0wt%, 4.5wt%, 5.0wt%, 5.5wt%, 6.0wt%, 6.5wt%, 7.0wt%, 7.5wt%, and the like.
Further, the halogen-free flame retardant polyamide composition comprises the following components in parts by weight:
further, the dialkyl phosphinate is one or more of methyl ethyl aluminum phosphinate, diethyl zinc phosphinate or diethyl titanium phosphinate.
In the halogen-free flame retardant polyamide composition, the content of the polyamide resin is not less than 28wt%. Such as, but not limited to, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, etc.
Further, the polyamide resin is a semiaromatic polyamide and/or an aliphatic polyamide.
Specifically, the semi-aromatic polyamide is selected from one or more of PA6T/66, PA6I, PA T/6I, PA T/M5T, PA9T, PA9T/66, PA10T, PA T/66, PA10T/10I, PA10T/1010 and PA12T, PA 12I.
The aliphatic polyamide is selected from one or more of PA6, PA66, PA610, PA612, PA1010, PA1012, PA1212, PA11 and PA 12.
The present invention has no special requirement on the relative viscosity of the polyamide resin. When the relative viscosity of the polyamide resin is 2.1-2.7, the anti-dripping performance of the prepared halogen-free flame retardant polyamide composition is ensured, and meanwhile, the processing performance of the material can be further improved.
Further, the polyamide resin has a relative viscosity of 2.1 to 2.4.
Specifically, the polyamide resin was tested with a relative viscosity measurement standard of ISO 307-2017.
Further, the glass fiber comprises chopped strands A-, E-, C-, D-, S-, R-glass fiber, and the glass fiber has a cross-sectional shape of one of a circle, an ellipse or a square.
Further, the halogen-free flame retardant polyamide composition also comprises 0.1 to 1 part of antioxidant.
The invention can select one or more of common antioxidants including hindered phenol antioxidants, phosphite antioxidants, diphenylamine antioxidants, copper salt antioxidants and thioether antioxidants.
Specifically, the hindered phenol antioxidant is one or more of N, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-phenyl-propionamide (Irganox 1098), tetra [1093,5-di-tert-butyl-4-hydroxy-phenyl) -propionic acid ] pentaerythritol ester (Irganox 1010), triethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionic acid ester (Iragnox 259), beta- (4-hydroxy-3, 5-di-tert-butylphenyl) propionic acid N-octadecyl ester (Iragno 1076) or spiro ethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionic acid ester ] (ADK AO-80).
The phosphite antioxidant is one or more of 2, 4-di-tert-butylphenol (Irganox 168), bis (2, 6-di-tert-butyl-4-tolyl) pentaerythritol phosphite (PEP-36) or 627A.
The diphenylamine antioxidant is 4,4 '-bis (alpha, alpha' -dimethylbenzyl) diphenylamine.
The copper salt antioxidant is a mixture of 8:1:1K/Cu/ZnBLEND or KI/CuI.
The thioether antioxidant is one or more of distearyl thiodipropionate, dilauryl thiodipropionate or pentaerythritol dodecyl thiopropyl.
The invention provides a preparation method for protecting the halogen-free flame retardant polyamide composition, which comprises the following steps:
and (3) carrying out melt blending, extrusion granulation on the polyamide resin, the glass fiber, the halogen-free flame retardant and the zinc-containing compound to obtain the halogen-free flame retardant composition.
Further, the extrusion granulation is performed in a twin screw extruder.
Further, the temperature of the first area of the double-screw extruder is 180-200 ℃, the temperature of the second area is 250-270 ℃, the temperature of the third area is 260-280 ℃, the temperature of the fourth area is 265-285 ℃, the temperature of the fifth area is 265-285 ℃, the temperature of the sixth area is 265-285 ℃, the temperature of the seventh area is 260-280 ℃, the temperature of the eighth area is 260-280 ℃, the temperature of the ninth area is 260-280 ℃, and the screw rotating speed of the double-screw extruder is 300-500 revolutions per minute.
The invention protects application of the halogen-free flame retardant polyamide composition in new energy connectors and energy storage connectors.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a halogen-free flame-retardant polyamide composition, wherein a zinc-containing compound with a melting point less than or equal to 600 ℃ is added into the polyamide composition, and the zinc-containing compound is ionized to generate zinc ions at a common flame temperature, so that the zinc ions can coordinate with polyamide resin and a halogen-free flame retardant, further, melt dripping during combustion is avoided, and the dripping-resistant mode has no obvious influence on the fluidity of the composition.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
The raw materials used in the examples and comparative examples of the present invention:
polyamide resin:
polyamide resin 1: PA 66U 2501, resin relative viscosity 2.1, available from inflight;
polyamide resin 2: PA 66U 3600 NC01, resin relative viscosity 2.4, available from inflight;
polyamide resin 3: PA 66U 4800 NC01, resin relative viscosity 2.7, available from inflight;
polyamide resin 4: PA6 HY-2500A, resin relative viscosity 2.5, purchased from Neumeida;
glass fiber: ECS10-30-568H, available from China boulder Co., ltd;
halogen-free flame retardant:
flame retardant 1: aluminum diethylphosphinate, LFR-8003, available from Jiangsu riside New Material Co., ltd;
flame retardant 2: red phosphorus master batch, FR9950T, purchased from new materials inc. Of tung city, inc;
zinc-containing compound:
zinc acetate: the melting point is 237 ℃;
zinc chloride: the melting point is 283 ℃;
basic zinc carbonate: melting point 300 ℃;
zinc bromide: the melting point is 394 ℃;
zinc phosphate: the melting point is 900 ℃;
zinc sulfide: melting point 1700 ℃;
sodium acetate: the melting point is 324 ℃;
polytetrafluoroethylene: x-010, available from Guangzhou Hui silicon composite Co., ltd;
an antioxidant: an antioxidant 1098; the antioxidants are commercially available, and the same antioxidants are used in the parallel experiments of the examples and the comparative examples.
Examples 1 to 10 and comparative examples 1 to 6
Halogen-free flame retardant polyamide compositions were prepared according to the formulations in tables 1-2 as follows:
the preparation method comprises the steps of (1) putting polyamide resin, glass fiber, halogen-free flame retardant and zinc-containing compound into a high-speed mixer to be mixed for 1-2 minutes at a rotating speed of 600-800 rpm, and then putting into a double-screw extruder to be subjected to melt blending, extrusion granulation to obtain a halogen-free flame retardant polyamide composition; the temperature of the first area of the double-screw extruder is 180-200 ℃, the temperature of the second area is 250-270 ℃, the temperature of the third area is 260-280 ℃, the temperature of the fourth area is 265-285 ℃, the temperature of the fifth area is 265-285 ℃, the temperature of the sixth area is 265-285 ℃, the temperature of the seventh area is 260-280 ℃, the temperature of the eighth area is 260-280 ℃, the temperature of the ninth area is 260-280 ℃, and the screw rotating speed of the double-screw extruder is 300-500 rpm.
Table 1 amounts of the components (parts by weight) of the halogen-free flame retardant polyamide compositions of examples 1 to 7
Table 2 amounts of the components (parts by weight) in the halogen-free flame retardant polyamide compositions of examples 8 to 10 and comparative examples 1 to 6
Performance testing
1. Test method
The halogen-free flame retardant polyamide compositions prepared in examples 1 to 10 and comparative examples 1 to 6 above were subjected to performance test:
(1) Combustion performance test: the halogen-free flame retardant polyamide compositions prepared in the above examples and comparative examples were tested according to the UL94-2009 standard, the test bar thickness was 1.5mm;
(2) Melt flow rate test: the halogen-free flame retardant polyamide compositions prepared in the above examples and comparative examples were tested according to standard ISO 1133-1-2022, wherein the test conditions were 280℃C/2.16 kg.
2. Test results
The results of the performance test of the halogen-free flame retardant polyamide compositions prepared in each of the examples and comparative examples are shown in Table 3.
TABLE 3 results of Performance test for examples 1-10 and comparative examples 1-6
As can be seen from Table 3, the melt flow rate of the halogen-free flame retardant polyamide composition prepared by each embodiment of the invention is 15-46 g/10min, and the halogen-free flame retardant polyamide composition has better processability in the range; and the flame retardant has good flame retardant property, the self-extinguishing time is not more than 3.3s, and the self-extinguishing time of most embodiments is not more than 2.6s.
As can be seen from comparative examples 1 and 2, when the melting point of the selected zinc-containing compound is higher than 600 ℃, the halogen-free flame retardant polyamide composition prepared still has a molten drop phenomenon because ionization cannot occur and coordination with the polyamide resin and the flame retardant cannot be performed when the melting point of the added zinc-containing compound is above the flame temperature, thereby failing to exert an anti-dripping effect.
As can be seen from comparative example 3, when other metal compounds are selected instead of the zinc-containing compound, the halogen-free flame retardant polyamide composition produced still has a molten drop phenomenon even if the melting point is not more than 600℃because the sodium element does not have a similar coordination ability, and it is impossible to prevent the dripping by the coordination.
As can be seen from comparative example 4, when polytetrafluoroethylene is selected instead of zinc-containing compound, the halogen-free flame retardant polyamide composition obtained has no melt dripping but has a melt flow rate of only 13g/10min, reduced flowability, shortened molding window during injection molding, and possibly occurrence of a gel shortage.
As can be seen from comparative example 5, when the zinc-containing compound is not added, the halogen-free flame retardant polyamide composition is produced which has a melt drop phenomenon and does not self-extinguish although the melt flow rate is high.
As can be seen from comparative example 6, when other halogen-free flame retardant agents are used instead of dialkylphosphinates, the halogen-free flame retardant polyamide composition obtained has a melt drop phenomenon.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. The halogen-free flame retardant polyamide composition is characterized by comprising the following components in parts by weight:
30-80 parts of polyamide resin;
10-40 parts of glass fiber;
10-30 parts of halogen-free flame retardant;
0.1 to 3 parts of zinc-containing compound;
the melting point of the zinc-containing compound is less than or equal to 600 ℃; the halogen-free flame retardant is dialkyl hypophosphite.
2. The halogen-free flame retardant polyamide composition according to claim 1, wherein the melting point of the zinc-containing compound is 200-400 ℃.
3. The halogen-free flame retardant polyamide composition according to claim 1, wherein the zinc-containing compound with the melting point less than or equal to 600 ℃ is one or more of zinc bromide, zinc chloride, zinc iodide, zinc sulfate, zinc acetate, zinc carbonate, zinc octoate, zinc nitrite, basic zinc carbonate and zinc carboxylate.
4. The halogen-free flame retardant polyamide composition according to claim 1, wherein the zinc-containing compound comprises 0.09 to 7.5 wt.% based on the sum of the weight of the polyamide resin and the weight of the dialkylphosphinate.
5. The halogen-free flame retardant polyamide composition according to claim 1, wherein the dialkylphosphinate is one or more of methylethylphosphinate aluminum, diethylphosphinate zinc or diethylphosphinate titanium.
6. The halogen-free flame retardant polyamide composition according to claim 1, wherein the polyamide resin is a semiaromatic polyamide and/or an aliphatic polyamide.
7. The halogen-free flame retardant polyamide composition according to claim 1, further comprising 0.1 to 1 part of an antioxidant.
8. The halogen-free flame retardant polyamide composition according to claim 7, wherein the antioxidant is one or more of hindered phenol antioxidants, phosphite antioxidants, diphenylamine antioxidants, copper salt antioxidants and thioether antioxidants.
9. The method for preparing a halogen-free flame retardant polyamide composition according to any one of claims 1 to 8, comprising the steps of:
the halogen-free flame retardant polyamide composition is prepared by melt blending, extrusion granulating of polyamide resin, glass fiber, halogen-free flame retardant and zinc-containing compound.
10. Use of the halogen-free flame retardant polyamide composition according to any one of claims 1 to 8 in new energy connectors, energy storage connectors.
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