CN115073819A - Aluminum phosphate salt flame retardant based on growth nucleus and preparation method and application thereof - Google Patents
Aluminum phosphate salt flame retardant based on growth nucleus and preparation method and application thereof Download PDFInfo
- Publication number
- CN115073819A CN115073819A CN202210672081.4A CN202210672081A CN115073819A CN 115073819 A CN115073819 A CN 115073819A CN 202210672081 A CN202210672081 A CN 202210672081A CN 115073819 A CN115073819 A CN 115073819A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- aluminum
- growth nucleus
- aluminum phosphate
- hypophosphite
- 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.)
- Granted
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 165
- 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 156
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 45
- 239000003365 glass fiber Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 21
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 21
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 26
- 229910052698 phosphorus Inorganic materials 0.000 claims description 26
- 239000011574 phosphorus Substances 0.000 claims description 25
- 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 compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 21
- -1 diphenyl hypophosphite Chemical compound 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 16
- 239000011152 fibreglass Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 125000000962 organic group Chemical group 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000004416 thermosoftening plastic 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
- 239000012264 purified product Substances 0.000 claims description 3
- 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 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 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 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 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 abstract description 16
- 229920006351 engineering plastic Polymers 0.000 abstract description 6
- 229920003023 plastic Polymers 0.000 abstract 1
- 238000000635 electron micrograph Methods 0.000 description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000007787 solid Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 17
- 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 17
- 238000010438 heat treatment Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000000725 suspension Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 11
- LPFYDEANGXVAOA-UHFFFAOYSA-M sodium;diethylphosphinate Chemical compound [Na+].CCP([O-])(=O)CC LPFYDEANGXVAOA-UHFFFAOYSA-M 0.000 description 10
- 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
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011162 core material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 229920000642 polymer 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
- 238000001556 precipitation Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 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
- 239000005909 Kieselgur Substances 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 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
- 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 description 2
- 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 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000000977 initiatory effect Effects 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
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229920006346 thermoplastic polyester elastomer Polymers 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
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 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
- 241000200821 Platypodium Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 244000292604 Salvia columbariae Species 0.000 description 1
- 235000012377 Salvia columbariae var. columbariae Nutrition 0.000 description 1
- 235000001498 Salvia hispanica Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-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
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 235000014167 chia Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 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
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
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- 239000000314 lubricant Substances 0.000 description 1
- 230000002535 lyotropic effect Effects 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
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- 230000005012 migration Effects 0.000 description 1
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- 229920003052 natural elastomer Polymers 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 230000035484 reaction time Effects 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
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- 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
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- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- 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
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- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Engineering & Computer Science (AREA)
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- Fireproofing Substances (AREA)
Abstract
The invention provides a preparation method of an aluminum phosphate salt flame retardant based on a growth nucleus, which is characterized in that when one or more compounds of hypophosphite, organic hypophosphite, phosphite and organic phosphite and aluminum salt are used as raw materials to prepare the aluminum phosphate salt flame retardant, the growth nucleus is added for reaction; 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 aluminum phosphate (phosphonate) flame retardant based on the growth nucleus provided by the invention 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 flame-retardant grade of UL94V0(0.8 mm).
Description
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to a growing nucleus-based aluminum phosphate salt flame retardant and a preparation method and application thereof.
Background
Along with the shortage of bromine resources worldwide and the strengthening of laws and regulations related to electronics and electricity in various countries, the flame-retardant engineering plastics gradually transit to non-halogenation. At present, phosphorus flame retardants mainly include inorganic phosphorus flame retardants represented by ammonium polyphosphate, aluminum phosphate systems represented by aluminum hypophosphite/diethyl aluminum hypophosphite/aluminum phosphite, and (poly) phosphate systems represented by RDP/BDP. Factors such as temperature resistance, precipitation risk, mechanics, electrical property and the like are comprehensively considered, and a flame retardant system based on aluminum phosphate (phosphonate) is more applied to the 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 generate synergistic action with a nitrogen-containing flame retardant, so that the high-efficiency flame retardance of the glass fiber reinforced engineering plastic is realized.
However, aluminum (phosph) ate flame retardant systems still suffer from some common problems:
1. the particles are unevenly distributed, causing the material properties to fluctuate: 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 precipitation particles is too large, and the particle size is smaller; the temperature is too low, the product crystallinity is high, but the reaction is insufficient, and the inclusion of impurities is excessive.
2. The addition amount is high, and the cost of the flame retardant is high: typically, commercial aluminum phosphate salt series flame retardants are formulated to achieve high phosphorus levels, e.g., 2% to 4% P, to achieve high flame retardant efficiency. Particularly after the energy limit in this year, the price of yellow phosphorus rises from 15000 yuan/ton to nearly 80000 yuan/ton, and the phosphorus-related industries in the whole world are seriously damaged.
Therefore, how to improve the flame retardant efficiency per unit mass of phosphorus is one of the important directions in future development of phosphorus flame retardants. One scheme is to increase the phosphorus content in the flame retardant as much as possible, for example, red phosphorus and hypophosphite flame retardants are used, and the flame retardant has high phosphorus content, but has the problems of fire initiation and easy migration; in addition, it has been found in research that, in the case of an additive flame retardant, the outer layer of the flame retardant is often used for flame retarding, while the inner layer is often not used for flame retarding. Many researchers have attempted to subject conventional flame retardants to ultrafine processing, such as nanocrystallization, but have faced the problem of high processing viscosity and entrapment with other ingredients.
Disclosure of Invention
Aiming at one or more problems in the prior art, the invention provides a growth nucleus-based aluminum phosphate salt flame retardant, a preparation method thereof, and application thereof in preparation of various thermoplastics and thermosetting plastics, in particular application in preparation of halogen-free flame-retardant glass fiber reinforced engineering plastics.
The invention provides a preparation method of an aluminum phosphate salt flame retardant based on a growth nucleus, which is characterized in that when a phosphorus-containing raw material and an aluminum salt are used as raw materials to prepare the aluminum phosphate salt flame retardant, the growth nucleus is added to carry out reaction; the phosphorus-containing raw material is one or more compounds 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 siliconA purified product of diatomaceous earth; preferably, the molecular sieve is natural zeolite or an artificially synthesized molecular sieve, and the molecular sieve comprises silicate, aluminosilicate molecular sieve, mesoporous molecular sieve and aluminum phosphate molecular sieve; the silicate, aluminosilicate type molecular sieves include type A, X, Y, M, ZSM; 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, ElAPO series.
According to one aspect of the invention, the hypophosphite, organic hypophosphite, phosphite, organic phosphite, is a lyotropic 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 an alkyl or phenyl phosphite.
The aluminum salt is soluble aluminum salt; examples of the inorganic salt include aluminum sulfate salt, aluminum chloride salt and aluminum nitrate salt, and aluminum sulfate salt is preferable.
According to one aspect of the invention, the weight ratio of the growth nuclei to the phosphorus-containing raw material is 1:10 to 11: 1; and/or
The D50 of the growth nucleus is 0.2-50 μm, preferably 1-30 μm; and/or
The reaction temperature during the reaction is as follows: the reaction is carried out at the temperature of 55-105 ℃.
The weight ratio of the growth nucleus to the phosphorus-containing raw material is selected because the growth nucleus is too much, the phosphate can be well dispersed on the growth nucleus, but the effective phosphorus content is too low; the growth nucleus is too small, and a part of the prepared phosphate flame retardant is independent of the growth nucleus and independently precipitated in the solution.
When the particle diameter of the growing core D50 is more than 50 μm, the surface energy is relatively low, the binding capacity of the flame retardant for surface growth is poor, the ratio of the actually loaded flame retardant is too low, and the particles are too large in a polymer, so that the dispersion is not uniform.
When the grain size of the D50 growing core is less than 0.2 μm, the viscosity during the manufacturing process is too high, and the size of the commercially available material is not too small.
According to another aspect of the invention, the preparation method comprises the following steps: one or more compounds of hypophosphite, organic hypophosphite, phosphite and organic phosphite are pre-adsorbed with the growth nucleus, and after the mixture is uniformly stirred, aluminum salt is dripped for reaction to prepare the aluminum phosphate salt flame retardant based on the growth nucleus.
The invention also provides a growing nucleus-based aluminum phosphate salt flame retardant which is prepared by applying the method.
The invention also provides the application of the aluminum phosphate salt flame retardant based on the growth nucleus in preparing thermoplastic plastics and thermosetting plastics;
preferably, the application is the application of the aluminum phosphate salt flame retardant based on the growth nucleus in combination with the glass fiber in preparing the halogen-free flame-retardant glass fiber reinforced plastic.
The invention also provides a thermoplastic plastic and a thermosetting plastic, and the preparation raw materials of the thermoplastic plastic and the thermosetting plastic comprise the aluminum phosphate salt flame retardant based on the growth nucleus.
The invention also provides a halogen-free flame-retardant glass fiber reinforced plastic, which comprises the following raw materials in percentage by weight:
resin base material: 18 to 84.5 percent;
the above-mentioned aluminum phosphate salt flame retardant based on growth nuclei: 10 to 30 percent;
glass fiber: 5 to 50 percent;
other processing aids: 0.5 to 2 percent.
The invention also provides a preparation method of the halogen-free flame-retardant glass fiber reinforced plastic, which comprises the following steps: 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 stable, adding glass fibers through a glass fiber adding port, feeding the aluminum phosphate flame retardant based on the growth nucleus through a side feeder, starting a host machine and the feeder to complete extrusion granulation of the material, and then drying the material.
The invention has the following beneficial effects:
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 a growth nucleus, and controllably leads the flame retardant to grow on the growth nucleus or to initiate crystallization by taking the growth nucleus as an initiation point. And the porous growing 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 usage amount of phosphorus; one theory holds that the particulate aluminum phosphate flame retardant has a major surface portion in the flame retardant process, while the internal flame retardant has little or no flame retardant effect. The invention utilizes the larger specific surface area of the growth core material to deposit most of the flame retardant on the surface, thereby exerting the flame retardant effect.
4. The aluminum phosphate (phosphonate) flame retardant based on the growth nucleus provided by the invention 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 flame-retardant grade of UL94V0(0.8 mm). 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, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic representation of aluminum phosph (on) ate growth on growth nuclei.
FIG. 2 is an electron micrograph of a flame retardant sample of example 1. Wherein A is a 5000-fold electron microscope photo; b is 10000 times of electron microscope photo; c is 30000 times of electron micrograph.
FIG. 3 is an electron micrograph of a flame retardant sample of example 2. Wherein A is a 5000-fold electron microscope photo; b is 10000 times of electron micrograph; c is 30000 times of electron micrograph.
FIG. 4 is an electron micrograph of a flame retardant sample of example 3. Wherein A is a 5000-fold electron microscope photo; b is 10000 times of electron microscope photo; c is 30000 times of electron micrograph.
FIG. 5 is an electron micrograph of a flame retardant sample of example 4. Wherein A is a 5000-fold electron microscope photo; b is 10000 times of electron microscope photo; c is 30000 times of electron micrograph.
FIG. 6 is an electron micrograph of a flame retardant sample of example 5. Wherein A is a 5000-fold electron microscope photo; b is 10000 times of electron microscope photo; c is 30000 times of electron micrograph.
FIG. 7 is an electron micrograph of a flame retardant sample of example 6. Wherein A is a 5000-fold electron microscope photo; b is 10000 times of electron microscope photo; c is 30000 times of electron micrograph.
FIG. 8 is an electron micrograph of a flame retardant sample of example 7. Wherein A is 25000 times of electron microscope photos; b is 37786 times of electron microscope picture; c is 120000 times of electron micrograph.
FIG. 9 is an electron micrograph of a flame retardant sample of example 8. Wherein A is a 2500-fold electron microscope photo; b is a 5000-fold electron microscope photo; c is 10000 times of electron micrograph.
FIG. 10 is an electron micrograph of a flame retardant sample of example 9. Wherein A is a 2500-fold electron microscope photo; b is a 5000-fold electron microscope photo; c is 10000 times of electron micrograph.
FIG. 11 is an electron micrograph of a flame retardant sample of example 10. Wherein A is a 2500-fold electron micrograph; b is a 5000-fold electron microscope photo; c is 10000 times of electron micrograph.
FIG. 12 is an electron micrograph of a flame retardant sample of example 11. Wherein A is 50000 times of electron microscope photos; b is a 60000-fold electron microscope photograph; c is 60000 times electron micrograph.
FIG. 13 is an electron micrograph of a flame retardant sample of example 12. Wherein A is a 2500-fold electron micrograph; b is a 5000-fold electron microscope photo; c is 10000 times of electron micrograph.
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all 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. To simplify the disclosure of the present invention, the components and arrangements of specific examples are described below. Of course, they are merely examples and are not intended to limit the present invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art may recognize applications of other processes and/or uses of other materials.
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it should be understood that they are presented herein only to illustrate and explain the present invention and not to limit the present invention.
The preparation method of the aluminum phosphate (phosphonate) flame retardant based on the growth nucleus comprises the following steps:
pre-adsorbing a phosphorus-containing raw material and a growth nucleus, uniformly stirring, dropwise adding aluminum salt, and reacting at the temperature of 55-105 ℃ to prepare an aluminum phosphate salt flame retardant based on the growth nucleus; the phosphorus-containing raw material is one or a plurality of compounds of hypophosphite, organic hypophosphite, phosphite and organic phosphite.
The growth core is a substance with a rough surface or a porous surface, and a material with a porous surface, such as a molecular sieve and diatomite, is preferably selected; wherein the molecular sieve is natural zeolite or artificially synthesized molecular sieve, and comprises silicate, aluminosilicate molecular sieve, mesoporous molecular sieve and aluminum phosphate molecular sieve, such as A, X, Y, M, ZSM type molecular sieve; the mesoporous molecular sieve is MCM-41 or SBA-15; the aluminum phosphate type molecular sieve, such as AlPO 4 Series, SAPO series, MeAPO, ElAPO series; the diatomite is natural diatomite or a purified product of diatomite.
The hypophosphite, organic hypophosphite, phosphite and organic phosphite can be easily soluble salts such as potassium salt, sodium salt, ammonium salt and the like.
The organic group of the organophosphinate may be a mono-, di-or bis-alkyl-phosphinate.
The organic group of the organic phosphite may be an alkyl or phenyl phosphite.
The aluminum salt may be a readily soluble aluminum salt such as an aluminum sulfate salt, an aluminum chloride salt, an aluminum nitrate salt, etc., and is preferably an aluminum sulfate salt.
Sulfate radicals have no explosion hidden trouble of nitrate, and chloride ions in chloride are not washed cleanly and easily corrode subsequent processing equipment; therefore, aluminum sulfate is preferable.
The aluminum salt is required to be slowly dripped when the aluminum salt is dripped, and the dripping time is required to be 2-8 h.
The reaction time at the temperature 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 nucleus is 0.2-50 μm, preferably 1-30 μm.
The supported aluminum phosphate salt 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 aluminum phosph (on) ate growth on growth nuclei.
The aluminum phosphate (phosphonate) flame retardant based on the growth nucleus can be independently used as a flame retardant, and can also be compounded with at least one of other flame retardants in the prior art, such as nitrogen-based, silicon-based, phosphorus-nitrogen-based, aluminum hydroxide or magnesium hydroxide synergistic flame retardants, and the like, and can be applied to the preparation of various thermoplastics, thermosetting plastics, polyolefins and the like in the prior art, such as polyester resin, polyamide resin, polyurethane, polyolefin materials or rubber, so that corresponding polymers with excellent flame retardance can be obtained. More specifically, the method is applied to the preparation of nylon 6, nylon 66, nylon MXD6, nylon 12, nylon 46, 4T, 6T, 9T, 10T, 12T and other high-temperature nylons; the method is applied to preparing polyester substrates such as PBT, PET, TPEE and the like; the preparation method is applied to preparation of polyurethanes such as TPU, thermosetting polyurethane and the like; the preparation method is applied to preparation of polyolefin materials such as polypropylene, polyethylene, polyvinyl alcohol, SEBS and compositions thereof, SBS and compositions thereof, PP, PE, EPDM and the like, and is applied to preparation of rubber materials such as ethylene propylene diene monomer, butyl rubber, natural rubber, butadiene rubber, cis-isoprene rubber and the like.
The aluminum phosphate (phosphonate) 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 composition of the raw materials comprises the following components in percentage by weight:
resin base material: 18 to 84.5 percent;
flame retardant: 10 to 30 percent;
glass fiber: 5 to 50 percent;
other processing aids: 0.5 to 2 percent.
The resin substrate may be selected from nylon or polyester. Nylon substrates include aliphatic polyamides 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 and TPEE.
The flame retardant is a functional auxiliary agent for endowing the high polymer material with flame retardant performance, and needs to account for 10-30% of the weight of the whole material system to meet the relevant standard requirements.
Extruding and granulating the 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, feeding a flame retardant through a side feeding machine, starting a main machine and the feeding machine to complete the extrusion granulation of the material, and then drying the material.
Application and test of the 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 (phosphonate) flame retardant (FR-1) based on the growth nucleus comprises the following steps:
weighing 1.10kg of diethyl sodium hypophosphite solid, dissolving the solid in 23.9kg of water to form a uniform solution, adding 11.0kg of 5A molecular sieve, uniformly stirring, and heating to 85 ℃; preparing 6.2kg of 41% (w/w) iron-free aluminum sulfate aqueous solution, slowly dropwise adding (dropwise adding time is 3h) into suspension formed by diethyl sodium hypophosphite and a 5A molecular sieve, after dropwise adding, continuously preserving heat for reaction for 3 hours, centrifugally separating, washing a centrifugal material cake for three times by using pure water, then placing the centrifugal material cake in a tray, and drying. And (5) obtaining a product.
Example 2
The preparation method of the aluminum phosphate (phosphonate) flame retardant (FR-2) based on the growth nucleus comprises the following steps:
weighing 11.0kg of diethyl sodium hypophosphite solid, dissolving the 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 3h) the solution into a suspension formed by sodium diethylhypophosphite and a 5A silicon-aluminum molecular sieve, continuously preserving heat and reacting for 3h after dropwise adding, centrifugally separating, washing the centrifugal material cake with pure water for three times, then placing the centrifugal material cake in a tray, and drying. And (5) obtaining a product.
Example 3
The preparation method of the aluminum phosphate (phosphonate) flame retardant (FR-3) based on the growth nucleus comprises the following steps:
weighing 1.10kg of diethyl sodium hypophosphite solid, dissolving the solid in 23.9kg of water to form a uniform solution, adding 11.0kg of SAPO-34 molecular sieve, uniformly stirring, and heating to 75 ℃; preparing 6.2kg of 41% (w/w) iron-free aluminum sulfate aqueous solution, slowly dropwise adding (dropwise adding time is 2.5h) into suspension formed by sodium diethylhypophosphite and an SAPO-34 molecular sieve, continuously preserving heat for reaction for 3 hours after dropwise adding, centrifugally separating, washing a centrifugal material cake for three times by using pure water, then placing the centrifugal material cake in a tray, and drying. And (5) obtaining a product.
Example 4
The preparation method of the aluminum phosphate (phosphonate) flame retardant (FR-4) based on the growth nucleus comprises the following steps:
weighing 11.0kg of diethyl sodium hypophosphite solid, dissolving the solid in 39kg of water to form a uniform solution, adding 1.0kg of SAPO-34 molecular sieve, uniformly stirring, and heating to 80 ℃; preparing 62kg of 13.8% (w/w) iron-free aluminum sulfate aqueous solution, slowly dropwise adding (dropwise adding time is 3hr) into suspension formed by sodium diethylhypophosphite and an SAPO-34 molecular sieve, continuously keeping the temperature for reaction for 3 hours after dropwise adding, carrying out centrifugal separation, washing the centrifugal cake with pure water for three times, then placing the centrifugal cake in a tray, and drying. And (5) obtaining a product.
Example 5
The preparation method of the aluminum phosphate (phosphonate) flame retardant (FR-5) based on the growth nucleus comprises the following steps:
weighing 1.10kg of diethyl sodium hypophosphite solid, dissolving the solid in 23.9kg of water to form a uniform solution, adding 10.0kg of diatomite, uniformly stirring, and heating to 75 ℃; preparing 6.2kg of 41% (w/w) iron-free aluminum sulfate aqueous solution, slowly dropwise adding (dropwise adding time is 2.5h) into a suspension formed by sodium diethylhypophosphite and diatomite, after dropwise adding, continuously preserving heat for reaction for 3 hours, centrifugally separating, washing a centrifugal material cake with pure water for three times, then placing the centrifugal material cake in a tray, and drying. And (5) obtaining a product.
Example 6
The preparation method of the aluminum phosphate (phosphonate) flame retardant (FR-6) based on the growth nucleus comprises the following steps:
weighing 11.0kg of diethyl sodium hypophosphite solid, dissolving the 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 dropwise adding (dropwise adding time is 3hr) into a suspension formed by diethyl sodium hypophosphite and diatomite, after dropwise adding, continuously preserving heat for reacting for 3 hours, centrifugally separating, washing the centrifugal material cake with pure water for three times, then placing the centrifugal material cake in a tray, and drying. And (5) obtaining a product.
Example 7
The preparation method of the aluminum phosphate (phosphine) salt flame retardant (FR-7) based on the growth nucleus comprises the following steps:
weighing 22.04kg of sodium phosphite pentahydrate solid, dissolving the sodium phosphite pentahydrate solid 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 33% (w/w) of iron-free aluminum sulfate aqueous solution 162.5kg, slowly dropwise adding (dropwise adding time is 2.5h) into suspension formed by sodium phosphite pentahydrate and a ZSM-5 molecular sieve, after dropwise adding, heating to 85 ℃, continuing to perform heat preservation reaction for 3 hours, performing centrifugal separation, washing the centrifugal cake with pure water for three times, then placing the centrifugal cake in a tray, and drying. And (5) obtaining a product.
Example 8
The preparation method of the aluminum phosphate (phosphonate) 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 5.0kg of SAPO-11 molecular sieve, uniformly stirring, and heating to 50 ℃; preparing 33% (w/w) of iron-free aluminum sulfate aqueous solution 162.5kg, slowly dropwise adding (dropwise adding time is 2.5h) into suspension formed by sodium pentahydrate phosphite and SAPO-11 molecular sieve, after dropwise adding, heating to 90 ℃, continuing to perform heat preservation reaction for 3 hours, performing centrifugal separation, washing the centrifugal cake with pure water for three times, then placing the centrifugal cake in a tray, and drying. And (5) obtaining a product.
Example 9
The preparation method of the aluminum phosphate (phosphonate) flame retardant (FR-9) based on the growth nucleus comprises the following steps:
weighing 22.04kg of sodium phosphite pentahydrate solid, dissolving the sodium phosphite pentahydrate solid in 77.96kg of water to form a uniform solution, adding 5.0kg of diatomite, uniformly stirring, and heating to 50 ℃; preparing 33% (w/w) of iron-free aluminum sulfate aqueous solution 162.5kg, slowly dropwise adding (dropwise adding time is 2.5h) into suspension formed by sodium phosphite pentahydrate and diatomite, after dropwise adding, heating to 95 ℃, continuing to perform heat preservation reaction for 3 hours, performing centrifugal separation, washing the centrifugal cake with pure water for three times, then placing the centrifugal cake in a tray, and drying. And (5) obtaining a product.
Example 10
The preparation method of the aluminum phosphate (phosphonate) flame retardant (FR-10) based on the growth nucleus comprises the following steps:
weighing 2.20kg of pentahydrate sodium phosphite solid and 9.97kg of diethyl sodium hypophosphite solid, dissolving in 38.9g of water to form a uniform solution, adding NAY g of silicon-aluminum molecular sieve, stirring uniformly, and heating to 80 ℃; preparing 72kg of 33% (w/w) iron-free aluminum sulfate aqueous solution, slowly dropwise adding (dropwise adding time is 2.5h) the solution into a suspension formed by sodium phosphite pentahydrate, sodium diethylhypophosphite and NAY molecular sieves, after dropwise adding, continuously preserving heat and reacting for 2 hours, centrifugally separating, washing a centrifugal material cake with pure water for three times, then placing the centrifugal material cake in a tray, and drying. And (5) obtaining a product.
Example 11
The preparation method of the aluminum phosphate (phosphine) salt flame retardant (FR-11) based on the growth nucleus comprises the following steps:
weighing 2.20kg of pentahydrate sodium phosphite solid and 9.97kg of diethyl sodium hypophosphite solid, dissolving in 38.9g of water to form a uniform solution, adding 3.33kg of SAPO-11 aluminophosphate molecular sieve, uniformly stirring, and heating to 80 ℃; preparing 72kg of 33% (w/w) iron-free aluminum sulfate aqueous solution, slowly dropwise adding (dropwise adding time is 2.5h) the solution into a suspension formed by sodium phosphite pentahydrate, sodium diethylhypophosphite and the SAPO-11 aluminophosphate molecular sieve, after dropwise adding, continuously preserving heat and reacting for 3 hours, centrifugally separating, washing a centrifugal material cake with pure water for three times, then placing the centrifugal material cake into a tray, and drying. And (5) obtaining a product.
Example 12
The preparation method of the aluminum phosphate (phosphine) salt flame retardant (FR-12) based on the growth nucleus comprises the following steps:
weighing 2.20kg of sodium pentahydrate phosphite solid and 9.97kg of diethyl sodium hypophosphite solid, dissolving in 38.9g of water to form a uniform solution, adding 50kg of diatomite, stirring uniformly, and heating to 80 ℃; preparing 72kg of 33% (w/w) iron-free aluminum sulfate aqueous solution, slowly dropwise adding (dropwise adding time is 2.5h) the solution into a suspension formed by sodium phosphite pentahydrate, sodium diethylhypophosphite and diatomite, after dropwise adding, continuously preserving heat for reaction for 4 hours, centrifugally separating, washing a centrifugal material cake with pure water for three times, then placing the centrifugal material cake in a tray, and drying. And (5) obtaining a product.
Table 1 shows the proportions of the respective raw materials and the theoretical phosphorus content in the flame retardant in examples 1 to 12(FR-1 to FR-12).
Wherein, the calculation method of the theoretical weight ratio (growth nucleus: aluminum salt) comprises the following steps: during calculation, reacting sodium diethylhypophosphite with aluminum sulfate to generate aluminum diethylhypophosphite, and calculating the mass of the added growth core according to the mass of the aluminum diethylhypophosphite theoretically generated; reacting sodium phosphite pentahydrate with aluminum sulfate to generate aluminum phosphite, and calculating the mass of the added growth nucleus according to the mass of the aluminum phosphite generated theoretically; in a mixed system of sodium phosphite pentahydrate and sodium diethylhypophosphite, the mass of the generated diethyl aluminum hypophosphite and aluminum phosphite is calculated, and the mass of the added growth nucleus is calculated.
TABLE 1 proportioning of raw materials and phosphorus content in flame retardant 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-fold electron microscope photo; b is 10000 times of electron microscope photo; c is 30000 times of electron micrograph.
FIG. 3 is an electron micrograph of a flame retardant sample of example 2. Wherein A is a 5000-fold electron microscope photo; b is 10000 times of electron microscope photo; c is 30000 times of electron micrograph.
FIG. 4 is an electron micrograph of a flame retardant sample of example 3. Wherein A is a 5000-fold electron microscope photo; b is 10000 times of electron microscope photo; c is 30000 times of electron micrograph.
FIG. 5 is an electron micrograph of a flame retardant sample of example 4. Wherein A is a 5000-fold electron microscope photo; b is 10000 times of electron microscope photo; c is 30000 times of electron micrograph.
FIG. 6 is an electron micrograph of a flame retardant sample of example 5. Wherein A is a 5000-fold electron microscope photo; b is 10000 times of electron microscope photo; c is 30000 times of electron micrograph.
FIG. 7 is an electron micrograph of a flame retardant sample of example 6. Wherein A is a 5000-fold electron microscope photo; b is 10000 times of electron micrograph; c is 30000 times of electron micrograph.
FIG. 8 is an electron micrograph of a flame retardant sample of example 7. Wherein A is 25000 times of electron microscope photos; b is 37786 times of electron microscope picture; c is 120000 times of electron micrograph.
FIG. 9 is an electron micrograph of a flame retardant sample of example 8. Wherein A is a 2500-fold electron microscope photo; b is a 5000-fold electron microscope photo; c is 10000 times of electron micrograph.
FIG. 10 is an electron micrograph of a flame retardant sample of example 9. Wherein A is a 2500-fold electron micrograph; b is a 5000-fold electron microscope photo; c is 10000 times of electron micrograph.
FIG. 11 is an electron micrograph of a flame retardant sample of example 10. Wherein A is a 2500-fold electron microscope photo; b is a 5000-fold electron microscope photo; c is 10000 times of electron micrograph.
FIG. 12 is an electron micrograph of a flame retardant sample of example 11. Wherein A is 50000 times of electron microscope photos; b is a 60000-fold electron microscope photograph; and C is a 60000-fold electron microscope photograph.
FIG. 13 is an electron micrograph of a flame retardant sample of example 12. Wherein A is a 2500-fold electron microscope photo; b is a 5000-fold electron microscope photo; c is 10000 times of electron micrograph.
Application examples 1-15 and comparative examples 1-19 for preparing halogen-free flame-retardant glass fiber reinforced plastic by using flame retardant
First, the source of raw material
PA6, 2400J, Hangzhou Polycis;
PA66, EPR27, platypodium;
PA6T/66, 1245, Qingdao three forces;
PBT, KH2083, Yingkoukanghui;
OP1230, OP1240, OP1400, clariant;
MPP: 200-70, melamine polyphosphate, basf;
safire400, melamine polyphosphate, qiubo;
amgardp pa1, polyphosphate, solvay;
MCA: MC-25, Fine chemical research institute of Sichuan province;
glass fiber, ECS301UW, Chongqing International composite Limited;
antioxidant, 1010, Tianjin Lianlong; 608, taiwan chia; h10: bluggeman;
lubricant, 540A, hounizzar;
nucleating agent, Cav102, clariant;
sodium hypophosphite monohydrate, developed in Hubei;
sodium diethylhypophosphite, Qingdao European-Prorey;
sodium phosphite pentahydrate, which is developed in Hubei province.
Formula of halogen-free flame-retardant glass fiber reinforced plastic
The formula of the halogen-free flame-retardant glass fiber reinforced plastic is shown in the table 2-table 5. Wherein S1 to S15 are application examples 1 to 15 in this order, and V1 to V19 are comparative examples 1 to 19 in this order.
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 (GF) through a glass fiber adding port, adding a Flame Retardant (FR) through a side feeding machine, starting a main machine and the feeding machine to complete the extrusion granulation of the material, and then drying the material.
Application and test of halogen-free flame-retardant glass fiber reinforced plastic
And (3) injecting the dried material into a standard sample in an injection molding machine according to UL 94V-0 test standard, and testing. Wherein "0.8 mm" in tables 2 to 5 means the thickness of the produced sample bar; "1.6 mm" means the thickness of the resulting specimen.
TABLE 2
| Composition of raw materials | 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 4
| Composition of raw materials | 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
| Composition of raw materials | 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 of the invention can reach the flame retardant grade of UL94V0(0.8 mm). 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: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a phosphate aluminum salt flame retardant based on growth nuclei is characterized by comprising the following steps: when a phosphorus-containing raw material and an aluminum salt are used as raw materials to prepare the aluminum phosphate flame retardant, adding a growth nucleus for reaction; the phosphorus-containing raw material is one or more compounds of hypophosphite, organic hypophosphite, phosphite and organic phosphite; the growth nucleus is a substance with a rough surface or a porous surface.
2. The method of claim 1 for preparing a growing core based aluminum phosphate salt flame retardant, wherein: the growth nucleus is a molecular sieve or diatomite; the diatomite is natural diatomite or a purified product of diatomite; preferably, the molecular sieve is natural zeolite or an artificially synthesized molecular sieve, and the molecular sieve comprises a silicate, an aluminosilicate molecular sieve, a mesoporous molecular sieve and an aluminum phosphate molecular sieve; the silicate, aluminosilicate type molecular sieves include type A, X, Y, M, ZSM; the mesoporous molecular sieve comprises MCM-41 and SBA-15 types; the aluminophosphate type molecular sieves include the AlPO4 series, SAPO series, MeAPO, ElAPO series.
3. The method of claim 1 for preparing a growth nucleus based aluminum phosphate salt flame retardant, wherein: the hypophosphite, organic hypophosphite, phosphite and organic phosphite are soluble salts; 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 soluble aluminum salt; examples of the metal salt include aluminum sulfate, aluminum chloride, and aluminum nitrate, and aluminum sulfate is preferable.
4. A method for preparing a growing core based aluminium phosphate salt flame retardant according to any one of claims 1 to 3, wherein: the weight ratio of the growth nucleus to the phosphorus-containing raw material is 1:10-11: 1; and/or
The D50 of the growth nucleus is 0.2-50 μm, preferably 1-30 μm; and/or
The reaction temperature during the reaction is as follows: the reaction is carried out at the temperature of 55-105 ℃.
5. The method of any one of claims 1 to 4 for preparing a growing core based aluminium phosphate salt flame retardant, wherein: the preparation method comprises the following steps: one or more compounds of hypophosphite, organic hypophosphite, phosphite and organic phosphite are pre-adsorbed with the growth nucleus, and after the mixture is uniformly stirred, aluminum salt is dripped for reaction to prepare the aluminum phosphate salt flame retardant based on the growth nucleus.
6. A growing core based aluminium phosphate salt flame retardant prepared using the method of any one of claims 1 to 5.
7. Use of the growing core based aluminium phosphate salt flame retardant of claim 6 for the preparation of thermoplastics, thermosets;
preferably, the application is the application of the aluminum phosphate salt flame retardant based on the growth nucleus in combination with the glass fiber in preparing the halogen-free flame-retardant glass fiber reinforced plastic.
8. A thermoplastic, thermoset, characterized by: the aluminum phosphate salt flame retardant based on growth nuclei of claim 6 is included in the raw materials for the preparation thereof.
9. 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:
resin base material: 18 to 84.5 percent;
the growth core based aluminum phosphate salt flame retardant of claim 6: 10 to 30 percent;
glass fiber: 5 to 50 percent;
other processing aids: 0.5 to 2 percent.
10. 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, feeding the aluminum phosphate salt flame retardant based on the growth nucleus in claim 6 through a side feeder, starting a main machine and the feeder to complete extrusion granulation of the material, and then drying the material.
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