CN115073819B - Growth-nucleus-based aluminum phosphate flame retardant, and preparation method and application thereof - Google Patents
Growth-nucleus-based aluminum phosphate flame retardant, and preparation method and application thereof Download PDFInfo
- Publication number
- CN115073819B CN115073819B CN202210672081.4A CN202210672081A CN115073819B CN 115073819 B CN115073819 B CN 115073819B CN 202210672081 A CN202210672081 A CN 202210672081A CN 115073819 B CN115073819 B CN 115073819B
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- China
- Prior art keywords
- flame retardant
- aluminum
- growth
- aluminum phosphate
- growth nucleus
- 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.)
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 167
- 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 152
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 45
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011574 phosphorus Substances 0.000 claims abstract description 31
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 31
- 239000003365 glass fiber Substances 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 25
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000002808 molecular sieve Substances 0.000 claims description 45
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [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 21
- 238000000034 method Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 239000011152 fibreglass Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 10
- 229920001187 thermosetting polymer Polymers 0.000 claims description 8
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 229920001169 thermoplastic Polymers 0.000 claims description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 6
- 125000000962 organic group Chemical group 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 241000269350 Anura Species 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 229920006351 engineering plastic Polymers 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 229920003023 plastic Polymers 0.000 abstract 1
- 238000000635 electron micrograph Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- -1 diphenyl hypophosphite Chemical compound 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 239000007787 solid Substances 0.000 description 18
- DWZJIMWMBCWAPW-UHFFFAOYSA-N trisodium;phosphite;pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])[O-] DWZJIMWMBCWAPW-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000000725 suspension Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000004321 preservation Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 7
- HJJOHHHEKFECQI-UHFFFAOYSA-N aluminum;phosphite Chemical compound [Al+3].[O-]P([O-])[O-] HJJOHHHEKFECQI-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- LPFYDEANGXVAOA-UHFFFAOYSA-M sodium;diethylphosphinate Chemical compound [Na+].CCP([O-])(=O)CC LPFYDEANGXVAOA-UHFFFAOYSA-M 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 3
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 229920003189 Nylon 4,6 Polymers 0.000 description 2
- 229920000007 Nylon MXD6 Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- HWTGNSKUIIUDOU-PEBGCTIMSA-N (5r,6r,7s,8r)-5-acetamido-6,7,8,9-tetrahydroxy-2-oxononanoic acid Chemical compound OC(=O)C(=O)CC[C@@H](NC(=O)C)[C@@H](O)[C@H](O)[C@H](O)CO HWTGNSKUIIUDOU-PEBGCTIMSA-N 0.000 description 1
- GJFHZJKEFLHDEL-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine zinc Chemical compound [Zn].N1=C(N)N=C(N)N=C1N GJFHZJKEFLHDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZCYDTLKUSYRURG-UHFFFAOYSA-K P([O-])([O-])=O.P(=O)([O-])(O)O.[Al+3] Chemical compound P([O-])([O-])=O.P(=O)([O-])(O)O.[Al+3] ZCYDTLKUSYRURG-UHFFFAOYSA-K 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- REBHQKBZDKXDMN-UHFFFAOYSA-M [PH2]([O-])=O.C(C)[Al+]CC Chemical compound [PH2]([O-])=O.C(C)[Al+]CC REBHQKBZDKXDMN-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000036528 appetite Effects 0.000 description 1
- 235000019789 appetite Nutrition 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 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
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a preparation method of an aluminum phosphate flame retardant based on a growth nucleus, wherein one or more compound substances in hypophosphite, organic hypophosphite, phosphite and organic phosphite and aluminum salt are used as raw materials, and the growth nucleus is added for reaction when the aluminum phosphate flame retardant is prepared; the growth nucleus is a substance with rough surface or porous surface. The invention also provides a corresponding flame retardant and application thereof in preparing various plastic products. The phosphorus (phosphonic) acid aluminum salt flame retardant based on the growth nucleus can be well suitable for a glass fiber reinforced engineering plastic system, and the prepared halogen-free flame-retardant glass fiber reinforced material can reach the UL94V0 (0.8 mm) flame retardant grade.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to an aluminum phosphate flame retardant based on a growth nucleus, and a preparation method and application thereof.
Background
Currently, phosphorus flame retardants mainly include inorganic phosphorus flame retardants typified by ammonium polyphosphate, aluminum phosphate systems typified by aluminum hypophosphite/diethyl aluminum hypophosphite/aluminum phosphite, and (poly) phosphate systems typified by RDP/BDP. Comprehensively considering the factors such as temperature resistance, precipitation risk, mechanical property, electrical property and the like, the flame retardant system based on the phosphorus (phosphonic) acid aluminum salt is widely applied to halogen-free flame-retardant glass fiber reinforced engineering plastics. For example, inorganic aluminum hypophosphite, aluminum phosphite or organic aluminum phosphate, diethyl aluminum phosphinate or a mixed flame retardant system compounded according to a certain proportion has higher phosphorus content, and can also produce synergistic effect with a nitrogen-containing flame retardant, so that the efficient flame retardance of the glass fiber reinforced engineering plastic is realized. However, aluminum phosphate flame retardant systems still have some common problems:
1. The particles are unevenly distributed, so that the material performance has fluctuation: most of the preparation methods of the aluminum phosphate (phosphonate) are precipitation reactions, and in the reaction process, under the condition of high temperature, the reaction is too fast, so that the size distribution of precipitated particles is too large, and the particle size is smaller; the temperature is too low, the crystallinity of the product is high, but the reaction is insufficient, and the impurity inclusion is too much.
2. The addition amount is high, and the cost of the flame retardant is high: in general, the commercial aluminum phosphate series flame retardant can achieve higher flame retardant efficiency only when the phosphorus content in the formulation is higher, for example, P% =2% -4%. Especially after this annual energy limit, the price of yellow phosphorus rises from 15000 yuan/ton to near 80000 yuan/ton, and the global phosphorus related industry is under heavy creation.
Therefore, how to improve the flame retardant efficiency per unit mass of phosphorus is one of the important directions for the future development of phosphorus flame retardants. One proposal is to raise the phosphorus content in the flame retardant as much as possible, such as red phosphorus and hypophosphite flame retardant, which has high phosphorus content, but also has the problems of fire and easy migration; in addition, it has been found in research that for additive flame retardants, the flame retardant effect tends to be that of the outer layer of the flame retardant, while the inner layer tends to be ineffective. Many researchers have attempted to ultra-fine process, e.g., nanocrystallize, common flame retardants, but have faced the problem of high processing viscosity and inclusion with other ingredients.
Disclosure of Invention
Aiming at one or more of the problems in the prior art, the invention provides an aluminum phosphate flame retardant based on a growth nucleus, a preparation method thereof and application thereof in preparing various thermoplastic plastics and thermosetting plastics, in particular to application in preparing halogen-free flame-retardant glass fiber reinforced engineering plastics.
The invention provides a preparation method of an aluminum phosphate flame retardant based on a growth nucleus, wherein the growth nucleus is added for reaction when the aluminum phosphate flame retardant is prepared by taking a phosphorus-containing raw material and aluminum salt as raw materials; the phosphorus-containing raw material is one or more compound of hypophosphite, organic hypophosphite, phosphite and organic phosphite; the growth nucleus is a substance with rough surface or porous surface.
According to one aspect of the invention, the growth nuclei are molecular sieves or diatomaceous earth; the diatomite is natural diatomite or a purification product of the diatomite; preferably, the molecular sieve is a natural zeolite or an artificial synthetic molecular sieve, and the molecular sieve comprises silicate, aluminum silicate type molecular sieve, mesoporous type molecular sieve and aluminum phosphate type molecular sieve; the silicate and aluminum silicate type molecular sieve comprises A, X, Y, M, ZSM types; the mesoporous molecular sieve comprises MCM-41 and SBA-15 types; the aluminum phosphate type molecular sieve comprises AlPO 4 series, SAPO series, meAPO series and ElAPO series.
According to one aspect of the invention, the hypophosphite, organic hypophosphite, phosphite, organic phosphite is a readily soluble salt; such as potassium, sodium, ammonium salts;
The organic group of the organic hypophosphite is monoalkyl, monophenyl, dialkyl or diphenyl hypophosphite;
the organic group of the organic phosphite is alkyl or phenyl phosphite.
The aluminum salt is easily soluble aluminum salt; such as aluminum sulfate, aluminum chloride, aluminum nitrate, preferably aluminum sulfate.
According to one aspect of the invention, the weight ratio of the growth nuclei to the phosphorus-containing raw material is 1:10-11:1; and/or
The D50 of the growth nuclei is 0.2-50. Mu.m, preferably 1-30. Mu.m; and/or
The reaction temperature during the reaction is as follows: the reaction is carried out at 55-105 ℃.
The weight ratio of the growth nuclei to the phosphorus-containing raw material is selected because the growth nuclei are too many, the dispersion of the phosphate on the growth nuclei is better, but the effective phosphorus content is too low; the growth nuclei are too few, and a part of the prepared phosphate flame retardant can be irrelevant to the growth nuclei and independently precipitate out of the solution.
When the D50 particle size of the growth nuclei is larger than 50 mu m, the surface energy is relatively low, the combination ability of the flame retardant for surface growth is poor, the proportion of the flame retardant actually loaded is too low, and meanwhile, in the macromolecule, the particles are too large, so that uneven dispersion is caused.
When the D50 particle size of the growth nuclei is less than 0.2 μm, the viscosity during the production process is too large, and the size of the commercially available materials is not too small.
According to another aspect of the invention, the preparation method comprises the following steps: pre-adsorbing one or more compound substances of hypophosphite, organic hypophosphite, phosphite and organic phosphite with the growth nucleus, uniformly stirring, and then dropwise adding aluminum salt for reaction to prepare the aluminum phosphate flame retardant based on the growth nucleus.
The invention also provides an aluminum phosphate flame retardant based on the growth nucleus, which is prepared by the method.
The invention also provides application of the aluminum phosphate flame retardant based on the growth nucleus in preparation of thermoplastic plastics and thermosetting plastics;
preferably, the application is the application of aluminum phosphate flame retardant combined with glass fiber based on growth cores in the preparation of halogen-free flame-retardant glass fiber reinforced plastic.
The invention also provides a thermoplastic plastic and a thermosetting plastic, wherein the preparation raw materials of the thermoplastic plastic and the thermosetting plastic comprise the aluminum phosphate flame retardant based on the growth nucleus.
The invention also provides halogen-free flame-retardant glass fiber reinforced plastic, which comprises the following raw materials in percentage by weight:
A resin base material: 18-84.5%;
the growth-nucleus-based aluminum phosphate flame retardant described above: 10-30%;
glass fiber: 5-50%;
other processing aids: 0.5-2%.
The invention also provides a preparation method of the halogen-free flame-retardant glass fiber reinforced plastic, which comprises the following steps: and after the temperature is stabilized, adding a base material and other processing aids from a hopper, adding glass fibers through a glass fiber adding port, adding the aluminum phosphate flame retardant based on the growth nuclei through a side feeder, starting a host machine and the feeder, extruding and granulating the materials, and drying the materials.
The beneficial effects of the invention are as follows:
1. The flame retardant prepared by the invention is easier to disperse in a high polymer system.
2. The invention adopts inert porous inorganic material as growth nucleus, and the flame retardant is controllably grown in the growth nucleus or crystallization is initiated by taking the growth nucleus as initiation point. The porous growth nucleus also has the function of enhancing the flame retardant effect. For example, more inorganic materials such as MCM, SBA-15, attapulgite and the like are reported to have obvious auxiliary effect on flame retardance.
3. The invention reduces the actual use amount of phosphorus; one theory holds that particulate aluminum phosphate flame retardants play a major role in the flame retarding process with only the surface portion and less or no flame retarding effect in the interior. The invention deposits most flame retardant on the surface by utilizing the larger specific surface area of the growth nuclear material, thereby playing the flame retardant effect.
4. The phosphorus (phosphonic) acid aluminum salt flame retardant based on the growth nucleus can be well suitable for a glass fiber reinforced engineering plastic system, and the prepared halogen-free flame-retardant glass fiber reinforced material can reach the UL94V0 (0.8 mm) flame retardant grade. Under the condition that the using amount of the phosphorus is the same as that in the prior art, the flame retardant effect is improved.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a schematic representation of the growth of aluminum phosphate on a growth nucleus.
FIG. 2 is an electron micrograph of a flame retardant sample of example 1. Wherein A is a 5000-time electron microscope photograph; b is 10000 times of electron microscope pictures; c is 30000 times of electron microscope photograph.
FIG. 3 is an electron micrograph of a flame retardant sample of example 2. Wherein A is a 5000-time electron microscope photograph; b is 10000 times of electron microscope pictures; c is 30000 times of electron microscope photograph.
FIG. 4 is an electron micrograph of a flame retardant sample of example 3. Wherein A is a 5000-time electron microscope photograph; b is 10000 times of electron microscope pictures; c is 30000 times of electron microscope photograph.
FIG. 5 is an electron micrograph of a flame retardant sample of example 4. Wherein A is a 5000-time electron microscope photograph; b is 10000 times of electron microscope pictures; c is 30000 times of electron microscope photograph.
FIG. 6 is an electron micrograph of a flame retardant sample of example 5. Wherein A is a 5000-time electron microscope photograph; b is 10000 times of electron microscope pictures; c is 30000 times of electron microscope photograph.
FIG. 7 is an electron micrograph of a flame retardant sample of example 6. Wherein A is a 5000-time electron microscope photograph; b is 10000 times of electron microscope pictures; c is 30000 times of electron microscope photograph.
FIG. 8 is an electron micrograph of a flame retardant sample of example 7. Wherein A is 25000 times of electron microscope photo; b is 37786 times of electron microscope pictures; c is 120000 times of electron microscope photograph.
FIG. 9 is an electron micrograph of a flame retardant sample of example 8. Wherein A is 2500 times of electron microscope photo; b is a 5000-time electron microscope photograph; c is 10000 times of electron microscope photo.
FIG. 10 is an electron micrograph of a flame retardant sample of example 9. Wherein A is 2500 times of electron microscope photo; b is a 5000-time electron microscope photograph; c is 10000 times of electron microscope photo.
FIG. 11 is an electron micrograph of a flame retardant sample of example 10. Wherein A is 2500 times of electron microscope photo; b is a 5000-time electron microscope photograph; c is 10000 times of electron microscope photo.
FIG. 12 is an electron micrograph of a flame retardant sample of example 11. Wherein A is 50000 times of electron microscope pictures; b is 60000 times of electron microscope photo; c is 60000 times of electron microscope photograph.
FIG. 13 is an electron micrograph of a flame retardant sample of example 12. Wherein A is 2500 times of electron microscope photo; b is a 5000-time electron microscope photograph; c is 10000 times of electron microscope photo.
Detailed Description
Hereinafter, only certain exemplary embodiments are briefly described. As will be recognized by those of skill in the pertinent art, the described embodiments may be modified in various different ways without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature and not as restrictive.
The following disclosure provides many different embodiments, or examples, for implementing different effects of the invention. In order to simplify the present disclosure, components and arrangements of specific examples are described below. They are, of course, merely examples and are not intended to limit the invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, which are for the purpose of brevity and clarity, and which do not themselves indicate the relationship between the various embodiments and/or arrangements discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art will recognize the application of other processes and/or the use of other materials.
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, it being understood that the preferred embodiments described herein are for illustration and explanation of the present invention only, and are not intended to limit the present invention.
The preparation method of the aluminum phosphate flame retardant based on the growth nucleus comprises the following steps:
Pre-adsorbing the phosphorus-containing raw material and the growth nucleus, uniformly stirring, dropwise adding aluminum salt, and reacting at 55-105 ℃ under heat preservation to prepare the aluminum phosphate flame retardant based on the growth nucleus; the phosphorus-containing raw material is one or more compound of hypophosphite, organic hypophosphite, phosphite and organic phosphite.
The growth nucleus is a substance with rough surface or porous surface, and preferably a material with porous surface, such as molecular sieve and diatomite; wherein the molecular sieve is natural zeolite or artificial synthetic molecular sieve, and the molecular sieve comprises silicate, aluminum silicate type molecular sieve, mesoporous type molecular sieve and aluminum phosphate type molecular sieve, and the silicate and aluminum silicate type molecular sieve is A, X, Y, M, ZSM type; mesoporous molecular sieves such as MCM-41, SBA-15 type; the aluminum phosphate type molecular sieve is such as AlPO 4 series, SAPO series, meAPO series and ElAPO series; the diatomite is natural diatomite or a purified product of the diatomite.
The hypophosphite, organic hypophosphite, phosphite and organic phosphite can be soluble salts such as potassium salt, sodium salt and ammonium salt.
The organic group of the organic hypophosphite may be a mono-alkyl, mono-phenyl, di-alkyl or di-phenyl hypophosphite.
The organic group of the organic phosphite may be an alkyl group or a phenyl phosphite.
The aluminum salt may be easily soluble aluminum salt such as aluminum sulfate, aluminum chloride, and aluminum nitrate, and preferably aluminum sulfate.
Sulfate radical has no hidden explosion hazard of nitrate, and chloride ions in chloride are not washed clean and are easy to corrode subsequent processing equipment; aluminum sulfate is preferred.
The aluminum salt is slowly added dropwise, and the adding time is 2-8h.
The reaction time under the heat preservation is 2-4 hours.
The weight ratio of the growth nucleus to the phosphorus-containing raw material is 1:10-11:1.
The D50 of the growth nuclei is 0.2 to 50. Mu.m, preferably 1 to 30. Mu.m.
The supported aluminum phosphate flame retardant prepared by the method comprises one or a mixture of aluminum hypophosphite, alkyl aluminum hypophosphite, aluminum phosphite or organic aluminum phosphite.
FIG. 1 is a schematic representation of the growth of aluminum phosphate on a growth nucleus.
The aluminum phosphate flame retardant based on the growth nuclei can be independently used as a flame retardant, can also be compounded with at least one of other flame retardants in the prior art, such as nitrogen-based flame retardants, silicon-based flame retardants, phosphorus-nitrogen-based flame retardants, aluminum hydroxide or magnesium hydroxide and the like, and can be applied to the preparation of various thermoplastics, thermosetting plastics, polyolefin and the like in the prior art, such as the preparation of polyester resin, polyamide resin, polyurethane, polyolefin material or rubber, so as to obtain corresponding polymers with excellent flame retardance. More specifically, for example, the method is applied to the preparation of nylon 6, nylon 66, nylon MXD6, nylon 12, and high-temperature nylons such as nylon 46, 4T, 6T, 9T, 10T, 12T and the like; is applied to the preparation of PBT, PET, TPEE and other polyester substrates; the method is applied to the preparation of polyurethane such as TPU, thermosetting polyurethane and the like; the method is applied to preparing polyolefin materials such as polypropylene, polyethylene, polyvinyl alcohol, SEBS and a composition thereof, SBS and a composition thereof, PP, PE, EPDM and the like, and is applied to preparing rubber materials such as ethylene propylene diene monomer rubber, butyl rubber, natural rubber, butadiene rubber, cis-isoprene rubber and the like.
The aluminum phosphate flame retardant based on the growth nucleus can be used together with glass fiber (glass fiber for short) to prepare halogen-free flame-retardant glass fiber reinforced plastic, and the raw materials comprise the following components in percentage by weight:
A resin base material: 18-84.5%;
flame retardant: 10-30%;
glass fiber: 5-50%;
other processing aids: 0.5-2%.
The resin substrate may be selected from nylon or polyester. Nylon substrates include aliphatic and semi-aromatic polyamides such as nylon 6, nylon 66, nylon MXD6, nylon 12, and nylon 46, 4T, 6T, 9T, 10T, 12T; the polyester substrate comprises PBT, PET, TPEE.
The flame retardant is a functional auxiliary agent for endowing the high polymer material with flame retardant property, and needs to account for 10-30% of the weight of the whole material system in order to meet relevant standard requirements.
Extrusion granulation of halogen-free flame-retardant glass fiber reinforced plastic:
Setting the temperature of each area of the double-screw extruder at a preset temperature, adding a base material and other processing aids from a hopper after the temperature is stabilized for 30min, adding glass fibers through a glass fiber adding port, adding flame retardants through a side feeder, starting a host machine and the feeder, finishing extrusion granulation of materials, and then drying the materials.
Application and test of halogen-free flame-retardant glass fiber reinforced plastic:
and (3) injecting the dried material into an injection molding machine to obtain a standard sample according to the UL94V0 test standard, and testing.
Example 1
The preparation method of the aluminum phosphate flame retardant (FR-1) based on the growth nucleus comprises the following steps:
1.10kg of diethyl sodium hypophosphite solid is weighed and dissolved in 23.9kg of water to form a uniform solution, and after the uniform solution is formed, 11.0kg of 5A molecular sieve is added and stirred uniformly, the temperature is raised to 85 ℃; preparing 6.2kg of 41% (w/w) iron-free aluminum sulfate aqueous solution, slowly dripping (dripping time is 3 h) into a suspension formed by diethyl sodium hypophosphite and a 5A molecular sieve, continuing to perform heat preservation reaction for 3 hours after dripping is finished, centrifugally separating, washing a centrifugal material cake with pure water for three times, and then placing the centrifugal material cake in a tray and drying. Obtaining the product.
Example 2
The preparation method of the aluminum phosphate flame retardant (FR-2) based on the growth nucleus comprises the following steps:
Weighing 11.0kg of diethyl sodium hypophosphite solid, dissolving the diethyl sodium hypophosphite solid in 39kg of water to form a uniform solution, adding 1.0kg of 5A silicon aluminum molecular sieve, uniformly stirring, and heating to 95 ℃; preparing 62kg of 33% (w/w) iron-free aluminum sulfate aqueous solution, slowly dropwise adding (dropwise adding time is 3 h) the solution into a suspension formed by diethyl sodium hypophosphite and 5A silicon aluminum molecular sieve, continuously carrying out heat preservation reaction for 3 hours after the dropwise adding is finished, centrifugally separating, washing a centrifugal material cake with pure water for three times, then placing the centrifugal material cake in a tray, and drying. Obtaining the product.
Example 3
The preparation method of the aluminum phosphate flame retardant (FR-3) based on the growth nucleus comprises the following steps:
1.10kg of diethyl sodium hypophosphite solid is weighed and dissolved in 23.9kg of water to form a uniform solution, 11.0kg of SAPO-34 molecular sieve is added and stirred uniformly, and the temperature is raised to 75 ℃; preparing 6.2kg of 41% (w/w) iron-free aluminum sulfate aqueous solution, slowly dripping (dripping time is 2.5 h) into a suspension formed by diethyl sodium hypophosphite and the SAPO-34 molecular sieve, continuing to perform heat preservation reaction for 3 hours after dripping, centrifugally separating, washing a centrifugal cake with pure water for three times, placing the centrifugal cake in a tray, and drying. Obtaining the product.
Example 4
The preparation method of the aluminum phosphate flame retardant (FR-4) based on the growth nucleus comprises the following steps:
Weighing 11.0kg of diethyl sodium hypophosphite solid, dissolving the diethyl sodium hypophosphite solid in 39kg of water to form a uniform solution, adding 1.0kg of SAPO-34 molecular sieve, stirring uniformly, and heating to 80 ℃; preparing 62kg of 13.8% (w/w) iron-free aluminum sulfate aqueous solution, slowly dropwise adding (dropwise adding time is 3 hr) into a suspension formed by diethyl sodium hypophosphite and the SAPO-34 molecular sieve, continuing to perform heat preservation reaction for 3 hours after dropwise adding, centrifugally separating, washing a centrifugal material cake with pure water for three times, placing the centrifugal material cake in a tray, and drying. Obtaining the product.
Example 5
The preparation method of the aluminum phosphate flame retardant (FR-5) based on the growth nucleus comprises the following steps:
1.10kg of diethyl sodium hypophosphite solid is weighed and dissolved in 23.9kg of water to form a uniform solution, 10.0kg of diatomite is added to the uniform solution, and the temperature is raised to 75 ℃ after the uniform solution is stirred uniformly; preparing 6.2kg of 41% (w/w) iron-free aluminum sulfate aqueous solution, slowly dripping (dripping time is 2.5 h) into a suspension formed by sodium diethyl hypophosphite and diatomite, continuing to perform heat preservation reaction for 3 hours after dripping, centrifugally separating, washing a centrifugal material cake with pure water for three times, placing the centrifugal material cake in a tray, and drying. Obtaining the product.
Example 6
The preparation method of the aluminum phosphate flame retardant (FR-6) based on the growth nucleus comprises the following steps:
weighing 11.0kg of diethyl sodium hypophosphite solid, dissolving the diethyl sodium hypophosphite solid in 39kg of water to form a uniform solution, adding 1.0kg of diatomite, uniformly stirring, and heating to 80 ℃; preparing 62kg of 13.8% (w/w) iron-free aluminum sulfate aqueous solution, slowly dripping (dripping time is 3 hr) into a suspension formed by diethyl sodium hypophosphite and diatomite, continuing to perform heat preservation reaction for 3 hours after dripping is finished, centrifugally separating, washing a centrifugal material cake with pure water for three times, placing the centrifugal material cake in a tray, and drying. Obtaining the product.
Example 7
The preparation method of the aluminum phosphate flame retardant (FR-7) based on the growth nucleus comprises the following steps:
Weighing 22.04kg of sodium phosphite pentahydrate solid, dissolving in 77.96g of water to form a uniform solution, adding 2.0kg of ZSM-5 molecular sieve, uniformly stirring, and heating to 50 ℃; preparing 162.5kg of 33% (w/w) iron-free aluminum sulfate aqueous solution, slowly dropwise adding (dropwise adding time is 2.5 h) into a suspension formed by sodium phosphite pentahydrate and ZSM-5 molecular sieve, heating to 85 ℃ after dropwise adding, continuously preserving heat for reaction for 3 hours, centrifugally separating, washing a centrifugal material cake with pure water for three times, placing the centrifugal material cake in a tray, and drying. Obtaining the product.
Example 8
The preparation method of the aluminum phosphate flame retardant (FR-8) based on the growth nucleus comprises the following steps:
Weighing 22.04kg of sodium phosphite pentahydrate solid, dissolving in 77.96g of water to form a uniform solution, adding 5.0 kg of SAPO-11 molecular sieve, stirring uniformly, and heating to 50 ℃; preparing 162.5kg of 33% (w/w) iron-free aluminum sulfate aqueous solution, slowly dropwise adding (dropwise adding time is 2.5 h) into suspension formed by sodium phosphite pentahydrate and SAPO-11 molecular sieve, heating to 90 ℃ after dropwise adding, continuously preserving heat for reaction for 3 hours, centrifugally separating, washing centrifugal cakes with pure water for three times, placing the centrifugal cakes in a tray, and drying. Obtaining the product.
Example 9
The preparation method of the aluminum phosphate flame retardant (FR-9) based on the growth nucleus comprises the following steps:
Weighing 22.04kg of sodium phosphite pentahydrate solid, dissolving in 77.96kg of water to form a uniform solution, adding 5.0 kg of diatomite, uniformly stirring, and heating to 50 ℃; preparing 162.5kg of 33% (w/w) iron-free aluminum sulfate aqueous solution, slowly dropwise adding (dropwise adding time is 2.5 h) into suspension formed by sodium phosphite pentahydrate and diatomite, heating to 95 ℃ after dropwise adding, continuously preserving heat for 3 hours, centrifugally separating, washing a centrifugal material cake with pure water three times, placing the centrifugal material cake in a tray, and drying. Obtaining the product.
Example 10
The preparation method of the aluminum phosphate flame retardant (FR-10) based on the growth nucleus comprises the following steps:
2.20kg of sodium phosphite pentahydrate solid and 9.97kg of sodium diethyl hypophosphite solid are weighed and dissolved in 38.9g of water to form a uniform solution, then NAY silicon aluminum molecular sieve 20kg is added and stirred uniformly, and then the temperature is raised to 80 ℃; preparing 72kg of 33% (w/w) iron-free aluminum sulfate aqueous solution, slowly dropwise adding (dropwise adding time is 2.5 h) into a suspension formed by sodium phosphite pentahydrate, sodium diethylphosphinate and NAY molecular sieves, continuously carrying out heat preservation reaction for 2 hours after the dropwise adding is finished, centrifugally separating, washing a centrifugal cake with pure water three times, placing the centrifugal cake in a tray, and drying. Obtaining the product.
Example 11
The preparation method of the aluminum phosphate flame retardant (FR-11) based on the growth nucleus comprises the following steps:
2.20kg of sodium phosphite pentahydrate solid and 9.97kg of sodium diethyl hypophosphite solid are weighed and dissolved in 38.9g of water to form a uniform solution, and after the uniform solution is formed, 3.33 kg of SAPO-11 phosphorus aluminum molecular sieve is added and stirred uniformly, the temperature is raised to 80 ℃; preparing 72kg of 33% (w/w) iron-free aluminum sulfate aqueous solution, slowly dropwise adding (dropwise adding time is 2.5 h) the solution into suspension formed by sodium phosphite pentahydrate, sodium diethyl hypophosphite and SAPO-11 phosphorus aluminum molecular sieve, continuing to perform heat preservation reaction for 3 hours after dropwise adding, centrifugally separating, washing a centrifugal material cake with pure water for three times, and then placing the centrifugal material cake in a tray for drying. Obtaining the product.
Example 12
The preparation method of the aluminum phosphate flame retardant (FR-12) based on the growth nucleus comprises the following steps:
2.20kg of sodium phosphite pentahydrate solid and 9.97kg of sodium diethyl hypophosphite solid are weighed and dissolved in 38.9g of water to form a uniform solution, and after adding diatomite 50 kg, stirring uniformly, heating to 80 ℃; preparing 72kg of 33% (w/w) iron-free aluminum sulfate aqueous solution, slowly dropwise adding (dropwise adding time is 2.5 h) the solution into a suspension formed by sodium phosphite pentahydrate, sodium diethylphosphinate and diatomite, continuously carrying out heat preservation reaction for 4 hours after the dropwise adding is finished, centrifugally separating, washing a centrifugal cake with pure water for three times, placing the centrifugal cake in a tray, and drying. Obtaining the product.
Table 1 shows the proportions of the respective raw materials in examples 1 to 12 (FR-1 to FR-12) and the theoretical phosphorus content in the flame retardant.
Wherein, the calculation method of the theoretical weight ratio (growth nucleus: aluminum salt) is as follows: during calculation, sodium diethyl hypophosphite reacts with aluminum sulfate to generate diethyl aluminum hypophosphite, and the mass of the added growth nucleus is calculated according to the mass of the theoretically generated diethyl aluminum hypophosphite; sodium phosphite pentahydrate reacts with aluminum sulfate to generate aluminum phosphite, and the mass of the added growth nucleus is calculated according to the mass of the theoretically generated aluminum phosphite; in a sodium phosphite pentahydrate and sodium diethylphosphinate mixed system, the mass of added growth nuclei is calculated to generate the mass of aluminum diethylphosphinate and aluminum phosphite.
TABLE 1 phosphorus content in the flame retardants by the ratios of the respective raw materials in examples 1 to 12 (FR-1 to FR-12)
FIG. 2 is an electron micrograph of a flame retardant sample of example 1. Wherein A is a 5000-time electron microscope photograph; b is 10000 times of electron microscope pictures; c is 30000 times of electron microscope photograph.
FIG. 3 is an electron micrograph of a flame retardant sample of example 2. Wherein A is a 5000-time electron microscope photograph; b is 10000 times of electron microscope pictures; c is 30000 times of electron microscope photograph.
FIG. 4 is an electron micrograph of a flame retardant sample of example 3. Wherein A is a 5000-time electron microscope photograph; b is 10000 times of electron microscope pictures; c is 30000 times of electron microscope photograph.
FIG. 5 is an electron micrograph of a flame retardant sample of example 4. Wherein A is a 5000-time electron microscope photograph; b is 10000 times of electron microscope pictures; c is 30000 times of electron microscope photograph.
FIG. 6 is an electron micrograph of a flame retardant sample of example 5. Wherein A is a 5000-time electron microscope photograph; b is 10000 times of electron microscope pictures; c is 30000 times of electron microscope photograph.
FIG. 7 is an electron micrograph of a flame retardant sample of example 6. Wherein A is a 5000-time electron microscope photograph; b is 10000 times of electron microscope pictures; c is 30000 times of electron microscope photograph.
FIG. 8 is an electron micrograph of a flame retardant sample of example 7. Wherein A is 25000 times of electron microscope photo; b is 37786 times of electron microscope pictures; c is 120000 times of electron microscope photograph.
FIG. 9 is an electron micrograph of a flame retardant sample of example 8. Wherein A is 2500 times of electron microscope photo; b is a 5000-time electron microscope photograph; c is 10000 times of electron microscope photo.
FIG. 10 is an electron micrograph of a flame retardant sample of example 9. Wherein A is 2500 times of electron microscope photo; b is a 5000-time electron microscope photograph; c is 10000 times of electron microscope photo.
FIG. 11 is an electron micrograph of a flame retardant sample of example 10. Wherein A is 2500 times of electron microscope photo; b is a 5000-time electron microscope photograph; c is 10000 times of electron microscope photo.
FIG. 12 is an electron micrograph of a flame retardant sample of example 11. Wherein A is 50000 times of electron microscope pictures; b is 60000 times of electron microscope photo; c is 60000 times of electron microscope photograph.
FIG. 13 is an electron micrograph of a flame retardant sample of example 12. Wherein A is 2500 times of electron microscope photo; b is a 5000-time electron microscope photograph; c is 10000 times of electron microscope photo.
Preparation of halogen-free flame retardant glass fiber reinforced plastics Using examples 1-15 and comparative examples 1-19 Using flame retardant
1. Sources of raw materials
PA6, 2400J, hangzhou syndication;
PA66, EPR27, zephyr-horse;
PA6T/66, 1245, peninsula tri-force;
PBT, KH2083, for good appetite;
OP1230, OP1240, OP1400, clariant;
MPP:200-70, melamine polyphosphate, basf;
safire400, melamine zinc polyphosphate Bo;
AmgardPA1, polyphosphate, sorrow;
MCA: MC-25, fine chemical institute of Sichuan province;
glass fiber, ECS301UW, chongqing International composite material Co., ltd;
Antioxidant, 1010, tianjin Li Anlong; 608, taiwan qi titanium; h10: bulgmann;
Lubricant, 540A, ganivill;
Nucleating agents, cav102, clariant;
sodium hypophosphite monohydrate, hubei Xingfu;
sodium diethylphosphinate, qingdao's europril;
sodium phosphite pentahydrate, hubei, developed.
2. Formula of halogen-free flame-retardant glass fiber reinforced plastic
The formulation of the halogen-free flame-retardant glass fiber reinforced plastic is shown in tables 2-5. Wherein S1-S15 are application examples 1-15 in order, and V1-V19 are comparative examples 1-19 in order.
3. Extrusion granulating of halogen-free flame-retardant glass fiber reinforced plastic
Setting the temperature of each area of the double-screw extruder at a preset temperature, adding a base material and other processing aids from a hopper after the temperature is stabilized for 30min, adding Glass Fiber (GF) through a glass fiber adding port, adding Flame Retardant (FR) through a side feeder, starting a host machine and the feeder, finishing extrusion granulation of materials, and then drying the materials.
4. Application and test of halogen-free flame-retardant glass fiber reinforced plastic
And (3) injecting the dried material into an injection molding machine to obtain a standard sample according to the UL 94V-0 test standard, and testing. Wherein, "0.8mm" in tables 2 to 5 means the thickness of the produced spline; "1.6mm" refers to the thickness of the resulting spline.
TABLE 2
| Raw material composition | S1 | S2 | V1 | V2 | V3 | V4 |
| PA6T/66 | 54 | 54 | 54 | 54 | 51 | 49 |
| GF | 30 | 30 | 30 | 30 | 30 | 30 |
| FR-2 | 15 | |||||
| FR-11 | 15 | |||||
| OP1230 | 15 | 18 | ||||
| OP1400 | 15 | 20 | ||||
| H10 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| 540A | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Cav102 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| 0.8mm | V-0 | V-0 | V-1 | V-1 | V-0 | V-0 |
| 1.6mm | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
TABLE 3 Table 3
| Raw material composition | S3 | S4 | V5 | V6 | V7 | S5 | S6 | V8 | V9 |
| PA66 | 53.2 | 53.2 | 53.2 | 53.2 | 51.2 | 53.2 | 53.2 | 53.2 | 51.2 |
| GF | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
| FR-6 | 10 | 10 | |||||||
| FR-7 | 16 | ||||||||
| FR-11 | 16 | ||||||||
| OP1230 | 10 | 10 | 12 | ||||||
| OP1400 | 16 | 18 | |||||||
| Safire400 | 6 | 6 | |||||||
| 200-70 | 6 | 6 | 6 | ||||||
| H10 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| 540A | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| 0.8mm | V-0 | V-0 | V-1 | V-1 | V-1 | V-0 | V-0 | V-1 | V-0 |
| 1.6mm | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
TABLE 4 Table 4
| Raw material composition | S7 | S8 | V10 | V11 | V12 | S9 | S10 | V13 | V14 |
| PA6 | 51.2 | 51.2 | 51.2 | 51.2 | 49.2 | 52.2 | 52.2 | 52.2 | 49.2 |
| GF | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
| FR-4 | 12 | 12 | |||||||
| FR-8 | 17 | ||||||||
| FR-11 | 17 | ||||||||
| OP1230 | 12 | 12 | 14 | ||||||
| OP1400 | 17 | 20 | |||||||
| Safire400 | 6 | 6 | |||||||
| AmgardPA1 | 6 | 6 | 6 | ||||||
| H10 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| 540A | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| 0.8mm | V-0 | V-0 | V-1 | V-1 | V-1 | V-0 | V-0 | V-1 | V-0 |
| 1.6mm | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
TABLE 5
| Raw material composition | S11 | S14 | S15 | V15 | V16 | S12 | S13 | V17 | V18 | V19 |
| PBT | 51 | 51 | 51 | 51 | 49 | 53 | 51 | 53 | 51 | 49 |
| GF | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
| FR-2 | 18 | 12 | 12 | |||||||
| FR-1 | 18 | |||||||||
| FR-10 | 6 | |||||||||
| OP1240 | 8 | 18 | 20 | 12 | 14 | 14 | ||||
| AmgardPA1 | 4 | 4 | 4 | 4 | ||||||
| MCA | 6 | 6 | ||||||||
| 1010 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| 608 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| 540A | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| 0.8mm | V-0 | HB | V-0 | V-2 | V-1 | V-0 | V-0 | V-2 | V-0 | V-0 |
| 1.6mm | V-0 | V-2 | V-0 | V-1 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
As can be seen from tables 2-5, the halogen-free flame retardant glass fiber reinforced material prepared by applying the flame retardant disclosed by the invention can reach the UL94V0 (0.8 mm) flame retardant grade. Under the condition that the using amount of the phosphorus is the same as that in the prior art, the flame retardant effect is improved.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. The preparation method of the aluminum phosphate flame retardant based on the growth nucleus is characterized by comprising the following steps: adding growth nuclei for reaction when preparing aluminum phosphate flame retardant by taking phosphorus-containing raw materials and aluminum salt as raw materials; the preparation method comprises the following steps: pre-adsorbing one or more compound substances of hypophosphite and phosphite with a growth nucleus, uniformly stirring, and then dropwise adding aluminum salt for reaction to prepare an aluminum phosphate flame retardant based on the growth nucleus;
The phosphorus-containing raw material is one or more compound of hypophosphite and phosphite; the phosphorus-containing raw material is soluble salt;
the aluminum salt is easily soluble aluminum salt;
The growth nucleus is a substance with rough surface or porous surface; the growth nucleus is molecular sieve or diatomite; the diatomite is natural diatomite or a purification product of the diatomite; the molecular sieve is natural zeolite or artificial synthetic molecular sieve, and comprises silicate, aluminum silicate type molecular sieve, mesoporous type molecular sieve and aluminum phosphate type molecular sieve; the silicate and aluminum silicate type molecular sieve comprises A, X, Y, M, ZSM types; the mesoporous molecular sieve comprises MCM-41 and SBA-15 types; the aluminum phosphate type molecular sieve comprises AlPO4 series, SAPO series, meAPO series and ElAPO series;
the weight ratio of the growth nucleus to the phosphorus-containing raw material is 1:10-11:1;
The D50 of the growth nucleus is 0.2-50 mu m;
The reaction temperature during the reaction is as follows: the reaction is carried out at 55-105 ℃.
2. The method for preparing the aluminum phosphate flame retardant based on the growth nucleus according to claim 1, wherein the method comprises the following steps: the phosphorus-containing raw material is one or more compounds of organic hypophosphite and organic phosphite.
3. The method for preparing the aluminum phosphate flame retardant based on the growth nucleus according to claim 2, wherein the method comprises the following steps: the organic group of the organic hypophosphite is monoalkyl, monophenyl, dialkyl or biphenyl;
The organic group of the organic phosphite is alkyl or phenyl.
4. A method for preparing a growth-nucleus-based aluminum phosphate flame retardant according to claim 3, wherein: the phosphorus-containing raw material is potassium salt, sodium salt and ammonium salt;
the aluminum salt is aluminum sulfate salt, aluminum chloride salt or aluminum nitrate salt.
5. The method for preparing the aluminum phosphate flame retardant based on the growth nucleus according to claim 4, wherein the method comprises the following steps: the aluminum salt is aluminum sulfate.
6. A method for preparing a growth-core-based aluminum phosphate flame retardant according to any one of claims 1-5, wherein: the D50 of the growth nucleus is 1-30 mu m.
7. An aluminum phosphate flame retardant based on a growth nucleus, which is prepared by using the method of any one of claims 1 to 6.
8. Use of the aluminum phosphate flame retardant based on growth nuclei according to claim 7 for preparing thermoplastics and thermosets.
9. The use according to claim 8, characterized in that: the application is the application of aluminum phosphate flame retardant combined glass fiber based on growth cores in the preparation of halogen-free flame-retardant glass fiber reinforced plastic.
10. A thermoplastic, thermoset, characterized by: the preparation raw materials comprise the aluminum phosphate flame retardant based on the growth nucleus as claimed in claim 7.
11. A halogen-free flame-retardant glass fiber reinforced plastic is characterized in that: the halogen-free flame-retardant glass fiber reinforced plastic comprises the following raw materials in percentage by weight:
A resin base material: 18-84.5%;
The growth-core based aluminum phosphate flame retardant of claim 7: 10-30%;
glass fiber: 5-50%;
other processing aids: 0.5-2%.
12. The preparation method of the halogen-free flame-retardant glass fiber reinforced plastic comprises the following steps: setting the temperature of each zone of the double-screw extruder at a preset temperature, adding a base material and other processing aids from a hopper after the temperature is stable, adding glass fibers through a glass fiber adding port, adding the aluminum phosphate flame retardant based on the growth nuclei according to claim 7 through a side feeder, starting a host machine and the feeder, extruding and granulating the materials, and drying the materials.
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