CN116444860A - Modified phosphorus-containing flame retardants, flame retardant polyamides, flame retardant polyurethanes and flame retardant polyolefins - Google Patents
Modified phosphorus-containing flame retardants, flame retardant polyamides, flame retardant polyurethanes and flame retardant polyolefins Download PDFInfo
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- CN116444860A CN116444860A CN202310547473.2A CN202310547473A CN116444860A CN 116444860 A CN116444860 A CN 116444860A CN 202310547473 A CN202310547473 A CN 202310547473A CN 116444860 A CN116444860 A CN 116444860A
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- CN
- China
- Prior art keywords
- flame retardant
- phosphorus
- polyurethane
- containing flame
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 168
- 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 148
- 239000004814 polyurethane Substances 0.000 title claims abstract description 71
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 70
- 150000003017 phosphorus Chemical class 0.000 title claims abstract description 45
- 239000004952 Polyamide Substances 0.000 title claims abstract description 23
- 229920002647 polyamide Polymers 0.000 title claims description 22
- 229920000098 polyolefin Polymers 0.000 title claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 54
- 239000011574 phosphorus Substances 0.000 claims abstract description 54
- 239000010410 layer Substances 0.000 claims abstract description 42
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 28
- 239000011247 coating layer Substances 0.000 claims abstract description 12
- -1 polyethylene Polymers 0.000 claims description 18
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 16
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 11
- 229920000388 Polyphosphate Polymers 0.000 claims description 10
- 239000001205 polyphosphate Substances 0.000 claims description 10
- 235000011176 polyphosphates Nutrition 0.000 claims description 10
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 9
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 8
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 8
- 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 8
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-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
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 229920000570 polyether Polymers 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
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims description 4
- 239000012745 toughening agent Substances 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229920000299 Nylon 12 Polymers 0.000 claims description 2
- 229920002292 Nylon 6 Polymers 0.000 claims description 2
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 2
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 2
- 229920006152 PA1010 Polymers 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- HJJOHHHEKFECQI-UHFFFAOYSA-N aluminum;phosphite Chemical compound [Al+3].[O-]P([O-])[O-] HJJOHHHEKFECQI-UHFFFAOYSA-N 0.000 claims description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 2
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 claims 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 23
- 239000011248 coating agent Substances 0.000 abstract description 22
- 239000002904 solvent Substances 0.000 abstract description 21
- 230000004048 modification Effects 0.000 abstract description 12
- 238000012986 modification Methods 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 11
- 239000002270 dispersing agent Substances 0.000 abstract description 7
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 7
- 229920006122 polyamide resin Polymers 0.000 abstract 1
- 229920005672 polyolefin resin Polymers 0.000 abstract 1
- 229920005749 polyurethane resin Polymers 0.000 abstract 1
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical class CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 229920006351 engineering plastic Polymers 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000009775 high-speed stirring Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 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 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- ALFUUYWXIJCFJV-UHFFFAOYSA-N 4-nitrosobenzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=C(N=O)C=C1 ALFUUYWXIJCFJV-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229920001688 coating polymer Polymers 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000003746 surface roughness Effects 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a modified phosphorus-containing flame retardant, and a preparation method and application thereof. The modified phosphorus-containing flame retardant comprises a phosphorus-containing flame retardant and a coating layer coated on the phosphorus-containing flame retardant, wherein the coating layer comprises a polyelectrolyte layer and a polyurethane layer which are sequentially coated on the phosphorus-containing flame retardant. Preferably, the polyurethane in the polyurethane layer is a cured polyurethane. The preparation method comprises the step of enabling the phosphorus-containing flame retardant to sequentially cover polyelectrolyte and polyurethane so as to prepare the polyelectrolyte layer and the polyurethane layer. The coating is preferably carried out in a solvent containing a dispersant and an inorganic salt. The phosphorus-containing flame retardant has obviously improved bulk density and thermal stability after coating modification, and can be used as a flame retardant for polyamide, polyurethane or polyolefin resin and the like.
Description
The invention relates to a modified phosphorus-containing flame retardant, a preparation method thereof and a divisional application of the modified phosphorus-containing flame retardant, wherein the application date is 2022, 8, 29 and 202211039226.3.
Technical Field
The invention relates to a modified phosphorus-containing flame retardant, and a preparation method and application thereof.
Background
With the rapid development of the basic chemical industry and the gradual perfection of national safety fire protection laws and regulations, the flame retardation in the field of engineering plastics becomes a trend of future development, and the overall promotion of the whole flame retardant industry is further promoted. At present, the halogen flame retardant is still mainly used as the national flame retardant, but the halogen flame retardant is gradually replaced by other flame retardants abroad due to the reasons of safety and the like. The future halogen-free flame retardant has wider market and development opportunities.
The phosphorus-containing flame retardant has the advantages of good heat stability, durable flame retardant effect, low smoke and toxicity, small addition amount, high flame retardant efficiency, suitability for various polymer materials and the like as a halogen-free flame retardant, and is widely applied to various engineering plastic substrates for flame retardance in recent years.
In order to achieve a certain flame-retardant effect in a flame-retardant substrate, a large amount of small-particle-size flame retardant powder is often required to be added into engineering plastics, and a large amount of dust is generated in the process, so that the environment is damaged and the physical health of processing workers is not facilitated. And because the particle size of the phosphorus-containing flame retardant is smaller and the specific surface area is large, the interface compatibility between the phosphorus-containing flame retardant and the substrate is poor in the process of adding the phosphorus-containing flame retardant to different engineering plastic substrates, so that the flame retardant powder is unevenly dispersed in the substrate, and defects can be brought to the performance of the composite material. In addition, the thermal stability of the phosphorus-containing flame retardant needs to be improved, for example, in the processing process of high-temperature nylon, part of the phosphorus-containing flame retardant can be decomposed to a certain extent under the high-temperature condition, so that the flame retardant efficiency is reduced, and even toxic gas is generated in the processing process, so that the application range of the phosphorus-containing flame retardant is limited.
Known Chinese patent document CN101376811A discloses a polyurethane microcapsule inorganic phosphorus-containing flame retardant, wherein polyurethane produced by polymerizing polyether glycol and diisocyanate as main monomers and crosslinking monomer pentaerythritol is used as a coating layer, and the inorganic phosphorus-containing flame retardant is used as a core to prepare the microcapsule flame retardant through in-situ polymerization, wherein the water resistance and flame retardant performance of the flame retardant are improved, but the bulk density and the thermal stability of the flame retardant are still not high enough.
In addition, known Chinese patent document CN114181433A discloses a polyurethane-based ionic liquid polymer coated red phosphorus flame retardant material, which is prepared from red phosphorus, polyhydroxy compound, ionic liquid and isocyanate serving as raw materials through in-situ polymerization, but the bulk density and the thermal stability of the material are still not high enough and still need to be improved.
Further known in chinese patent document CN114163688A is a preparation method of clay layer-by-layer self-assembled coated ammonium polyphosphate, in which purified ammonium polyphosphate is repeatedly dispersed in a positive electrolyte solution and a negative electrolyte solution, and the ammonium polyphosphate is coated by self-assembly, wherein the positive electrolyte is one or more of polyethylenimine, polyacrylamide, chitosan, polyallylamine chloride, polyvinylamine and gelatin, and the negative electrolyte is one or more of nano-scale montmorillonite, halloysite and kaolin. The flame retardance of the coated ammonium polyphosphate is improved, but the bulk density and the thermal stability of the ammonium polyphosphate are still to be improved.
Further known in chinese patent document CN111961254a is a method for preparing a modified aluminum hypophosphite flame retardant, wherein aluminum hydroxide, hypophosphorous acid, a silane coupling agent and polyethylene are used as raw materials in a kneader, aluminum hypophosphite is synthesized through a neutralization reaction, and the modified aluminum hypophosphite flame retardant is obtained through a thermal cladding treatment of the silane coupling agent and the polyethylene. The particle size of the modified flame retardant product obtained by the method is uniform, but the bulk density and the thermal stability of the modified flame retardant product are still to be improved.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention provides a modified phosphorus-containing flame retardant which has higher bulk density and improved heat stability, and the flame retardance is improved when the modified phosphorus-containing flame retardant is used for flame retardance of plastics.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the modified phosphorus-containing flame retardant comprises a phosphorus-containing flame retardant and a coating layer coated on the phosphorus-containing flame retardant, wherein the coating layer comprises a polyelectrolyte layer and a polyurethane layer which are sequentially coated on the phosphorus-containing flame retardant.
In some embodiments of the invention, the polyelectrolyte in the polyelectrolyte layer is selected from the group consisting of sodium polyacrylate, sodium polystyrene sulfonate, polydiallyl dimethyl ammonium chloride, sodium polyethylene sulfonate, polyphosphate, polyacrylamide hydrochloride, and a combination of one or more of polyethylene imine hydrochloride.
In some embodiments of the invention, the polyurethane in the polyurethane layer is selected from one or more of polyether polyurethane, polyester polyurethane, and polyether polyester hybrid polyurethane. Polyurethanes are generally polymerized from polyols and diisocyanates, wherein the polyols may be polyether polyols, polyester polyols or mixed polyols, and the diisocyanates are preferably Toluene Diisocyanate (TDI) or Hexamethylene Diisocyanate (HDI).
In some embodiments of the invention, the polyurethane is a cured polyurethane.
In some embodiments of the invention, the cured polyurethane is obtained by curing a polyurethane and a curing agent.
In some embodiments of the invention, the curing agent is selected from the group consisting of one or more of a mono-isocyanate, a di-isocyanate, and a polyisocyanate.
In some embodiments of the invention, the diisocyanate is selected from the group consisting of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), and Lysine Diisocyanate (LDI).
In some embodiments of the invention, the phosphorus-containing flame retardant is a phosphorus-containing aluminum salt flame retardant.
In some embodiments of the invention, the phosphorus-containing aluminum salt flame retardant is selected from the group consisting of one or more of aluminum hypophosphite, aluminum phosphite, aluminum polyphosphate, and aluminum alkyl hypophosphite, wherein the alkyl groups in the aluminum alkyl hypophosphite are C1-C6 alkyl groups.
In some embodiments of the invention, the aluminum alkyl phosphinate is selected from the group consisting of one or more of aluminum ethyl phosphinate, aluminum butyl phosphinate, aluminum diethyl phosphinate, and aluminum dibutyl phosphinate. In some embodiments of the invention, the modified phosphorus-containing flame retardant is prepared by coating a polyelectrolyte with the phosphorus-containing flame retardant in a solvent in the presence of a dispersant, followed by coating with polyurethane.
In some embodiments of the invention, the mass ratio of the phosphorus-containing flame retardant, polyelectrolyte, and polyurethane is 200-600:1-10:1-30.
In some embodiments of the invention, the dispersant is selected from the group consisting of polyvinylpyrrolidone, polyacrylamide, nonionic surfactant, and a combination of one or more of anionic surfactants.
In some embodiments of the invention, the polyacrylamide is an anionic polyacrylamide.
In some embodiments of the present invention, the nonionic surfactant is selected from the group consisting of one or more of fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, fatty acid polyoxyethylene esters, polyoxyethylene alkylamines, polyoxyethylene alkyl alcohol amides, and polyethers.
In some embodiments of the invention, the anionic surfactant is selected from one or more of fatty acid salts, sulfonic acid salts, sulfuric acid ester salts, phosphoric acid ester salts, amino acid salts, phenolic salts, enolic salts, and ketosulfanilates.
The inventor finds that the phosphorus-containing flame retardant powder has hydrophobic performance, the surface energy is larger, and the specific surface area is generally large, so that the surface of the phosphorus-containing flame retardant powder is more adsorbed with more air, the distance between particles of the phosphorus-containing flame retardant powder is larger, the powder is fluffy, and the bulk density is not large. And interaction such as Van der Waals force, electrostatic force and hydrogen bond exists between the coated polyelectrolyte layer and the polyurethane layer, the mutual coordination of the acting forces can effectively realize the uniform coating of the polymer on the surface of the phosphorus-containing flame retardant, the coated polyurethane layer is subjected to curing reaction by the curing agent, and the coating layer is more compact and can form more stable interfacial acting force with the phosphorus-containing flame retardant powder, so that the stacking density and the thermal stability of the phosphorus-containing flame retardant after coating modification are obviously improved, the damage of dust in the processing process of the flame retardant powder can be improved, and meanwhile, the flame retardant efficiency can be improved when the flame retardant is used for matrix materials such as polymers.
The invention also provides a preparation method of the modified phosphorus-containing flame retardant, which comprises the step of coating polyelectrolyte and polyurethane with the phosphorus-containing flame retardant in sequence to prepare a polyelectrolyte layer and a polyurethane layer.
In some embodiments of the invention, the coating is performed in a solvent containing a dispersant and an inorganic salt.
In some embodiments of the invention, the inorganic salt is selected from the group consisting of one or more of sodium sulfate, potassium sulfate, and aluminum sulfate.
In some embodiments of the invention, the solvent is selected from the group consisting of one or more of water, methanol, ethanol, propanol, and acetone.
In some embodiments of the invention, the inorganic salt is present in the solvent at a molar concentration of 0.05 to 1.0mol/L.
In some embodiments of the invention, the mass ratio of the phosphorus-containing flame retardant to the solvent is 1:2 to 1:10.
In some embodiments of the invention, the dispersant is present in the solvent at a mass concentration of 0.1 to 3g/L.
In some embodiments of the invention, the method of preparation comprises the steps of: 1) Dispersing the phosphorus-containing flame retardant, a dispersing agent and inorganic salt into the solvent, adding polyelectrolyte, and coating a polyelectrolyte layer on the phosphorus-containing flame retardant; 2) Heating the solvent to 40-70 ℃, adding aqueous polyurethane into the solvent, and coating a polyurethane layer on the polyelectrolyte layer.
In some embodiments of the present invention, the step 2) specifically includes heating the solvent to 40-70 ℃, dropwise adding aqueous polyurethane into the solvent, stirring for 0.5-3 hours, adding a curing agent into the solvent, and coating the cured polyurethane layer on the polyelectrolyte layer.
In some embodiments of the invention, the method of preparation comprises the steps of: 1) Dispersing the phosphorus-containing flame retardant and the dispersing agent into the solvent, stirring for 0.5-2 h, adding the inorganic salt into the solvent, and stirring for 0.5-2 h to coat the polyelectrolyte layer on the phosphorus-containing flame retardant; 2) Heating the solvent to 40-70 ℃, adding aqueous polyurethane into the solvent, stirring for 0.5-3 h, adding a curing agent into the solvent, heating the solvent to 60-100 ℃, carrying out curing reaction for 1-5 h, and coating the cured polyurethane layer on the polyelectrolyte layer.
In some embodiments of the invention, the aqueous polyurethane is a polyurethane emulsion.
In some embodiments of the invention, the preparation method further comprises post-treatment steps of cooling, centrifuging, washing with water, drying.
The invention also provides application of the modified phosphorus-containing flame retardant: the modified phosphorus-containing flame retardant is used as a flame retardant for polyamide, polyurethane or polyolefin.
The invention also provides a flame retardant composition comprising the modified phosphorus-containing flame retardant described above.
The invention also provides a halogen-free flame retardant polyamide, which comprises polyamide and a flame retardant, wherein the flame retardant comprises the modified phosphorus-containing flame retardant.
In some embodiments of the invention, the flame retardant further comprises a combination of one or more of zinc borate, melamine polyphosphate, and melamine cyanurate.
In some embodiments of the invention, the modified phosphorus-containing flame retardant, zinc borate, melamine polyphosphate and melamine cyanurate are present in a mass ratio of 10 to 15:0-9.8:0-8.6:0-9.5.
In some embodiments of the invention, the modified phosphorus-containing flame retardant, zinc borate, melamine polyphosphate and melamine cyanurate are present in a mass ratio of 10 to 15:0.2-2.5:3.5-5:4.5-6.
In some embodiments of the present invention, the halogen-free flame retardant polyamide comprises the following components in parts by weight: 40-85 parts of polyamide, 5-15 parts of modified phosphorus-containing flame retardant, 2-12 parts of other flame retardants, 0.2-5 parts of toughening agent, 0.1-6 parts of antioxidant and 0.1-4 parts of coupling agent.
In some embodiments of the invention, the polyamide is selected from the group consisting of one or more of PA6, PA66, PA1010, PA-610, PA-612, PA-12, PA-46, PA-6T, and PA-9T; and/or, other flame retardants are selected from one or more combinations of zinc borate, melamine polyphosphate, melamine cyanurate, and ammonium polyphosphate; and/or the toughening agent is selected from one or a combination of more of POE grafted maleic anhydride and EPDM grafted maleic anhydride; and/or the antioxidant is selected from one or a plurality of phenolic antioxidants 1098, 1076, 1010, 1024, 9228 and BHT, phosphorus antioxidants 168, 636, 626, 450 and 686, thioether antioxidants DLTP and DSTP; and/or the coupling agent is selected from one or more of a silane coupling agent, an aluminate coupling agent and a titanate coupling agent.
Compared with the prior art, the invention has the following advantages:
the modified phosphorus-containing flame retardant comprises the polyelectrolyte layer and the polyurethane layer which are sequentially coated on the phosphorus-containing flame retardant, and the polyurethane layer is more hydrophilic relative to the phosphorus-containing flame retardant, so that the surface energy of the polyurethane layer can be reduced, the bulk density of the modified phosphorus-containing flame retardant is further improved after coating, and the influence of dust on the environment and the harm of human health in the processing process of the flame retardant powder can be effectively improved. The phosphorus-containing flame retardant has obviously improved thermal stability after coating modification, can be independently used as the flame retardant of polyamide, polyurethane or polyolefin materials, or can be compounded with other flame retardants to be used as the compound flame retardant of the polymer materials, so that the polymer materials have good flame retardant property.
Drawings
FIG. 1 is a Fourier infrared spectrum of example 2 before coating modification of aluminum diethylphosphinate;
FIG. 2 is a Fourier infrared spectrum of the modified coating of aluminum diethylphosphinate of example 2;
FIG. 3 is an SEM image of coated modified aluminum diethylphosphinate obtained in example 2.
Detailed Description
The invention provides a modified phosphorus-containing flame retardant, which is mainly characterized in that a polyelectrolyte layer and a polyurethane layer are sequentially coated on the phosphorus-containing flame retardant. Because the polyurethane contains carbonyl and other hydrophilic groups in the structure, the polyurethane is more hydrophilic than phosphorus-containing flame retardant powder, and is favorable for reducing the surface energy of the polyurethane, further reducing the air adsorbed on the surface of the powder and increasing the bulk density of the powder. And interaction such as Van der Waals force, electrostatic force, hydrogen bond and the like exists between the coated polyelectrolyte layer and the polyurethane layer, and the interaction of the acting forces can effectively realize uniform coating of the polymer on the surface of the phosphorus-containing flame retardant, and after the coated polyurethane layer is subjected to curing reaction of the curing agent, the coating layer is more compact and can form more stable interface acting force with the phosphorus-containing flame retardant powder, so that the stacking density and the thermal stability of the phosphorus-containing flame retardant after coating modification are obviously improved.
The invention is characterized in that the modified phosphorus-containing flame retardant is coated in the solvent phase, so that polyelectrolyte and polyurethane can be uniformly and compactly coated on the surface of the phosphorus-containing flame retardant, and the modification process is simple and the condition is mild. According to the invention, the inorganic salt is added into the solvent phase of the coating process to adjust the ionic strength, so that the coating utilization rate of polyelectrolyte and polyurethane is improved.
The invention is further described below with reference to examples. The present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions which are not noted are conventional conditions in the industry. The technical features of the various embodiments of the present invention may be combined with each other as long as they do not collide with each other.
Example 1
The embodiment provides a coated modified diethyl aluminum hypophosphite, which is prepared by the following steps:
1.2g of polyvinylpyrrolidone was dissolved in 1.25L of water to obtain an aqueous solution, and 200g of aluminum diethylphosphinate (D50 of 2.72 μm, D95 of 8.21 μm, bulk density of 0.4 g/cm) was added to the aqueous solution under high-speed stirring 3 ) Stirring was carried out at room temperature for 2 hours to obtain a mixed solution. To the mixture was added a certain amount of sodium sulfate so that the ionic strength of the mixture became 0.1M, and 1.25g of polydiallyl dimethyl ammonium chloride (PDDA) was added thereto and stirred for 0.5h. 500mL of polyester aqueous polyurethane with the concentration of 3.5g/L is added into the mixed solution dropwise, the temperature is increased to 50 ℃, the mixture is stirred at a constant speed for 2 hours, and then the temperature is reduced to room temperature. Then 83mL of hexamethylene diisocyanate aqueous solution with the concentration of 1.5g/L is added, the temperature is firstly raised to 60 ℃ and kept for 1h, and then the temperature is raised to 85 ℃ and kept for 3h, so as to carry out curing reaction. And after the reaction is finished, centrifuging to remove water, centrifuging for three times, washing with water, and drying in an oven at 120 ℃ to obtain the coated modified diethyl aluminum hypophosphite.
Example 2
The embodiment provides a coated modified diethyl aluminum hypophosphite, which is prepared by the following steps:
1.37g of polyoxyethylene alkyl alcohol amide was dissolved in 2L of water to obtain an aqueous solution, to which 450g of aluminum diethylphosphinate (D50 of 2.72 μm, D95 of 8.21 μm, bulk density of 0.4 g/cm) was added with stirring at high speed 3 ) Stirring was carried out at room temperature for 2 hours to obtain a mixed solution. To the mixture was added a certain amount of sodium sulfate so that the ionic strength of the mixture became 0.25M, and 2.15g of sodium polystyrene sulfonate was added thereto and stirred for 0.5h. 200mL of polyester aqueous polyurethane with the concentration of 10.5g/L is added into the mixed solution dropwise, the temperature is raised to 40 ℃ and stirred at a constant speed for 2 hours, and then the temperature is reduced to room temperature. Then 200mL of hexamethylene diisocyanate aqueous solution with the concentration of 1.5g/L is added, the temperature is firstly raised to 60 ℃ and kept for 1h, and then the temperature is raised to 85 ℃ and kept for 3h, so as to carry out the curing reaction. And after the reaction is finished, centrifuging to remove water, centrifuging for three times, washing with water, and drying in an oven at 120 ℃ to obtain the coated modified diethyl aluminum hypophosphite.
Fourier infrared spectrograms before and after coating modification of diethyl aluminum hypophosphite are respectively shown in figures 1-2, and are obtained fromAs can be seen from a comparison of FIGS. 1-2, after coating the aluminum diethylphosphinate with polyurethane, the aluminum diethylphosphinate film was coated at 1726.8cm -1 A c=o double bond vibration absorption peak was detected at the wavelength, which suggests that the polyurethane was effectively modified to the surface of the aluminum diethylphosphinate powder. The SEM spectrogram of the coated modified aluminum diethyl phosphinate is shown in figure 3, and the surface roughness of the aluminum diethyl phosphinate is reduced and the surface is smoother after the modification of sodium polystyrene sulfonate and polyurethane.
Example 3
The embodiment provides a coated modified diethyl aluminum hypophosphite, which is prepared by the following steps:
7.8g of anionic polyacrylamide was dissolved in 10L of water to obtain an aqueous solution, and 4kg of aluminum diethylphosphinate (D50 of 2.72 μm, D95 of 8.21 μm, bulk density of 0.4 g/cm) was added to the aqueous solution under high-speed stirring 3 ) Stirring was carried out at room temperature for 2 hours to obtain a mixed solution. To the mixture was added an amount of aluminum sulfate such that the ionic strength of the mixture became 0.1M, 18.5g of polyethyleneimine hydrochloride was added thereto and stirred for 0.5h. 800mL of 50.8g/L polyester aqueous polyurethane is added into the mixed solution dropwise, the temperature is raised to 40 ℃ and stirred at a constant speed for 2 hours, and then the temperature is reduced to room temperature. 200mL of isophorone diisocyanate aqueous solution with the concentration of 1.5g/L is added, the temperature is firstly increased to 60 ℃ and kept for 1h, and then the temperature is increased to 85 ℃ and kept for 3h, so that the curing reaction is carried out. And after the reaction is finished, centrifuging to remove water, centrifuging for three times, washing with water, and drying in an oven at 120 ℃ to obtain the coated modified diethyl aluminum hypophosphite.
Example 4
The present embodiment provides a coated modified aluminum dibutyl hypophosphite, the preparation process of the present embodiment is basically the same as that of embodiment 1, and the difference is that: the aluminum diethylphosphinate of example 1 (D50 of 2.72 μm, D95 of 8.21 μm, bulk density of 0.4 g/cm) 3 ) Replaced with aluminum dibutyl hypophosphite (D50 of 6.17 microns, D95 of 13.21 microns, bulk density of 0.3 g/cm) 3 )。
Comparative example 1
The comparative example provides a coated modified aluminum diethylphosphinate, which is prepared as follows:
1.2g of polyvinylpyrrolidone was dissolved in 1.25L of water to obtain an aqueous solution, and 200g of aluminum diethylphosphinate (D50 of 2.72 μm, D95 of 8.21 μm, bulk density of 0.4 g/cm) was added to the aqueous solution under high-speed stirring 3 ) Stirring was carried out at room temperature for 2 hours to obtain a mixed solution. Then, a certain amount of sodium sulfate was added to the mixed solution so that the ionic strength of the mixed solution was 0.1M. 500mL of polyester aqueous polyurethane with the concentration of 3.5g/L is added into the mixed solution dropwise, the temperature is increased to 50 ℃, the mixture is stirred at a constant speed for 2 hours, and then the temperature is reduced to room temperature. Then 83mL of hexamethylene diisocyanate aqueous solution with the concentration of 1.5g/L is added, the temperature is firstly raised to 60 ℃ and kept for 1h, and then the temperature is raised to 85 ℃ and kept for 3h, so as to carry out curing reaction. And after the reaction is finished, centrifuging to remove water, centrifuging for three times, washing with water, and drying in an oven at 120 ℃ to obtain the coated modified diethyl aluminum hypophosphite.
Comparative example 2
The comparative example provides a coated modified aluminum diethylphosphinate, which is prepared as follows:
1.2g of polyvinylpyrrolidone was dissolved in 1.25L of water to obtain an aqueous solution, and 200g of aluminum diethylphosphinate (D50 of 2.72 μm, D95 of 8.21 μm, bulk density of 0.4 g/cm) was added to the aqueous solution under high-speed stirring 3 ) Stirring was carried out at room temperature for 2 hours to obtain a mixed solution. Then, a certain amount of sodium sulfate was added to the mixed solution so that the ionic strength of the mixed solution became 0.1M, and 1.25g of polydiallyl dimethyl ammonium chloride (PDDA) was added thereto as a coating polymer layer and stirred for 0.5h. Then 83mL of hexamethylene diisocyanate aqueous solution with the concentration of 1.5g/L is added, the temperature is raised to 60 ℃ for 1h, and then the temperature is raised to 85 ℃ for 3h. And after the reaction is finished, centrifuging to remove water, centrifuging for three times, washing with water, and drying in an oven at 120 ℃ to obtain the coated modified diethyl aluminum hypophosphite.
The modified flame retardants D50 and D95 particle sizes, bulk density in examples 1-4, comparative examples 1-2 were tested by laser particle sizer and multifunctional powder bulk densitometer methods, respectively, and thermal weight loss temperatures at different thermal weight loss percentages were tested by thermal weight loss analysis, TGA. The results of the particle size and bulk density are shown in table 1 below.
TABLE 1 particle size and bulk Density of modified flame retardants in examples 1-4 and comparative examples 1-2
It can be seen that the bulk density of the modified phosphorus-containing flame retardant of the invention is significantly improved compared with that before modification, while in comparative examples 1 and 2, when the phosphorus-containing flame retardant is coated with only the polyelectrolyte layer or the polyurethane layer, the bulk density of the modified phosphorus-containing flame retardant is maintained substantially unchanged and is not improved. The particle size of the modified phosphorus-containing flame retardant is not greatly different from that before modification, the thickness of the coating layer is between tens and hundreds of nanometers, the nano-scale regulation and control of the thickness of the coating layer can be realized, and the particle size of the modified phosphorus-containing flame retardant is not greatly increased because the coating layer is thinner, so that the flame retardant effect of the modified phosphorus-containing flame retardant can be ensured when the modified phosphorus-containing flame retardant is subsequently used for a resin material, and meanwhile, the modified phosphorus-containing flame retardant has better compatibility with the resin material, and the comprehensive mechanical property of the resin material can be improved.
The thermal weight loss temperatures at the different thermal weight loss percentages are shown in table 2 below.
TABLE 2 thermal weight loss temperature of modified flame retardants in examples 1-4, comparative examples 1-2
It can be seen that the thermal stability of the modified phosphorus-containing flame retardant is significantly improved, while in comparative examples 1 and 2, the thermal stability of the modified phosphorus-containing flame retardant remains substantially unchanged when the phosphorus-containing flame retardant is coated with only the polyelectrolyte layer or the polyurethane layer.
Examples 5 to 10
The coated modified aluminum diethylphosphinate of examples 1-3 was used in the flame retardance of PA66, respectively, and the flame retardance PA66 material was prepared as follows: the coated modified diethyl aluminum hypophosphite and other raw materials (see table 3) in examples 1-3 are respectively weighed according to parts by weight, poured into a high-speed mixer for mixing, stirred for 10 minutes under the condition of 900r/min, and granulated by a double-screw extruder after sample discharging to obtain the halogen-free flame-retardant reinforced PA66 material, and the halogen-free flame-retardant reinforced PA66 material is subjected to drying treatment and injection molding standard samples.
Comparative examples 3 to 5
The preparation process of the flame-retardant PA66 material, which uses pure diethyl aluminum hypophosphite without coating modification in the flame retardance of PA66, is the same as that of examples 5-10, and the raw material composition is shown in Table 3.
TABLE 3 raw material compositions of examples 7-9, comparative example 3
The mechanical properties and flame retardant properties of the PA66 materials of examples 5-10 and comparative examples 3-5 were tested by the methods of impact strength (GB/T1843-2008), flexural strength (GB/T9341-2008), tensile strength (GB/T1040.2-2006), oxygen index (GB/T2406.2-2009), vertical combustion (GB/T2408-2008), and the like, respectively, and the results are shown in table 4.
TABLE 4 results of Performance test of examples 7-9, comparative examples 3-5
The modified phosphorus-containing flame retardant can ensure the mechanical property of the polyamide material when being used for the polyamide material, and can improve the flame retardant property of the polyamide material to a certain extent, such as the oxygen index and whiteness of the polyamide material, compared with the uncoated modified phosphorus-containing flame retardant.
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 (13)
1. A modified phosphorus-containing flame retardant comprising a phosphorus-containing flame retardant and a coating layer coated on the phosphorus-containing flame retardant, characterized in that: the coating layer comprises a polyelectrolyte layer and a polyurethane layer which are sequentially coated on the phosphorus-containing flame retardant.
2. The modified phosphorus-containing flame retardant of claim 1, wherein: the polyelectrolyte in the polyelectrolyte layer is selected from one or more of sodium polyacrylate, sodium polystyrene sulfonate, polydiallyl dimethyl ammonium chloride, sodium polyethylene sulfonate, polyphosphate, polyacrylamide hydrochloride and polyethyleneimine hydrochloride.
3. The modified phosphorus-containing flame retardant of claim 1, wherein: the polyurethane in the polyurethane layer is selected from one or a combination of more of polyether polyurethane, polyester polyurethane and polyether polyester mixed polyurethane; and/or the polyurethane in the polyurethane layer is cured polyurethane.
4. The modified phosphorus-containing flame retardant of claim 1, wherein: the phosphorus-containing flame retardant is selected from one or more of phosphorus-containing aluminum salt flame retardants, melamine phosphate, melamine cyanurate, ammonium polyphosphate, and melamine pyrophosphate.
5. The modified phosphorus-containing flame retardant of claim 4, wherein: the phosphorus-containing aluminum salt flame retardant is selected from one or a combination of a plurality of aluminum hypophosphite, aluminum phosphite, polyaluminum phosphite and aluminum alkyl hypophosphite, wherein the alkyl in the aluminum alkyl hypophosphite is C1-C6 alkyl.
6. The modified phosphorus-containing flame retardant of claim 7, wherein: the mass ratio of the phosphorus-containing flame retardant to the polyelectrolyte to the polyurethane is 200-600:1-10:1-30.
7. The halogen-free flame-retardant polyurethane comprises polyurethane and a flame retardant, and is characterized in that: the flame retardant comprising the modified phosphorus-containing flame retardant of any of claims 1-6.
8. A halogen-free flame retardant polyolefin comprising a polyolefin and a flame retardant, characterized in that: the flame retardant comprising the modified phosphorus-containing flame retardant of any of claims 1-6.
9. A halogen-free flame retardant polyamide comprising a polyamide and a flame retardant, characterized in that: the flame retardant comprising the modified phosphorus-containing flame retardant of any of claims 1-6.
10. The halogen-free flame retardant polyamide according to claim 9, wherein: the flame retardant further comprises a combination of one or more of zinc borate, melamine polyphosphate and melamine cyanurate.
11. The halogen-free flame retardant polyamide according to claim 10, wherein: the mass ratio of the modified phosphorus-containing flame retardant to the zinc borate to the melamine polyphosphate to the melamine cyanurate is 10-15:0-9.8:0-8.6:0-9.5.
12. The halogen-free flame retardant polyamide according to claim 9, wherein: the halogen-free flame retardant polyamide comprises the following components in parts by weight: 40-85 parts of polyamide, 5-15 parts of modified phosphorus-containing flame retardant, 2-12 parts of other flame retardants, 0.2-5 parts of toughening agent, 0.1-6 parts of antioxidant and 0.1-4 parts of coupling agent.
13. The halogen-free flame retardant polyamide according to claim 12, wherein: the polyamide is selected from one or more of PA6, PA66, PA1010, PA-610, PA-612, PA-12, PA-46, PA-6T and PA-9T; and/or the other flame retardant is selected from one or more of zinc borate, melamine polyphosphate, melamine cyanurate and ammonium polyphosphate; and/or the toughening agent is selected from one or two of POE grafted maleic anhydride and EPDM grafted maleic anhydride; and/or the antioxidant is selected from one or a plurality of phenolic antioxidants 1098, 1076, 1010, 1024, 9228 and BHT, phosphorus antioxidants 168, 636, 626, 450 and 686, thioether antioxidants DLTP and DSTP; and/or the coupling agent is selected from one or more of a silane coupling agent, an aluminate coupling agent and a titanate coupling agent.
Priority Applications (1)
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