CN112608592A - High-dispersibility high-concentration nylon-based halogen-free flame-retardant master batch and preparation method thereof - Google Patents
High-dispersibility high-concentration nylon-based halogen-free flame-retardant master batch and preparation method thereof Download PDFInfo
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- CN112608592A CN112608592A CN202011345320.2A CN202011345320A CN112608592A CN 112608592 A CN112608592 A CN 112608592A CN 202011345320 A CN202011345320 A CN 202011345320A CN 112608592 A CN112608592 A CN 112608592A
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- Prior art keywords
- nylon
- retardant
- free flame
- master batch
- concentration
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 158
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 239000004677 Nylon Substances 0.000 title claims abstract description 125
- 229920001778 nylon Polymers 0.000 title claims abstract description 125
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000004383 yellowing Methods 0.000 claims abstract description 48
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 239000002270 dispersing agent Substances 0.000 claims abstract description 32
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 31
- 230000001050 lubricating effect Effects 0.000 claims abstract description 30
- 150000007974 melamines Chemical class 0.000 claims abstract description 28
- 238000012545 processing Methods 0.000 claims description 51
- 239000000843 powder Substances 0.000 claims description 28
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 19
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 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 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229920000388 Polyphosphate Polymers 0.000 claims description 6
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 6
- 239000001205 polyphosphate Substances 0.000 claims description 6
- 235000011176 polyphosphates Nutrition 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 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 claims description 2
- DBKFYOISCCPYTQ-UHFFFAOYSA-K C1(=CC=CC=C1)P([O-])=O.[Al+3].C1(=CC=CC=C1)P([O-])=O.C1(=CC=CC=C1)P([O-])=O Chemical compound C1(=CC=CC=C1)P([O-])=O.[Al+3].C1(=CC=CC=C1)P([O-])=O.C1(=CC=CC=C1)P([O-])=O DBKFYOISCCPYTQ-UHFFFAOYSA-K 0.000 claims 1
- QVKQNISQFCPYGN-UHFFFAOYSA-K aluminum;dimethylphosphinate Chemical compound [Al+3].CP(C)([O-])=O.CP(C)([O-])=O.CP(C)([O-])=O QVKQNISQFCPYGN-UHFFFAOYSA-K 0.000 claims 1
- 229920005862 polyol Polymers 0.000 claims 1
- 150000003077 polyols Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 238000012216 screening Methods 0.000 abstract description 5
- 238000011049 filling Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 39
- 238000000034 method Methods 0.000 description 26
- 239000003365 glass fiber Substances 0.000 description 20
- 230000008569 process Effects 0.000 description 20
- 239000002245 particle Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- -1 diethyl phosphinic acid aluminum Chemical compound 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 241000519995 Stachys sylvatica Species 0.000 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 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- MFNFHZVOHDNCDN-UHFFFAOYSA-N 4,6-bis[(2,2,6,6-tetramethylpiperidin-3-yl)amino]benzene-1,3-dicarboxamide Chemical group CC1(NC(CCC1NC1=CC(=C(C=C1C(=O)N)C(=O)N)NC1C(NC(CC1)(C)C)(C)C)(C)C)C MFNFHZVOHDNCDN-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical group 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- ORVACBDINATSAR-UHFFFAOYSA-N dimethylaluminum Chemical compound C[Al]C ORVACBDINATSAR-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007908 dry granulation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ANVBJJYOOMUNBJ-UHFFFAOYSA-N methyl(phenyl)alumane Chemical compound [AlH](C)C1=CC=CC=C1 ANVBJJYOOMUNBJ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 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 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic 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
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- 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
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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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
- C08K5/20—Carboxylic acid amides
-
- 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
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- 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
- C08K5/34928—Salts
-
- 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
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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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
- C08K5/49—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'
Abstract
The high-dispersibility high-concentration nylon-based halogen-free flame-retardant master batch comprises a nylon resin carrier, an organic hypophosphite and a melamine derivative, wherein the mass percentage content of the nylon resin carrier is 20-45%, the mass percentage content of the organic hypophosphite is 25-60%, the mass percentage content of the melamine derivative is 15-40%, the relative viscosity of the nylon resin carrier is 1.8-3.0, and the effective concentration of the flame-retardant master batch is 50-75%. The nylon carrier is high in filling property by screening nylon resin, a lubricating dispersant and a yellowing resistant agent, and the prepared organic hypophosphite and melamine derivative compound flame retardant master batch has the effective concentration of 50-75% and high flame retardant efficiency. The invention also provides a preparation method of the halogen-free flame-retardant master batch.
Description
Technical Field
The invention relates to the technical field of preparation of high polymer materials, in particular to a high-dispersibility high-concentration nylon-based halogen-free flame-retardant master batch and a preparation method thereof.
Background
The halogen-free flame-retardant nylon and the glass fiber reinforced nylon product have the characteristics of excellent mechanical and heat-resistant properties, excellent electrical insulation property, high flame-retardant efficiency, low smoke toxicity and the like, so that the halogen-free flame-retardant nylon and the glass fiber reinforced nylon product are widely applied to the fields of electrical appliances, electronic appliances, rail transit and the like. The phosphorus-nitrogen flame retardant has high flame retardant efficiency, no halogen and good electrical property and is widely applied to nylon and glass fiber reinforced nylon flame retardant modified materials. The flame retardant mechanism of the phosphorus-nitrogen halogen-free flame retardant is solidification phase and gas phase synergistic flame retardant, and the phosphorus-nitrogen halogen-free flame retardant has high temperature resistance and high flame retardant efficiency, so the phosphorus-nitrogen halogen-free flame retardant is more applied to a nylon-based flame retardant modified system. However, with the recent strict requirements of national economic transformation and upgrade and safety and environmental protection, more and more plastic processing enterprises begin to upgrade manufacturing equipment and process flow lines, and improve the field environment of a workshop to reduce the health risks of employees. In the process of upgrading preparation equipment and a process flow line, because a large number of weightlessness scales are used, the auxiliary agent powder needs to have good fluidity, is easy to weigh and does not fly dust. However, the existing phosphorus-nitrogen halogen-free flame retardant is generally white powder with small particle size, low bulk density and light powder, so the existing phosphorus-nitrogen halogen-free flame retardant is easy to fly and bridge in the mixing and conveying processes, the flame retardant cannot be effectively dispersed, the problems of easy generation of scorching substances, impurity particles and flame retardant white spots in the processing process, low production efficiency and the like are caused, and finally the performance and quality of the halogen-free flame retardant material are unstable, which becomes a pain point in the application process.
In the prior art, the phosphorus-nitrogen halogen-free flame retardant is granulated and formed by a dry method or prepared into flame-retardant master batches, so that the apparent density and transportability of the flame-retardant master batches can be improved, and the problems are solved to a certain extent. However, the dry granulated halogen-free flame retardant is easy to partially agglomerate into non-dispersible white spots during secondary extrusion dispersion due to the process, thereby affecting the appearance and performance. In addition, dry granulation particles are brittle and are easily broken during storage, transportation and processing to form new dust, so that the problem is not completely solved.
The phosphorus-nitrogen halogen-free flame-retardant master batch taking polyolefin or toughening agent as a carrier can well solve the problems of dust and mixing, has relatively low processing difficulty and is easy to produce, but the introduction of carrier resin can seriously influence the physical property and the heat resistance of a nylon material, and meanwhile, because the internal mixing is adopted in the processing, the dispersibility of powder cannot be guaranteed, and the stability of the flame-retardant property is not facilitated. Patent CN102382459A discloses a method for preparing decabromodiphenylethane flame-retardant masterbatch using nylon as carrier, but the nylon carrier used in the method needs to be pulverized at low temperature, which increases processing cost, and the effective content is 49% -63%. It is difficult to stably process a master batch having a high concentration of 65% or more. Patents CN102363671A and CN103627168B disclose methods for preparing Melamine Cyanurate (MCA) flame-retardant master batches of nylon carriers, but the MCA flame-retardant master batches can only be used in nylon resin systems, but cannot be used in glass fiber reinforced nylon systems required by UL 94V-0 flame-retardant rating. Patent CN109575586A discloses flame retardant masterbatch of melamine polyphosphate and its derivative (MPP) prepared by using nylon as carrier, which has poor flame retardant property when used alone in nylon, and needs to be used in combination with diethyl phosphinic acid aluminum powder, and does not solve the problems of discoloration and degradation of nylon carrier in primary masterbatch processing of two components. In patent CN110922747A, a silicon-containing synergist and an organic phosphinate compound flame retardant are used to prepare a flame retardant masterbatch, but the flame retardant system has low flame retardant efficiency, poor compatibility between silicone and materials, reduced thermal and mechanical properties and surface printability, and higher cost. Therefore, the development of the nylon-based halogen-free flame-retardant master batch with high flame-retardant efficiency, good apparent performance and no influence on material performance has better economic benefit.
Disclosure of Invention
In view of the above, the invention aims to provide a high-concentration high-dispersibility nylon-based halogen-free flame-retardant master batch and a preparation method thereof, and further solves the problems of poor fluidity, difficult processing, rough surface, degradation and yellowing in production and the like when the effective concentration of the flame-retardant master batch is more than 65%.
The high-dispersibility high-concentration nylon-based halogen-free flame-retardant master batch is characterized by comprising a nylon resin carrier, an organic hypophosphite and a melamine derivative, wherein the mass percentage content of the nylon resin carrier is 20-45%, the mass percentage content of the organic hypophosphite is 25-60%, the mass percentage content of the melamine derivative is 15-40%, the relative viscosity of the nylon resin carrier is 1.8-3.0, and the effective concentration of the flame-retardant master batch is 50-75%.
Further, the nylon resin carrier is selected from one or a mixture of two of PA6, PA66, PA610 and PA 12.
Further, the organic hypophosphite is selected from one or a mixture of two of diethyl aluminum hypophosphite, dimethyl aluminum hypophosphite, phenyl methyl aluminum hypophosphite, dialkyl zinc hypophosphite and dialkyl iron hypophosphite.
Further, the melamine derivative is selected from one or a mixture of two of melamine polyphosphate and melamine cyanurate.
Further, the highly dispersible high-concentration nylon-based halogen-free flame-retardant master batch also comprises a lubricating dispersant and a yellowing-resistant agent.
Further, the lubricating and dispersing agent is selected from one or a mixture of more of polyhydroxy compound, stearate, Ethylene Bis Stearamide (EBS), pentaerythritol stearate (PETS), TAF and silicone powder.
Further, the anti-yellowing agent consists of an antioxidant, phosphate and a hindered amine stabilizer.
Further, the mass fraction of the lubricating dispersant is 1-5%, and the mass fraction of the yellowing resistant agent is 0.5-3%.
The preparation method of the high-dispersibility high-concentration nylon-based halogen-free flame-retardant master batch comprises the following steps:
step S1: providing a nylon resin carrier, an organic hypophosphite and a melamine derivative, wherein the mass percentage content of the nylon resin carrier is 20-45%, the mass percentage content of the organic hypophosphite is 25-60%, and the mass percentage content of the melamine derivative is 15-40%;
step S2: compounding the organic hypophosphite and the melamine derivative into the halogen-free flame retardant in proportion, and fully mixing in a mixing device;
step S3: providing a lubricating dispersant and a yellowing resistant agent, wherein the mass percent of the lubricating dispersant is 1-5%, and the mass percent of the yellowing resistant agent is 0.5-3%;
step S4: premixing the granular nylon resin carrier, the lubricating dispersant and the anti-yellowing agent in a mixer according to a proportion, and then adding the halogen-free flame retardant to mix uniformly;
step S5: and adding the nylon premix into a double-screw extruder, and performing melt blending and extrusion to obtain the high-concentration high-dispersibility nylon-based halogen-free flame-retardant master batch.
Further, the processing temperature of the double-screw extruder is 180-230 ℃, and the length-diameter ratio of the double-screw extruder is 48: 1-56: 1.
Compared with the prior art, the invention has the following advantages:
(1) the nylon carrier is high in filling property by screening nylon resin, a lubricating dispersant and a yellowing resistant agent, and the prepared organic hypophosphite and melamine derivative compound flame retardant master batch has the effective concentration of 50-75% and high flame retardant efficiency.
(2) The master batch using the elastomer as the carrier has the problems of reduced flame retardant efficiency and heat resistance, poor compatibility, low mechanical property and the like, and the master batch prepared by using the nylon as the carrier has little influence on the flame retardant efficiency and the thermal stability of the flame retardant, and is completely suitable for the processing temperature of the nylon material.
(3) By adding the yellowing resistant agent, the problem of yellowing of the organic phosphate and melamine derivative compounded flame retardant in the processing process of the master batch is effectively solved, and stable processing of the high-concentration high-dispersion master batch of the flame retardant system is realized.
(4) Through the optimized control of processing equipment and process, the high-concentration flame retardant powder has good dispersibility in a nylon carrier, stable processing and continuous production, and can not generate degradation, yellowing or coke materials.
(5) The master batch has smooth and flat surface, no obvious granular feeling, good compatibility with nylon materials and high product strength, and is suitable for high-efficiency flame retardance of nylon and glass fiber reinforced nylon.
Detailed Description
Specific examples of the present invention will be described in further detail below. It should be understood that the description herein of embodiments of the invention is not intended to limit the scope of the invention.
The high-dispersibility high-concentration nylon-based halogen-free flame-retardant master batch provided by the invention is composed of a nylon resin carrier, organic hypophosphite and melamine derivatives. The fluidity, the fillability and the compatibility with the target product of the nylon resin carrier are important factors influencing the selection of the flame-retardant master batch carrier, and meanwhile, the nylon resin carrier can bear a flame retardant and various auxiliary agents to ensure the uniform dispersion of the master batch in the product. It will be understood, of course, that the amount of the nylon resin carrier is controlled to achieve granulation and to maximize the concentration of the flame-retardant masterbatch. The carrier of the existing flame-retardant master batch usually adopts toughening agents such as EVA, EBA, POE and the like or polyolefin carriers, the powder can be filled in a large amount and is easy to process, but the processing temperature of the carrier resin is 100-180 ℃, and the processing temperature of a nylon material is 220-270 ℃, so that the problems of poor compatibility, coke material processing and the like can occur when the carrier is used for the nylon flame-retardant material, and the mechanical property and the heat resistance of the nylon are greatly influenced. Therefore, screening of the corresponding nylon resin as a flame retardant carrier is an effective method for solving the above-mentioned problems of processing, compatibility and flame retardancy. Meanwhile, the nylon resin carrier should select nylon with certain fluidity as the master batch carrier to avoid the defect of low powder fillability caused by the structure and characteristics of the nylon resin, and meanwhile, the high fillability of the flame retardant powder is realized through the compatibility of the processing aids. The relative viscosity, also known as the viscosity ratio, is the ratio of the absolute viscosity of a liquid to the absolute viscosity of another liquid at a certain temperature, and the liquid used for comparison is usually water or a suitable liquid. The master batches with too high viscosity of the nylon resin carrier cannot be extruded smoothly, and the physical properties of the modified material are reduced when the viscosity is too low for downstream application. In the present application, the relative viscosity of the nylon resin carrier should be 1.8 to 3.0, and more preferably 2.0 to 2.4. Meanwhile, in the application, the mass percentage content of the nylon resin carrier is 20-45%.
The organic hypophosphite is one or a mixture of two of aluminum diethylphosphinate, aluminum dimethylphosphite, phenyl methyl aluminium phosphinate, zinc dialkylphosphinate and iron dialkylphosphinate. The melamine derivative is selected from one or a mixture of two of melamine polyphosphate and melamine cyanurate.
The mass percentage content of the organic hypophosphite is 25-60%, and the mass percentage content of the melamine derivative is 15-40%. The synergistic flame retardant of melamine polyphosphate (MPP) and organic hypophosphite (particularly diethyl aluminium phosphinate (ADP)) has higher phosphorus content, and the synergistic action of phosphorus and nitrogen can realize high-efficiency flame retardance on nylon and glass fiber reinforced nylon, the flame retardance stably passes UL 94V-0 level (0.8mm), and no toxic gases such as phosphine and the like can be generated in the high-temperature processing process. However, the organic hypophosphite and the melamine derivative are in a powder form, and are added in a large amount, and are easily adsorbed on the wall of the feeding hopper in the production process, so that the problems of bridging of the feeding, uneven feeding, easy breakage of granulation and the like are caused, and the processing stability is further influenced. In the application, the high-dispersibility high-concentration nylon-based halogen-free flame-retardant master batch is prepared from the flame retardant through screening of a nylon resin carrier and a processing aid, so that the problems can be effectively solved.
Meanwhile, in order to improve the flame retardant efficiency of the organic hypophosphite and melamine derivative compounded flame retardant, metal oxide can be added into the high-dispersible high-concentration nylon-based halogen-free flame retardant master batch, and the mass percentage content of the metal oxide is adjusted according to the formula cost requirement. The metal oxide can be one or more of zinc oxide, zinc borate, magnesium oxide, aluminum oxide, calcium oxide, zinc stannate, hydrotalcite, boehmite and titanium oxide, and zinc oxide or zinc borate is preferred. The metal oxide can promote the flame retardant to form carbon in a condensed phase, so that the quality of a carbon layer and the compactness and continuity of the carbon layer are improved, and the flame retardant efficiency is improved. Meanwhile, the flame retardant can release a small amount of acid gas in the processing process, and the metal oxide can be used as an acid-absorbing agent to reduce the overflowing amount of the acid gas and the corrosion of the acid gas to equipment.
Furthermore, the highly dispersible high-concentration nylon-based halogen-free flame-retardant master batch can also comprise a lubricating dispersant and a yellowing-resistant agent. The corresponding lubricating system and dispersing system are selected according to the mechanism characteristics of the nylon resin carrier and the organic phosphorus flame retardant, the matching among the resin, the flame retardant and the auxiliary agent is comprehensively considered, and the influence of various auxiliary agents on the flame retardant property of the modified material is reduced. According to the application, the lubricating dispersant and the yellowing resistant agent which are suitable for nylon materials are screened out through two indexes of thermal decomposition temperature and processing compatibility. The lubricating and dispersing agent is selected from one or a mixture of more of polyhydroxy compound, stearate, Ethylene Bis Stearamide (EBS), pentaerythritol stearate (PETS), TAF and silicone powder. On the premise of not influencing or improving the flame retardance, the lubricating dispersant can ensure the processability of master batches at high concentration, improve the physical properties of final products and simultaneously improve the dispersibility of high-concentration flame retardant powder in resin. The mass percentage content of the lubricating dispersant is 1-5%.
Because nylon is easy to absorb water and molecules are unstable at high temperature, when organic hypophosphite and melamine polyphosphate compounded flame retardant powder is directly mixed with nylon and then extruded out by a double screw for granulation, released trace moisture and trace free melamine can induce the nylon to discolor and degrade, thereby causing serious reduction of mechanical properties. Therefore, the proper anti-yellowing agent is added in the processing process of the flame retardant master batch, so that the degradation and oxidation speed of the material can be delayed, and the processing stability, oxidation resistance and yellowing resistance of the material are improved. The anti-yellowing agent consists of an antioxidant, phosphate and a hindered amine stabilizer, and the mass percentage content of the anti-yellowing agent is 0.5-3%. The antioxidant can be one or the combination of more than two of phenolic antioxidant, phosphorus antioxidant, thioether antioxidant or metal salt antioxidant. Wherein, the phenolic antioxidant is preferably antioxidant 1098, antioxidant 1010, antioxidant BHT or antioxidant 1076. The phosphorus antioxidant is preferably antioxidant 168, antioxidant 626 or antioxidant 627. The thioether antioxidant is preferably antioxidant DLTP or antioxidant DSTP. Preferably, the antioxidant is a combination of antioxidant 1010 and antioxidant 168. The phosphate is selected from heat stabilizers such as H10 or H160. In the extrusion granulation process, the phosphate can chelate and passivate active functional groups generated by nylon chain scission, and is used as a synergistic stabilizer of an antioxidant to resist degradation and yellowing problems of a nylon carrier and realize stable processing, and H10 or H160 is particularly suitable for enhanced nylon. The hindered amine stabilizer is selected from bis (2,2,6, 6-tetramethyl-3-piperidyl amino) -isophthalamide. The structure is compatible with nylon through molecular recognition and cross-linked amidation, can stabilize the pressure of nylon melt, stabilizes the processing process, is bonded with nylon molecules, and has good compatibility, so that the stability of the structure to nylon exceeds the limit of the traditional light stabilizer.
The invention also provides a preparation method of the high-concentration high-dispersibility nylon-based halogen-free flame-retardant master batch, which comprises the following steps:
step S1: providing a nylon resin carrier, an organic hypophosphite and a melamine derivative, wherein the mass percentage content of the nylon resin carrier is 20-45%, the mass percentage content of the organic hypophosphite is 25-60%, and the mass percentage content of the melamine derivative is 15-40%;
step S2: compounding the organic hypophosphite and the melamine derivative into the halogen-free flame retardant in proportion, and fully mixing in a mixing device;
step S3: providing a lubricating dispersant and a yellowing resistant agent, wherein the mass percent of the lubricating dispersant is 1-5%, and the mass percent of the yellowing resistant agent is 0.5-3%;
step S4: premixing the granular nylon resin carrier, the lubricating dispersant and the anti-yellowing agent in a mixer according to a proportion, and then adding the halogen-free flame retardant to mix uniformly;
step S5: and adding the nylon premix into a double-screw extruder, and performing melt blending and extrusion to obtain the high-concentration high-dispersibility nylon-based halogen-free flame-retardant master batch.
In step S4, the halogen-free flame retardant, the lubricating dispersant and the anti-yellowing agent powder are mixed together in a mixing device according to a certain ratio, and then added to the nylon particles to be melt-blended and extruded. However, the addition amount of the lubricating dispersant and the anti-yellowing agent is small, the flame retardant powder is large, the dispersant and the anti-yellowing agent are difficult to be uniformly mixed in the flame retardant in the three-component mixing, and the due effect is difficult to be exerted in the extrusion processing. In the preparation method, the dispersing agent, the yellowing-resistant agent and the nylon particles are premixed, so that a small amount of powder can be directly wrapped on the surfaces of the nylon resin carrier particles, the mixture is uniformly dispersed, and then the flame retardant is added, so that the functions of various additives are fully exerted in the processing, and the dispersibility and the yellowing resistance are improved.
In step S5, the processing temperature of the twin-screw extruder is 180-230 ℃, and the length-diameter ratio is 48: 1-56: 1. The length-diameter ratio of the double-screw extruder is an important parameter for processing, and needs to be comprehensively considered according to the performance of the processed material and the requirement on the product quality. The larger the length-diameter ratio is, the longer the residence time of the material in the screw is, which is beneficial to the sufficient plasticization and mixing of the material, but the higher the requirement on the thermal stability of the flame retardant is. In the processing process of the master batch, the powder filling amount is larger, on the premise of ensuring the thermal stability of the flame retardant, the length-diameter ratio of the screw rod needs to be increased, so that the materials are fully melted and mixed, the uniform dispersion of the powder is improved, and the surface of the particle is smooth and flat. When the length of the screw is relatively small, the powder is not uniformly dispersed, the pulling and the cutting are difficult, and the surface of the particles is rough.
Compared with the prior art, the invention has the following advantages:
(1) the nylon carrier is high in filling property by screening nylon resin, a lubricating dispersant and a yellowing resistant agent, and the prepared organic hypophosphite and melamine derivative compound flame retardant master batch has the effective concentration of 50-75% and high flame retardant efficiency.
(2) The master batch using the elastomer as the carrier has the problems of reduced flame retardant efficiency and heat resistance, poor compatibility, low mechanical property and the like, and the master batch prepared by using the nylon as the carrier has little influence on the flame retardant efficiency and the thermal stability of the flame retardant, and is completely suitable for the processing temperature of the nylon material. (3) By adding the yellowing resistant agent, the problem of yellowing of the organic phosphate and melamine derivative compounded flame retardant in the master batch processing process is effectively solved, and stable processing of high-concentration dispersed master batches of the flame retardant system is realized.
(4) Through the optimized control of processing equipment and process, the high-concentration flame retardant powder has good dispersibility in a nylon carrier, stable processing and continuous production, and can not generate degradation, yellowing or coke materials.
(5) The master batch has smooth and flat surface, no obvious granular feeling, good compatibility with nylon materials and high product strength, and is suitable for high-efficiency flame retardance of nylon and glass fiber reinforced nylon.
In the following embodiments or examples, unless otherwise specified, all the raw material components are commercial products that can be purchased from the market or products that can be prepared by a known method by those skilled in the art.
Sample test methods and standards are as follows:
1) vertical combustion order: testing according to the GB/T2408 standard.
2) Tensile strength: testing according to the GB/T1040.2 standard.
3) Impact strength: testing according to GB/T1843 standard.
4) Bending strength: testing according to GB/T9341 standard.
5) And (3) processing stability: the material is pumped smoothly or the material is pumped and broken.
6) Yellowing: the color of the flame-retardant master batch is manually evaluated, and the flame-retardant master batch is free from yellowing, slightly yellowing or severely yellowing.
7) Surface smoothness: manually evaluating the surface smoothness of the sample strips extruded by the extruder, wherein a mark indicates that the surface of the sample strips is smooth and has no granular feel; delta represents that the surface smoothness of the sample strip is general and has a slight granular feeling; the X represents the rough surface and the large grain feeling of the sample.
Examples A1-A8 and comparative examples 1-3:
examples A1-A8 and comparative examples 1-3 are prepared into the nylon-based halogen-free flame-retardant master batch according to the mass ratio of the components in the table 1 and the following processing and preparation method:
(1) compounding organic hypophosphite and melamine derivative or metal oxide into a halogen-free flame retardant in proportion, and fully mixing in a mixing device;
(2) premixing nylon carrier particles, a lubricating dispersant and a yellowing resistant agent in a mixer according to a proportion, and then adding a halogen-free flame retardant and mixing uniformly;
(3) and adding the nylon premix into a double-screw extruder, and performing melt blending and extrusion to obtain the halogen-free flame-retardant master batch.
TABLE 1 formula and processing Properties of nylon carrier flame-retardant master batch
As shown in the processing and performance test comparison of the flame-retardant master batch in the table 1, the flame-retardant master batch with the concentration of 65% prepared by only adding the flame retardant in the comparative example 1 has serious powder bridging during processing, extrusion granulation is easy to break, the processability is poor, the master batch is yellowed, the surface smoothness is poor, and the granular feeling is large. The lubricating dispersant is added in the comparative example 2, so that the processing performance and the master batch surface smoothness are slightly improved compared with the comparative example 1, but the problems of strip breakage and master batch yellowing still exist. The comparative example 3 is added with the yellowing resistant agent, but the master batch still has a certain yellowing, which may be caused by that no lubricating dispersant is added, powder bridging exists, the blanking is not uniform, and a certain amount of coke materials are yellow during extrusion granulation. In examples A1-A8, the lubricating dispersant and the anti-yellowing agent were added to the flame-retardant masterbatch of different concentrations, and the masterbatch was smooth to process without yellowing, and had good particle surface smoothness and almost no granular feel.
Examples B1-B8:
the nylon-based flame-retardant master batches processed in the above examples A1-A8 and having different flame retardant concentrations were added to a glass fiber reinforced PA6 system to obtain a flame-retardant glass fiber reinforced nylon material B1-B8, and the amounts and performance tests of the master batches, the nylon resin and the glass fibers in each example are listed in Table 2.
TABLE 2 formulation and Properties of masterbatch flame-retardant glass fiber reinforced PA6 Material
Comparative example 4:
comparative example 4 adopts ADP and MPP compounded flame retardant powder, lubricating dispersant and anti-yellowing agent to retard flame of the glass fiber reinforced PA6 material, and the use amounts and preparation methods of the components are as follows:
11.25 parts by mass of ADP, 5 parts by mass of MPP, 0.25 part by mass of EBS, 0.25 part by mass of PETS, 0.125 part by mass of 1010, 0.125 part by mass of 168, 0.25 part by mass of H10, 0.25 part by mass of S-EED and 52.5 parts by mass of PA6 were mixed, 30 parts by mass of glass fiber was added to prepare flame-retardant glass fiber reinforced PA6, and the processing and performance tests are shown in Table 3.
Comparative example 5:
comparative example 5 is a glass fiber reinforced PA6 material that was flame retarded with the EBA carrier masterbatch of the same flame retardant and flame retardant concentration as in example a1, with the following components and preparation method:
25 parts by mass of EBA carrier master batch and 45 parts by mass of PA6 are mixed, 30 parts by mass of glass fiber is added to prepare the flame-retardant glass fiber reinforced PA6, and the processing and performance tests are listed in Table 3.
TABLE 3 processing and Properties of flame retardant glass fiber reinforced PA6 Material
Comparative example 4 the content of the flame retardant powder and the additive used in the flame retardant glass fiber reinforced PA6 material is the same as that in example B1, comparing the two groups of flame retardant materials, it can be seen that the flame retardant materials prepared by directly using the flame retardant powder and indirectly using the flame retardant masterbatch have similar test data of flame retardant property and mechanical property, which indicates that the flame retardant masterbatch using nylon as the carrier does not reduce the material property in the secondary processing. However, the comparative processing and the particle appearance performance have a large difference, the processing problems such as bridging, strip breakage and the like are easy to occur when the powder is directly used, the particles are slightly yellowed due to unstable production, the surface is not smooth, and the particle has slight granular feel, but the embodiment B1 adopting the flame-retardant master batch processing mode does not have the problems, which shows that the flame-retardant master batch can better improve the processing performance on the premise of not influencing the performance of the flame-retardant material, the compatibility and the dispersibility of the master batch and the matrix are better, and the particle surface is smooth and has no granular feel.
Comparative example 5 adopts the EBA carrier flame-retardant masterbatch to prepare the glass fiber reinforced PA6 flame-retardant material, and comparing the performance data with that in example B1, it can be seen that the flame-retardant masterbatch prepared with the EBA elastomer as the carrier can reduce the flame-retardant efficiency of the flame retardant and the mechanical properties of the flame-retardant material, because the EBA carrier has a low thermal deformation temperature, and the EBA elastomer as the carrier can reduce the processing temperature tolerance of the flame-retardant masterbatch, and simultaneously, the EBA and PA6 resin have poor compatibility, which reduces the flame-retardant efficiency and the mechanical properties of the material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, and any modifications, equivalents or improvements that are within the spirit of the present invention are intended to be covered by the following claims.
Claims (10)
1. The high-dispersibility high-concentration nylon-based halogen-free flame-retardant master batch is characterized by comprising a nylon resin carrier, an organic hypophosphite and a melamine derivative, wherein the mass percentage content of the nylon resin carrier is 20-45%, the mass percentage content of the organic hypophosphite is 25-60%, the mass percentage content of the melamine derivative is 15-40%, the relative viscosity of the nylon resin carrier is 1.8-3.0, and the effective concentration of the flame-retardant master batch is 50-75%.
2. The highly dispersible high-concentration nylon-based halogen-free flame-retardant masterbatch according to claim 1, wherein the nylon resin carrier is selected from one or a mixture of two of PA6, PA66, PA610 and PA 12.
3. The highly dispersible highly concentrated nylon-based halogen-free flame-retardant masterbatch according to claim 1, wherein the organic hypophosphite is one or a mixture of two of aluminum diethylphosphinate, aluminum dimethylphosphinate, aluminum phenylphosphinate, zinc dialkylphosphinate and iron dialkylphosphinate.
4. The highly dispersible high concentration nylon-based halogen-free flame retardant masterbatch according to claim 1, wherein the melamine derivative is selected from one or a mixture of two of melamine polyphosphate and melamine cyanurate.
5. The highly dispersible high-concentration nylon-based halogen-free flame-retardant masterbatch according to claim 1, wherein the highly dispersible high-concentration nylon-based halogen-free flame-retardant masterbatch further comprises a lubricating dispersant and a yellowing-resistant agent.
6. The highly dispersible high concentration nylon-based halogen-free flame retardant masterbatch according to claim 5, wherein the lubricant dispersant is selected from one or more of polyol, stearate, Ethylene Bis Stearamide (EBS), pentaerythritol stearate (PETS), TAF, silicone powder.
7. The highly dispersible high-concentration nylon-based halogen-free flame-retardant master batch according to claim 5, wherein the yellowing-resistant agent is composed of an antioxidant, a phosphate and a hindered amine stabilizer.
8. The highly dispersible high-concentration nylon-based halogen-free flame-retardant master batch as claimed in claim 1, wherein the mass fraction of the lubricating dispersant is 1-5%, and the mass fraction of the yellowing-resistant agent is 0.5-3%.
9. The preparation method of the high-dispersibility high-concentration nylon-based halogen-free flame-retardant master batch comprises the following steps:
step S1: providing a nylon resin carrier, an organic hypophosphite and a melamine derivative, wherein the mass percentage content of the nylon resin carrier is 20-45%, the mass percentage content of the organic hypophosphite is 25-60%, and the mass percentage content of the melamine derivative is 15-40%;
step S2: compounding the organic hypophosphite and the melamine derivative into the halogen-free flame retardant in proportion, and fully mixing in a mixing device;
step S3: providing a lubricating dispersant and a yellowing resistant agent, wherein the mass percent of the lubricating dispersant is 1-5%, and the mass percent of the yellowing resistant agent is 0.5-3%;
step S4: premixing the granular nylon resin carrier, the lubricating dispersant and the anti-yellowing agent in a mixer according to a proportion, and then adding the halogen-free flame retardant to mix uniformly;
step S5: and adding the nylon premix into a double-screw extruder, and performing melt blending and extrusion to obtain the high-concentration high-dispersibility nylon-based halogen-free flame-retardant master batch.
10. The preparation method of the highly dispersible high concentration nylon-based halogen-free flame retardant masterbatch of claim 9, wherein: the processing temperature of the double-screw extruder is 180-230 ℃, and the length-diameter ratio of the double-screw extruder is 48: 1-56: 1.
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Address after: 166 Chenggong Road, Huimin street, Jiashan County, Jiaxing City, Zhejiang Province Applicant after: Zhejiang xusen flame retardant Co.,Ltd. Address before: 166 Chenggong Road, Huimin street, Jiashan County, Jiaxing City, Zhejiang Province Applicant before: ZHEJIANG XUSEN HALOGEN FREE SMOKE ABATEMENT FIRE RETARDANT CO.,LTD. |
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Application publication date: 20210406 |