CN117777545A - Modified alkyl hypophosphite flame retardant and preparation method and application thereof - Google Patents
Modified alkyl hypophosphite flame retardant and preparation method and application thereof Download PDFInfo
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- CN117777545A CN117777545A CN202311813258.9A CN202311813258A CN117777545A CN 117777545 A CN117777545 A CN 117777545A CN 202311813258 A CN202311813258 A CN 202311813258A CN 117777545 A CN117777545 A CN 117777545A
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- Prior art keywords
- flame retardant
- component
- hypophosphite
- layer
- alkyl hypophosphite
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 117
- 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 92
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 title claims abstract description 60
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000010410 layer Substances 0.000 claims abstract description 93
- -1 alkyl hypophosphite Chemical compound 0.000 claims abstract description 48
- 238000000576 coating method Methods 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 39
- 239000011247 coating layer Substances 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 29
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 21
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 10
- 235000011152 sodium sulphate Nutrition 0.000 claims description 10
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 9
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 9
- 235000002949 phytic acid Nutrition 0.000 claims description 9
- 239000000467 phytic acid Substances 0.000 claims description 9
- 229940068041 phytic acid Drugs 0.000 claims description 9
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 229920002873 Polyethylenimine Polymers 0.000 claims description 8
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 8
- 235000010413 sodium alginate Nutrition 0.000 claims description 8
- 239000000661 sodium alginate Substances 0.000 claims description 8
- 229940005550 sodium alginate Drugs 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- 229920000388 Polyphosphate Polymers 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
- 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 7
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 7
- 239000001205 polyphosphate Substances 0.000 claims description 7
- 235000011176 polyphosphates Nutrition 0.000 claims description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- AWBASQCACWFTGD-UHFFFAOYSA-N [5-amino-2-[[[5-amino-2-(hydroxymethyl)oxolan-3-yl]oxy-hydroxyphosphoryl]oxymethyl]oxolan-3-yl] (5-amino-3-hydroxyoxolan-2-yl)methyl hydrogen phosphate Chemical compound O1C(N)CC(O)C1COP(O)(=O)OC1C(COP(O)(=O)OC2C(OC(N)C2)CO)OC(N)C1 AWBASQCACWFTGD-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- WSFMFXQNYPNYGG-UHFFFAOYSA-M dimethyl-octadecyl-(3-trimethoxysilylpropyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCC[Si](OC)(OC)OC WSFMFXQNYPNYGG-UHFFFAOYSA-M 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 229910052725 zinc Chemical group 0.000 claims description 3
- 239000011701 zinc Chemical group 0.000 claims description 3
- BSQWCPPAKRSDNZ-UHFFFAOYSA-N [PH2](O)=O.C(C)[Zn]CC Chemical compound [PH2](O)=O.C(C)[Zn]CC BSQWCPPAKRSDNZ-UHFFFAOYSA-N 0.000 claims description 2
- ZTGZQYUPRFFTHM-UHFFFAOYSA-L [PH2]([O-])=O.C(C)[Al+2].[PH2]([O-])=O Chemical compound [PH2]([O-])=O.C(C)[Al+2].[PH2]([O-])=O ZTGZQYUPRFFTHM-UHFFFAOYSA-L 0.000 claims description 2
- REBHQKBZDKXDMN-UHFFFAOYSA-M [PH2]([O-])=O.C(C)[Al+]CC Chemical compound [PH2]([O-])=O.C(C)[Al+]CC REBHQKBZDKXDMN-UHFFFAOYSA-M 0.000 claims description 2
- RBUNRLBCSKCWSF-UHFFFAOYSA-M [PH2]([O-])=O.C(CCC)[Al+]CCCC Chemical compound [PH2]([O-])=O.C(CCC)[Al+]CCCC RBUNRLBCSKCWSF-UHFFFAOYSA-M 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 239000002028 Biomass Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 44
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 34
- 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 32
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical class CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- 239000011574 phosphorus Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 229920002302 Nylon 6,6 Polymers 0.000 description 7
- 238000009775 high-speed stirring Methods 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- GWTCIAGIKURVBJ-UHFFFAOYSA-L dipotassium;dodecyl phosphate Chemical compound [K+].[K+].CCCCCCCCCCCCOP([O-])([O-])=O GWTCIAGIKURVBJ-UHFFFAOYSA-L 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000003017 phosphorus Chemical class 0.000 description 3
- 239000012745 toughening agent Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 229920006052 Chinlon® Polymers 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a modified alkyl hypophosphite flame retardant and a preparation method and application thereof, wherein the modified alkyl hypophosphite flame retardant comprises alkyl hypophosphite and a coating layer coated on the alkyl hypophosphite, the coating layer comprises a negative charge layer and a positive charge layer which are sequentially and alternately coated, the negative charge layer is composed of a first component which is negatively charged and is of biomass origin, the first component at least contains sulfonic acid groups and/or phosphoric acid groups, the positive charge layer is composed of a second component which is positively charged and contains nitrogen, and the molecular weight difference of one of the first component and the second component relative to the other is more than 20000; when the preparation is carried out, the coating step of the first component and the coating step of the second component are sequentially and alternately carried out in the presence of inorganic salt and in the second solvent; the modified alkyl hypophosphite flame retardant disclosed by the invention can realize excellent flame retardance, temperature resistance and other performances with fewer coating times, does not need high temperature in the preparation process, has low energy consumption, and can obviously improve the flame retardance when being used for flame retardance of resin.
Description
Technical Field
The invention relates to the field of flame-retardant materials, in particular to a modified alkyl hypophosphite flame retardant and a preparation method and application thereof.
Background
With the rapid development of the science and technology of the high polymer materials and the continuous update of the molding processing technology, the performance and quality of the high polymer material products are greatly improved, and the high polymer material products are widely applied to various fields of daily life such as buildings, packages, electronic appliances and the like. However, most of the polymer materials are inflammable materials, so that fire hazard is easy to occur, environmental hazard and large economic loss are caused once fire occurs, and large casualties are caused seriously. It is increasingly recognized that the use of flame retardant materials is one of the strategic measures to prevent and reduce fires, as demonstrated by the practice of some countries. Undoubtedly, research, production and application of flame retardants and flame retardant materials are important actions related to the environment and human beings.
The addition of flame retardant to polymer is a simple and effective polymer flame retarding technology, which can increase the ignition difficulty of polymer material, reduce the heat release rate in the combustion process, slow down the exchange of heat and pyrolysis substances, and inhibit the further propagation and spread of flame, thereby reducing or minimizing the fire hazard of the material. The most commonly used and effective flame retardants contain halogen elements which are preferentially released and cut off free radical transfer when the polymer burns, thereby slowing the polymer pyrolysis process. Halogen-containing compounds released from such flame retardants accumulate in the living body and exist in nature for a long period of time, which can greatly jeopardize the survival safety of animals as well as humans.
With the concern of environmental protection and human health of various countries, the requirements on halogen-free, low-smoke and low-toxicity flame retardant materials are urgent. The phosphorus flame retardant has a plurality of outstanding advantages as a high-efficiency halogen-free environment-friendly flame retardant: high phosphorus content, no halogen, low price, good flame retardant effect on various polymers, etc.
The alkyl hypophosphite which is one of the phosphorus flame retardants is relatively suitable for materials such as polyester, nylon and TPE cables because of containing alkyl, organic phosphorus and the like, has certain precipitation resistance, is better in temperature resistance than the common phosphorus flame retardants, and is a relatively common phosphorus flame retardant. However, there are some problems in the application process, such as poor compatibility with materials and high addition amount, which affect the mechanical properties of the materials, and for this problem, patent CN115260594B proposes an improved solution, specifically discloses a modified phosphorus-containing flame retardant, which includes a phosphorus-containing flame retardant and a coating layer coated on the phosphorus-containing flame retardant, and the coating layer includes a polyelectrolyte layer and a polyurethane layer sequentially coated on the phosphorus-containing flame retardant; the polyurethane in the polyurethane layer is cured polyurethane, the cured polyurethane is obtained by curing polyurethane and a curing agent, and the curing agent is selected from one or two of diisocyanate and polyisocyanate; although the patent realizes better compatibility between the modified phosphorus-containing flame retardant and the resin material, the preparation process of the modified phosphorus-containing flame retardant needs to adopt high temperature, even needs to be cured at the temperature of 85 ℃, has higher energy consumption, and also needs to use diisocyanate and polyisocyanate which have great harm to human bodies.
Disclosure of Invention
The invention aims to overcome one or more defects in the prior art and provide an improved modified alkyl hypophosphite flame retardant which can realize excellent flame retardance, temperature resistance and other performances at a small coating frequency, does not need high temperature in the preparation process, has low energy consumption and can obviously improve the flame retardance when used for flame retardance of resin.
The invention also provides a preparation method of the modified alkyl hypophosphite flame retardant.
The invention also provides application of the modified alkyl hypophosphite flame retardant in preparing halogen-free flame retardant and halogen-free flame retardant composite materials.
In order to achieve the above purpose, the invention adopts a technical scheme that:
a modified alkyl hypophosphite flame retardant comprising alkyl hypophosphite and a coating layer coated on the alkyl hypophosphite, characterized in that the coating layer comprises a negatively charged layer and a positively charged layer which are coated alternately in sequence, the negatively charged layer is composed of a first component which is negatively charged and is of biological origin, the first component at least contains sulfonic acid groups and/or phosphoric acid groups, the positively charged layer is composed of a second component which is positively charged and contains nitrogen, and the molecular weight difference of one of the first component and the second component relative to the other is more than 20000.
According to some preferred aspects and in particular aspects of the invention, the molecular weight of one of the first and second components relative to the other differs by above 40000.
According to some preferred aspects of the invention, the first component is a combination of one or more selected from sodium alginate, phytic acid, sodium lignin sulfonate.
According to some preferred aspects of the invention, the second component is a combination of one or more selected from the group consisting of dimethyloctadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, polyaluminum chloride, polydiallyldimethyl ammonium chloride, chitosan, deoxyribonucleic acid sodium salt, polyethylenimine.
Further, in some preferred embodiments of the present invention, the first component is phytic acid and the second component is a combination of one or more selected from chitosan, polydiallyl dimethyl ammonium chloride, polyethylenimine.
Further, in some preferred embodiments of the present invention, the first component is sodium alginate and/or sodium lignin sulfonate, and the second component is a combination of one or more selected from the group consisting of dimethyloctadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, deoxyribonucleic acid sodium salt, polyaluminum chloride, polydiallyldimethyl ammonium chloride, polyethylenimine.
According to some preferred aspects of the present invention, the number of coating layers of the negative charge layer and the number of coating layers of the positive charge layer are respectively equal to or greater than 2.
Further, the number of coating layers of the negative charge layer and the number of coating layers of the positive charge layer are respectively 2-20.
In some embodiments of the present invention, when the outermost layer of the coating layer is a negatively charged layer, the number of coating layers of the negatively charged layer is one more than the number of coating layers of the positively charged layer, and when the outermost layer of the coating layer is a positively charged layer, the number of coating layers of the negatively charged layer and the number of coating layers of the positively charged layer are the same.
In some embodiments of the invention, the alkyl phosphinate has a structure of formula (i):
in the formula (I), R 1 、R 2 Independently selected from C 1-20 Alkyl, X is a metal ion, and t is 1-4.
Further, R 1 、R 2 Independently selected from methyl, ethyl, propyl, isopropyl or butyl.
Further, X is aluminum or zinc. Further, when X is aluminum, t is 3, when X is zinc, t is 2.
According to some specific aspects of the invention, the alkyl phosphinate is one or a combination of more selected from monoethyl aluminum phosphinate, ethyl zinc phosphinate, diethyl aluminum phosphinate, diethyl zinc phosphinate, butyl aluminum phosphinate, dibutyl aluminum phosphinate.
According to some preferred aspects of the present invention, the alkyl hypophosphite is a pretreated alkyl hypophosphite obtained by mixing and stirring alkyl hypophosphite, a dispersant and a first solvent, centrifuging and washing. In the invention, the pretreated alkyl hypophosphite is more favorable for coating, and the uniformity of coating and the like can be improved.
In some embodiments of the invention, the dispersant is a combination of one or more selected from anionic surfactants, nonionic surfactants, and cationic surfactants.
In some embodiments of the invention, the anionic surfactant is a combination of one or more selected from sulfonates, phosphate salts.
In some embodiments of the present invention, the nonionic surfactant is one or more selected from alkylphenol ethoxylates, fatty alcohol ethoxylates, fatty acid polyoxyethylene esters, and alkyl alcohol amides.
In some embodiments of the invention, the cationic surfactant is selected from one or more of a polyethylene polyamine salt, a quaternary ammonium salt.
In some embodiments of the invention, the first solvent is selected from one or more of water, methanol, ethanol, isopropanol.
In some embodiments of the invention, the wash may be performed with water, and the number of washes may be 1-6, preferably 2-4, for example 3 washes may be performed with water.
In some embodiments of the invention, the mass ratio of the alkyl hypophosphite to the first solvent is controlled to be 1:1 to 1:6 during the preparation of the pretreated alkyl hypophosphite;
in some embodiments of the invention, the dispersant is controlled to have a mass concentration in the first solvent of 0.1 to 3.5g/L during the preparation of the pretreated alkylphosphinate.
The invention provides another technical scheme that: the preparation method of the modified alkyl hypophosphite flame retardant comprises the following steps: the coating step of the first component and the coating step of the second component are sequentially and alternately performed on the alkyl hypophosphite in the presence of an inorganic salt in a second solvent.
According to some preferred aspects of the invention, the coating step is carried out at a temperature of 10-30 ℃. Further, the coating step may be performed at 15-30 ℃. According to a particular aspect of the invention, the coating step may be performed at room temperature.
According to some preferred aspects of the invention, the inorganic salt is a combination of one or more selected from sodium sulfate, aluminum sulfate, zinc sulfate. In the invention, inorganic salt is added to adjust the ionic strength, which is beneficial to improving the coating rate of positive and negative charge solution.
In some embodiments of the invention, the second solvent is selected from one or more of water, methanol, ethanol, isopropanol.
In some preferred embodiments of the invention, embodiments of the method of preparation comprise:
(1) Dispersing the first component and the inorganic salt in a second solvent to prepare a negative charge solution; dispersing the second component and the inorganic salt in a second solvent to prepare a positive charge solution;
(2) Adding alkyl hypophosphite into the negative charge solution, stirring, centrifuging and washing to obtain alkyl hypophosphite coated with the first negative charge layer;
(3) Adding the alkyl hypophosphite coated with the first negative charge layer into the positive charge solution, stirring, centrifuging and washing to obtain the alkyl hypophosphite sequentially coated with the first negative charge layer and the first positive charge layer;
(4) Repeating the step (2) and the step (3) for a plurality of times.
In some embodiments of the invention, the stirring time in step (2) and step (3) is from 0.5 to 3 hours.
According to some preferred aspects of the invention, the mass concentration of the first component in the negatively charged solution is controlled to be 0.5-5g/L.
According to some preferred aspects of the invention, the mass concentration of the second component in the positively charged solution is controlled to be 0.5-5g/L.
According to some preferred aspects of the invention, the molar concentration of the inorganic salt in the negatively charged solution or the positively charged solution is controlled to be 0.05 to 2mol/L.
In some embodiments of the invention, the pH of the positively charged solution and the negatively charged solution are both 2 to 7.
The invention provides another technical scheme that: a halogen-free flame retardant comprising the modified alkyl hypophosphite flame retardant described above.
According to some preferred aspects of the invention, the halogen-free flame retardant further comprises a combination of one or more selected from zinc borate, melamine polyphosphate and melamine cyanurate.
In some preferred embodiments of the present invention, the halogen-free flame retardant consists of a modified alkyl hypophosphite flame retardant, zinc borate, melamine polyphosphate and melamine cyanurate.
According to some preferred aspects of the invention, the modified alkyl hypophosphite flame retardant, the zinc borate, the melamine polyphosphate and the melamine cyanurate are dosed in a mass ratio of 8-16:0.1-3:1.5-8:0-5.
The invention provides another technical scheme that: the modified alkyl hypophosphite flame retardant or the application of the halogen-free flame retardant in preparing halogen-free flame retardant composite materials.
Further, the raw materials of the halogen-free flame-retardant composite material comprise a resin matrix, a flame retardant, a toughening agent, an antioxidant and a coupling agent, wherein the flame retardant is the modified alkyl hypophosphite flame retardant or the halogen-free flame retardant.
In some embodiments of the invention, the resin matrix may be polyamide, polyurethane or polyolefin.
Further, the polyamide may be a combination of one or more selected from the group consisting of PA6, PA66, PA-612, PA-12, PA-6T and PA-9T.
In some embodiments of the present invention, the toughening agent may be one or a combination of two selected from POE grafted maleic anhydride, EPDM grafted maleic anhydride.
In some embodiments of the present invention, the antioxidant may be a combination of one or more selected from the group consisting of phenolic antioxidants 1098, 1076, 1010, 1024, phosphorus antioxidants 168, 636, 626, composite antioxidants 215, 225.
In some embodiments of the present invention, the coupling agent may be a combination of one or more selected from the group consisting of a silane coupling agent, an aluminate coupling agent, and a titanate coupling agent.
In some embodiments of the invention, the halogen-free flame retardant composite material comprises, by mass, 45-85 parts of a resin matrix, 5-15 parts of a modified alkyl hypophosphite flame retardant, 2-10 parts of other flame retardants, 0.15-4.5 parts of a toughening agent, 0.1-5 parts of an antioxidant and 0.1-4.5 parts of a coupling agent; the other flame retardant comprises a combination of one or more selected from zinc borate, melamine polyphosphate and melamine cyanurate.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
in the practical process, the inventor of the invention carries out modification research on alkyl hypophosphite, and unexpectedly discovers that coating of a negative charge layer on the alkyl hypophosphite is more favorable for more complete coating and has high coating rate, then the positive charge layer is coated through electrostatic adsorption, and the positive charge layer is sequentially and alternately coated according to the sequence, when the molecular weight of components in the negative charge layer and the molecular weight of components in the positive charge layer have obvious differences, especially reach 20000 or more, the temperature resistance and the flame retardant performance of the modified alkyl hypophosphite can be obviously improved under the condition of fewer coating times (or layers), and the dispersibility in the resin matrix is better, so that the improvement of mechanical properties is favorable; further, according to a great amount of experimental study by the inventor, it is considered that the alkyl hypophosphite has stronger acidity, when dispersed in a solvent such as water, when mixed with biomass source components having a strongly acidic group sulfonic acid group and/or phosphoric acid group, coating can be better realized on the surface of the alkyl hypophosphite, the coated substance is more complete and compact, if the substance is positively charged, a certain risk exists for reacting with part of positively charged substance, and further unexpected new physical properties can occur, which are unfavorable for the use of flame retardant, and meanwhile, when the components in the negatively charged layer and the components in the positively charged layer have obvious differences in molecular weight, substances with smaller molecular weight can be inserted or filled between substance gaps with larger molecular weight, so that two substances which are mutually inserted or complementary to each other in the gaps are combined together through electrostatic attraction, the two substances are also provided with a denser film layer and a more tightly connected relation mutually combined, and can also be coated with a larger amount of substances in unit time, and the same impregnation, and the method can be used for coating uniformly and more completely and completely, more completely, and further improving the flame-retardant stability.
Meanwhile, the negative charge layer adopts biomass-derived components, which is not only beneficial to environmental protection, but also biomass-derived substances usually have rich carbon sources, such as carbon rings, carbon chains and the like containing saturation or unsaturation, and are more beneficial to carbon formation under the action of phosphorus in the alkyl hypophosphite to realize flame retardance, and meanwhile, substances in the positive charge layer are preferably nitrogen-containing components, so that nitrogen and phosphorus synergistic flame retardance can be realized in the flame retardance process.
In addition, the specific modified alkyl hypophosphite flame retardant disclosed by the invention has the advantages that the preparation process is simpler, the operation difficulty is reduced, the high-temperature auxiliary preparation is not needed, and the energy consumption is saved.
Detailed Description
The above-described aspects are further described below in conjunction with specific embodiments; it should be understood that these embodiments are provided to illustrate the basic principles, main features and advantages of the present invention, and that the present invention is not limited by the scope of the following embodiments; the implementation conditions employed in the examples may be further adjusted according to specific requirements, and the implementation conditions not specified are generally those in routine experiments.
All starting materials are commercially available or prepared by methods conventional in the art, not specifically described in the examples below.
Example 1
The embodiment provides a preparation method of a modified diethyl aluminum hypophosphite flame retardant and the modified diethyl aluminum hypophosphite flame retardant prepared by the preparation method, wherein the preparation method of the modified diethyl aluminum hypophosphite flame retardant comprises the following steps:
(1) 0.6g of potassium monododecyl phosphate was dissolved in 1.2L of water to obtain an aqueous solution, and 400g of aluminum diethylphosphinate (D50 of 26.2 μm, D95 of 62.3 μm, bulk density of 0.70g/cm was added to the aqueous solution under high-speed stirring 3 ) Stirring for 6 hours at room temperature, centrifuging and washing for three times to obtain dispersed diethyl aluminum hypophosphite;
(2) Dissolving 2.4g of sodium alginate (purchased from Aba Ding Shiji, with the molecular weight of about 50000) and 15g of sodium sulfate in 1.2L of water, stirring for 0.5h to obtain a negative charge solution, putting the aluminum diethyl hypophosphite dispersed in the step (1) into the negative charge solution, stirring for 1h at room temperature, centrifuging and washing for three times, and coating the surface of the aluminum diethyl hypophosphite with a first negative charge layer;
(3) Dissolving 2.4g of dimethyl octadecyl [3- (trimethoxy silicon based) propyl ] ammonium chloride and 15g of sodium sulfate in 1.2L of water, stirring for 0.5h to obtain a positive charge solution, putting the coated diethyl aluminum hypophosphite in the step (2) into the positive charge solution, stirring for 1h at room temperature, centrifuging and washing for three times, and coating a first positive charge layer on the surface of the first negative charge layer;
(4) Repeating the steps (2) and (3), and stopping when the surface of the aluminum diethyl phosphinate is coated with 8 layers, thus obtaining the modified aluminum diethyl phosphinate.
Example 2
The embodiment provides a preparation method of a modified diethyl aluminum hypophosphite flame retardant and the modified diethyl aluminum hypophosphite flame retardant prepared by the preparation method, wherein the preparation method of the modified diethyl aluminum hypophosphite flame retardant comprises the following steps:
(1) 1g of fatty alcohol-polyoxyethylene ether ammonium sulfate was dissolved in 1.6L of water to obtain an aqueous solution, and 500g of aluminum diethylphosphinate (D50 of 26.2 μm, D95 of 62.3 μm, bulk density of 0.70 g/cm) was added to the aqueous solution under high-speed stirring 3 ) Stirring for 5 hours at room temperature, centrifuging and washing for three times to obtain dispersed diethyl aluminum hypophosphite;
(2) Dissolving 3g of sodium lignin sulfonate (purchased from Linyi n-nuo chemical industry Co., ltd., molecular weight is about 30000) and 15g of aluminum sulfate in 1.5L of water, stirring for 0.5h to obtain a negative charge solution, putting the aluminum diethyl hypophosphite dispersed in the step (1) into the negative charge solution, stirring for 1h at room temperature, centrifuging and washing for three times, and coating a first negative charge layer on the surface of the aluminum diethyl hypophosphite;
(3) Dissolving 3g of deoxyribonucleic acid sodium salt (purchased from Aba Ding Shiji and having a molecular weight of about 523) and 15g of aluminum sulfate in 1.5L of water, stirring for 0.5h to obtain a positive charge solution, putting the coated diethyl aluminum hypophosphite in the step (2) into the positive charge solution, stirring for 1h at room temperature, centrifuging and washing with water for three times, and coating the surface of the first negative charge layer with the first positive charge layer;
(4) Repeating the steps (2) and (3), and stopping when the surface of the aluminum diethyl phosphinate is coated with 8 layers, thus obtaining the modified aluminum diethyl phosphinate.
Example 3
The embodiment provides a preparation method of a modified diethyl aluminum hypophosphite flame retardant and the modified diethyl aluminum hypophosphite flame retardant prepared by the preparation method, wherein the preparation method of the modified diethyl aluminum hypophosphite flame retardant comprises the following steps:
(1) 1g of polyvinylpyrrolidone was dissolvedAn aqueous solution was obtained in 1.6L of water, and 500g of diethyl aluminum hypophosphite (D50 of 26.2 μm, D95 of 62.3 μm, bulk density of 0.70g/cm was added to the aqueous solution under high-speed stirring 3 ) Stirring for 5 hours at room temperature, centrifuging and washing for three times to obtain dispersed diethyl aluminum hypophosphite;
(2) Dissolving 3g of phytic acid and 15g of sodium chloride in 1.5L of water, stirring for 0.5h to obtain a negative charge solution, putting the aluminum diethyl hypophosphite dispersed in the step (1) into the negative charge solution, stirring for 1h at room temperature, centrifuging and washing for three times, and coating a first negative charge layer on the surface of the aluminum diethyl hypophosphite;
(3) Dissolving 3g of polydiallyl dimethyl ammonium chloride (purchased from Aba Ding Shiji with the molecular weight of 200000-350000) and 15g of sodium chloride in 1.5L of water, stirring for 0.5h to obtain a positive charge solution, putting the coated aluminum diethylphosphinate in the step (2) into the positive charge solution, stirring for 1h at room temperature, centrifuging and washing with water for three times, and coating the surface of the first negative charge layer with the first positive charge layer;
(4) Repeating the steps (2) and (3), and stopping when the surface of the aluminum diethyl phosphinate is coated with 8 layers, thus obtaining the modified aluminum diethyl phosphinate.
Example 4
The embodiment provides a preparation method of a modified diethyl aluminum hypophosphite flame retardant and the modified diethyl aluminum hypophosphite flame retardant prepared by the preparation method, wherein the preparation method of the modified diethyl aluminum hypophosphite flame retardant comprises the following steps:
(1) 0.85g of sodium polyacrylate was dissolved in 1.6L of water to obtain an aqueous solution, and 500g of aluminum diethylphosphinate (D50 of 26.2 μm, D95 of 62.3 μm, bulk density of 0.70 g/cm) was added to the aqueous solution under high-speed stirring 3 ) Stirring for 5 hours at room temperature, centrifuging and washing for three times to obtain dispersed diethyl aluminum hypophosphite;
(2) Dissolving 3g of phytic acid and 15g of aluminum sulfate in 1.5L of water, stirring for 0.5h to obtain a negative charge solution, putting the aluminum diethyl hypophosphite dispersed in the step (1) into the negative charge solution, stirring for 1h at room temperature, centrifuging and washing for three times, and coating a first negative charge layer on the surface of the aluminum diethyl hypophosphite;
(3) Dissolving 3g of polyethyleneimine (purchased from Aba Ding Shiji and having a molecular weight of about 25000) and 15g of aluminum sulfate in 1.5L of water, stirring for 0.5h to obtain a positive charge solution, putting the coated diethyl aluminum hypophosphite in the step (2) into the positive charge solution, stirring for 1h at room temperature, centrifuging and washing with water for three times, and coating the surface of the first negative charge layer with the first positive charge layer;
(4) Repeating the steps (2) and (3), and stopping when the surface of the aluminum diethyl phosphinate is coated with 8 layers, thus obtaining the modified aluminum diethyl phosphinate.
Example 5
The embodiment provides a preparation method of a modified diethyl aluminum hypophosphite flame retardant and the modified diethyl aluminum hypophosphite flame retardant prepared by the preparation method, wherein the preparation method of the modified diethyl aluminum hypophosphite flame retardant comprises the following steps:
(1) 2.25g of sodium polyacrylate was dissolved in 4.0L of water to obtain an aqueous solution, and 1000g of aluminum diethylphosphinate (D50 of 26.2 μm, D95 of 62.3 μm, bulk density of 0.70 g/cm) was added to the aqueous solution under high-speed stirring 3 ) Stirring for 5 hours at room temperature, centrifuging and washing for three times to obtain dispersed diethyl aluminum hypophosphite;
(2) Dissolving 7.2g of phytic acid and 31g of aluminum sulfate in 4.0L of water, stirring for 0.5h to obtain a negative charge solution, putting the aluminum diethyl hypophosphite dispersed in the step (1) into the negative charge solution, stirring for 1h at room temperature, centrifuging and washing for three times, and coating a first negative charge layer on the surface of the aluminum diethyl hypophosphite;
(3) Dissolving 7.2g of polyethyleneimine (purchased from Aba Ding Shiji, with the molecular weight of about 25000) and 31g of aluminum sulfate in 4.0L of water, stirring for 0.5h to obtain a positive charge solution, putting the coated aluminum diethylphosphinate in the step (2) into the positive charge solution, stirring for 1h at room temperature, centrifuging and washing with water for three times, and coating the surface of the first negative charge layer with the first positive charge layer;
(4) Repeating the steps (2) and (3), and stopping when the surface of the aluminum diethyl hypophosphite is covered with 12 layers, thus obtaining the modified aluminum diethyl hypophosphite.
Example 6
This example provides a modified diethylThe preparation process of this example is basically the same as that of example 1, except that: the aluminum diethylphosphinate of example 1 (D50 of 26.2 μm, D95 of 62.3 μm, bulk density of 0.70 g/cm) 3 ) Replaced with zinc diethylphosphinate (D50 of 18.8 microns, D95 of 45.6 microns, bulk density of 0.58 g/cm) 3 )。
Example 7
This example provides a modified aluminum dibutyl hypophosphite, the preparation process of this example is substantially the same as that of example 1, except that: the aluminum diethylphosphinate of example 1 (D50 of 26.2 μm, D95 of 62.3 μm, bulk density of 0.70 g/cm) 3 ) Replaced with aluminum dibutyl hypophosphite (D50 of 22.3 microns, D95 of 55.9 microns, bulk density of 0.67 g/cm) 3 )。
Example 8
The embodiment provides a preparation method of a modified diethyl aluminum hypophosphite flame retardant and the modified diethyl aluminum hypophosphite flame retardant prepared by the preparation method, wherein the preparation method of the modified diethyl aluminum hypophosphite flame retardant comprises the following steps:
(1) 400g of aluminum diethylphosphinate (D50 of 26.2 microns, D95 of 62.3 microns, bulk density of 0.70g/cm was selected 3 )；
(2) Dissolving 2.4g of sodium alginate (purchased from Aba Ding Shiji, with a molecular weight of about 50000) and 15g of sodium sulfate in 1.2L of water, stirring for 0.5h to obtain a negative charge solution, putting the aluminum diethyl hypophosphite in the step (1) into the negative charge solution, stirring for 1h at room temperature, centrifuging and washing for three times, and coating the surface of the aluminum diethyl hypophosphite with a first negative charge layer;
(3) Dissolving 2.4g of dimethyl octadecyl [3- (trimethoxy silicon based) propyl ] ammonium chloride and 15g of sodium sulfate in 1.2L of water, stirring for 0.5h to obtain a positive charge solution, putting the coated diethyl aluminum hypophosphite in the step (2) into the positive charge solution, stirring for 1h at room temperature, centrifuging and washing for three times, and coating a first positive charge layer on the surface of the first negative charge layer;
(4) Repeating the steps (2) and (3), and stopping when the surface of the aluminum diethyl phosphinate is coated with 8 layers, thus obtaining the modified aluminum diethyl phosphinate.
Comparative example 1
Substantially the same as in example 1, the only difference is that: and (3) exchanging the sequence of the step (2) and the step (3).
The preparation process comprises the following steps:
(1) 0.6g of potassium monododecyl phosphate was dissolved in 1.2L of water to obtain an aqueous solution, and 400g of aluminum diethylphosphinate (D50 of 26.2 μm, D95 of 62.3 μm, bulk density of 0.70g/cm was added to the aqueous solution under high-speed stirring 3 ) Stirring for 6 hours at room temperature, centrifuging and washing for three times to obtain dispersed diethyl aluminum hypophosphite;
(3) Dissolving 2.4g of dimethyl octadecyl [3- (trimethoxy silicon based) propyl ] ammonium chloride and 15g of sodium sulfate in 1.2L of water, stirring for 0.5h to obtain a positive charge solution, putting the aluminum diethyl hypophosphite dispersed in the step (1) into the positive charge solution, stirring for 1h at room temperature, centrifuging and washing for three times, and coating a first positive charge layer on the surface of the aluminum diethyl hypophosphite;
(2) Dissolving 2.4g of sodium alginate (purchased from Aba Ding Shiji, with the molecular weight of about 50000) and 15g of sodium sulfate in 1.2L of water, stirring for 0.5h to obtain a negative charge solution, putting the coated diethyl aluminum hypophosphite in the step (2) into the negative charge solution, stirring for 1h at room temperature, centrifuging and washing with water for three times, and coating the surface of the first positive charge layer with the first negative charge layer;
(4) Repeating the steps (2) and (3), and stopping when the surface of the aluminum diethyl phosphinate is coated with 8 layers, thus obtaining the modified aluminum diethyl phosphinate.
Comparative example 2
Substantially the same as in example 1, the only difference is that: sodium alginate is replaced by phytic acid.
The preparation process comprises the following steps:
(1) 0.6g of potassium monododecyl phosphate was dissolved in 1.2L of water to obtain an aqueous solution, and 400g of aluminum diethylphosphinate (D50 of 26.2 μm, D95 of 62.3 μm, bulk density of 0.70g/cm was added to the aqueous solution under high-speed stirring 3 ) Stirring for 6 hours at room temperature, centrifuging and washing for three times to obtain dispersed diethyl aluminum hypophosphite;
(2) Dissolving 2.4g of phytic acid and 15g of sodium sulfate in 1.2L of water, stirring for 0.5h to obtain a negative charge solution, putting the aluminum diethyl hypophosphite dispersed in the step (1) into the negative charge solution, stirring for 1h at room temperature, centrifuging and washing for three times, and coating a first negative charge layer on the surface of the aluminum diethyl hypophosphite;
(3) Dissolving 2.4g of dimethyl octadecyl [3- (trimethoxy silicon based) propyl ] ammonium chloride and 15g of sodium sulfate in 1.2L of water, stirring for 0.5h to obtain a positive charge solution, putting the coated diethyl aluminum hypophosphite in the step (2) into the positive charge solution, stirring for 1h at room temperature, centrifuging and washing for three times, and coating a first positive charge layer on the surface of the first negative charge layer;
(4) Repeating the steps (2) and (3), and stopping when the surface of the aluminum diethyl phosphinate is coated with 8 layers, thus obtaining the modified aluminum diethyl phosphinate.
Comparative example 3
Substantially the same as comparative example 2, the only difference is that: stopping when the surface of the diethyl aluminum hypophosphite is coated with 16 layers.
Performance test 1
(1) The modified flame retardants of examples 1 to 8 and comparative examples 1 to 3 were tested for D50 and D95 particle diameters and bulk densities by a laser particle sizer and a multifunctional powder bulk densitometer method, respectively, and specific results are shown in Table 1.
TABLE 1
As is clear from Table 1, the present invention of example 1 can obtain a higher bulk density than that of comparative examples 1 to 3, which is advantageous for the subsequent processing and reduces the generation of processing dust, and in particular, the coating effect of comparative example 3 cannot be obtained even when double the number of layers is coated.
(2) The modified flame retardants in examples 1 to 8, comparative examples 1 to 3 were tested for thermal weight loss temperature at a mass percent of 2% thermal weight loss by thermal weight analysis TGA test, and specific results are shown in table 2.
TABLE 2
As can be seen from Table 2, the modified thermal weight loss temperature of example 1 prepared by the coating method of the present invention is higher than that of comparative examples 1 to 3, and the coating effect is excellent, and the thermal stability is improved, and in particular, the thermal stability effect of the present application cannot be obtained when the coating layer of comparative example 3 is double.
Application examples 1 to 8
The modified aluminum diethylphosphinate flame retardants in examples 1-8 were used in flame retardant of PA66 (purchased from Chongqing Huafeng chinlon fiber Co., ltd.) respectively, and the preparation process of the flame retardant PA66 material was as follows: respectively weighing the modified diethyl aluminum hypophosphite flame retardant and other raw materials (see table 3) in examples 1-8 in parts by weight, pouring the materials into a high-speed mixer for mixing, stirring for 15 minutes under the condition of the rotating speed of 1200r/min, granulating by a double-screw extruder after sample discharging to obtain a halogen-free flame retardant reinforced PA66 material, and drying and injection molding a standard sample;
wherein, the extrusion process parameters are as follows:
extruder temperature distribution for flame-retardant glass fiber reinforced nylon 66 processing technology
Host screw speed: 176n/min, feeding speed: 7.6HZ, host current: 28A.
The injection molding process parameters are as follows: flame-retardant PA66 standard sample preparation: t1=265 ℃, t2=270 ℃, t3=270 ℃, nozzle 265 ℃, mold clamping force 100MPa, melt back pressure 0MPa, melt distance 60mm, melt back distance 5mm. Heating temperature of the die temperature machine: 120 ℃.
Comparative example 1 was used
Substantially the same as in application example 1, the only difference is that: the modified aluminum diethylphosphinate flame retardant of example 1 was replaced with the modified aluminum diethylphosphinate prepared in comparative example 1. See in particular table 3.
Comparative example 2 was used
Substantially the same as in application example 1, the only difference is that: the modified aluminum diethylphosphinate flame retardant of example 1 was replaced with the modified aluminum diethylphosphinate prepared in comparative example 2. See in particular table 3.
Comparative example 3 was used
Substantially the same as in application example 1, the only difference is that: the modified aluminum diethylphosphinate flame retardant of example 1 was replaced with the modified aluminum diethylphosphinate prepared in comparative example 3. See in particular table 3.
TABLE 3 Table 3
Performance test 2
The mechanical properties and flame retardant properties of flame retardant PA66 materials of application examples 1-8 and application comparative examples 1-3 were tested by impact strength (GB/T1843-2008), flexural strength (GB/T9341-2008), tensile strength (GB/T1040.2-2006), oxygen index (GB/T2406.2-2009), vertical burning (GB/T2408-2008), glow wire ignition temperature GWIT (GB/T5169.13-2013) of the materials, and the like, respectively, and the results are shown in table 4.
TABLE 4 Table 4
The modified alkyl hypophosphite flame retardant prepared by the method can not only obtain excellent dispersion in a resin system, but also can obviously improve the flame retardant property of the resin material; in particular, compared with application example 1, when the comparative example 3 is used to coat double layers, although the flame retardant property is improved to some extent, the excellent dispersing effect of the present application cannot be obtained, and the mechanical property is still lacking, and importantly, such a large number of coating layers is obviously unfavorable for enterprises to save production cost and is unfavorable for industrial application.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (21)
1. A modified alkyl hypophosphite flame retardant comprising alkyl hypophosphite and a coating layer coated on the alkyl hypophosphite, characterized in that the coating layer comprises a negatively charged layer and a positively charged layer which are coated alternately in sequence, the negatively charged layer is composed of a first component which is negatively charged and is of biological origin, the first component at least contains sulfonic acid groups and/or phosphoric acid groups, the positively charged layer is composed of a second component which is positively charged and contains nitrogen, and the molecular weight difference of one of the first component and the second component relative to the other is more than 20000.
2. The modified alkyl hypophosphite flame retardant according to claim 1, characterized in that one of the first component and the second component has a molecular weight difference of 40000 or more relative to the other.
3. The modified alkyl hypophosphite flame retardant according to claim 1, wherein the first component is a combination of one or more selected from sodium alginate, phytic acid, sodium lignin sulfonate.
4. The modified alkyl hypophosphite flame retardant according to claim 1, wherein the second component is a combination of one or more selected from the group consisting of dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, polyaluminum chloride, polydiallyl dimethyl ammonium chloride, chitosan, deoxyribonucleic acid sodium salt, polyethylenimine.
5. The modified alkyl hypophosphite flame retardant according to claim 1, 3 or 4, characterized in that the first component is phytic acid and the second component is a combination of one or more selected from chitosan, polydiallyl dimethyl ammonium chloride, polyethylenimine; or alternatively, the first and second heat exchangers may be,
the first component is sodium alginate and/or sodium lignin sulfonate, and the second component is one or a combination of a plurality of dimethyl octadecyl [3- (trimethoxy silicon based) propyl ] ammonium chloride, deoxyribonucleic acid sodium salt, polyaluminum chloride, polydiallyl dimethyl ammonium chloride and polyethylenimine.
6. The modified alkyl hypophosphite flame retardant according to claim 1, wherein the number of coating layers of the negative charge layer and the number of coating layers of the positive charge layer are 2 or more, respectively.
7. The modified alkyl hypophosphite flame retardant according to claim 6, wherein the number of coating layers of the negative charge layer and the number of coating layers of the positive charge layer are respectively 2-20; and/or when the outermost layer of the coating layer is a negative charge layer, the number of coating layers of the negative charge layer is one more than that of the positive charge layer, and when the outermost layer of the coating layer is a positive charge layer, the number of coating layers of the negative charge layer and the number of coating layers of the positive charge layer are the same.
8. The modified alkyl hypophosphite flame retardant according to claim 1, characterized in that the alkyl hypophosphite has the structure of formula (i):
in the formula (I), R 1 、R 2 Independently selected from C 1-20 Alkyl, X is a metal ion, and t is 1-4.
9. The modified alkyl hypophosphite flame retardant according to claim 8, characterized in that R 1 、R 2 Independently selected from methyl, ethyl, propyl, isopropyl, or butyl; and/or X is aluminum or zinc.
10. The modified alkyl phosphinate flame retardant of claim 1, wherein the alkyl phosphinate is a combination of one or more selected from the group consisting of monoethyl aluminum phosphinate, ethyl zinc phosphinate, diethyl aluminum phosphinate, diethyl zinc phosphinate, butyl aluminum phosphinate, dibutyl aluminum phosphinate.
11. The modified alkyl hypophosphite flame retardant according to claim 1, wherein the alkyl hypophosphite is a pretreated alkyl hypophosphite obtained by mixing and stirring alkyl hypophosphite, a dispersant and a first solvent, centrifuging and washing.
12. The modified alkyl hypophosphite flame retardant according to claim 11, characterized in that the dispersant is a combination of one or more selected from anionic surfactant, nonionic surfactant and cationic surfactant; and/or the first solvent is one or a combination of more selected from water, methanol, ethanol and isopropanol.
13. A method of preparing the modified alkyl hypophosphite flame retardant according to any one of claims 1 to 12, characterized in that the method comprises: the coating step of the first component and the coating step of the second component are sequentially and alternately performed on the alkyl hypophosphite in the presence of an inorganic salt in a second solvent.
14. The method for preparing a modified alkyl hypophosphite flame retardant according to claim 13, characterized in that the coating step is performed at 10-30 ℃.
15. The method for preparing a modified alkyl hypophosphite flame retardant according to claim 13, characterized in that the inorganic salt is one or a combination of more selected from sodium sulfate, aluminum sulfate and zinc sulfate; and/or the second solvent is one or a combination of more selected from water, methanol, ethanol and isopropanol.
16. The method of preparing a modified alkyl hypophosphite flame retardant according to claim 13, characterized in that an embodiment of the preparation method comprises:
(1) Dispersing the first component and the inorganic salt in a second solvent to prepare a negative charge solution; dispersing the second component and the inorganic salt in a second solvent to prepare a positive charge solution;
(2) Adding alkyl hypophosphite into the negative charge solution, stirring, centrifuging and washing to obtain alkyl hypophosphite coated with the first negative charge layer;
(3) Adding the alkyl hypophosphite coated with the first negative charge layer into the positive charge solution, stirring, centrifuging and washing to obtain the alkyl hypophosphite sequentially coated with the first negative charge layer and the first positive charge layer;
(4) Repeating the step (2) and the step (3) for a plurality of times.
17. The method for producing a modified alkyl hypophosphite flame retardant according to claim 16, characterized in that the mass concentration of the first component in the negative charge solution is controlled to be 0.5 to 5g/L;
controlling the mass concentration of the second component in the positive charge solution to be 0.5-5g/L;
controlling the molar concentration of the inorganic salt in the negative charge solution or the positive charge solution to be 0.05-2mol/L.
18. A halogen-free flame retardant comprising the modified alkyl hypophosphite flame retardant according to any of claims 1 to 12.
19. The halogen-free flame retardant of claim 18 further comprising a combination of one or more selected from the group consisting of zinc borate, melamine polyphosphate and melamine cyanurate.
20. The halogen-free flame retardant according to claim 19, wherein the halogen-free flame retardant is composed of a modified alkyl hypophosphite flame retardant, zinc borate, melamine polyphosphate and melamine cyanurate, and the mass ratio of the modified alkyl hypophosphite flame retardant, the zinc borate, the melamine polyphosphate and the melamine cyanurate is 8-16:0.1-3:1.5-8:0-5.
21. Use of a modified alkyl hypophosphite flame retardant according to any of claims 1-12 or a halogen free flame retardant according to any of claims 18-20 for the preparation of a halogen free flame retardant composite.
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