CN111171257A - Preparation method of high-performance flame retardant compounded by isocyanuric acid triphosphate and derivatives thereof - Google Patents
Preparation method of high-performance flame retardant compounded by isocyanuric acid triphosphate and derivatives thereof Download PDFInfo
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- CN111171257A CN111171257A CN202010082369.7A CN202010082369A CN111171257A CN 111171257 A CN111171257 A CN 111171257A CN 202010082369 A CN202010082369 A CN 202010082369A CN 111171257 A CN111171257 A CN 111171257A
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- Prior art keywords
- flame retardant
- triphosphate
- trioxo
- triazine
- preparation
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 85
- 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 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- RWTOLOITMVNYHA-UHFFFAOYSA-N OP(O)(=O)OP(=O)(O)OP(=O)(O)O.O=C1NC(NC(N1)=O)=O Chemical compound OP(O)(=O)OP(=O)(O)OP(=O)(O)O.O=C1NC(NC(N1)=O)=O RWTOLOITMVNYHA-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229920002635 polyurethane Polymers 0.000 claims abstract description 44
- 239000004814 polyurethane Substances 0.000 claims abstract description 44
- 239000001226 triphosphate Substances 0.000 claims abstract description 36
- 101000588130 Homo sapiens Microsomal triglyceride transfer protein large subunit Proteins 0.000 claims abstract description 22
- 102100031545 Microsomal triglyceride transfer protein large subunit Human genes 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 13
- -1 rare earth ions Chemical class 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 229920005862 polyol Polymers 0.000 claims description 14
- 150000003077 polyols Chemical class 0.000 claims description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 13
- 229920000570 polyether Polymers 0.000 claims description 13
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 claims description 12
- 238000013329 compounding Methods 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 10
- 150000002513 isocyanates Chemical class 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 239000004088 foaming agent Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 150000008301 phosphite esters Chemical class 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229950009390 symclosene Drugs 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QPGWLKQGHLHETJ-UHFFFAOYSA-N [ethoxy(hydroxy)phosphoryl] phosphono hydrogen phosphate Chemical compound CCOP(O)(=O)OP(O)(=O)OP(O)(O)=O QPGWLKQGHLHETJ-UHFFFAOYSA-N 0.000 claims description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 2
- 229940048102 triphosphoric acid Drugs 0.000 claims description 2
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 claims description 2
- QOPBTFMUVTXWFF-UHFFFAOYSA-N tripropyl phosphite Chemical compound CCCOP(OCCC)OCCC QOPBTFMUVTXWFF-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 2
- 229910052749 magnesium Inorganic materials 0.000 claims 2
- 239000011777 magnesium Substances 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- VYGUBTIWNBFFMQ-UHFFFAOYSA-N [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical group [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O VYGUBTIWNBFFMQ-UHFFFAOYSA-N 0.000 claims 1
- 238000006757 chemical reactions by type Methods 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 235000021317 phosphate Nutrition 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000000123 paper Substances 0.000 abstract description 2
- 239000004753 textile Substances 0.000 abstract description 2
- 239000002023 wood Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- FWXNJWAXBVMBGL-UHFFFAOYSA-N 9-n,9-n,10-n,10-n-tetrakis(4-methylphenyl)anthracene-9,10-diamine Chemical compound C1=CC(C)=CC=C1N(C=1C2=CC=CC=C2C(N(C=2C=CC(C)=CC=2)C=2C=CC(C)=CC=2)=C2C=CC=CC2=1)C1=CC=C(C)C=C1 FWXNJWAXBVMBGL-UHFFFAOYSA-N 0.000 description 27
- 102000003978 Tissue Plasminogen Activator Human genes 0.000 description 27
- 108090000373 Tissue Plasminogen Activator Proteins 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- FSNCEEGOMTYXKY-JTQLQIEISA-N Lycoperodine 1 Natural products N1C2=CC=CC=C2C2=C1CN[C@H](C(=O)O)C2 FSNCEEGOMTYXKY-JTQLQIEISA-N 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 229910052751 metal Chemical class 0.000 description 7
- 239000002184 metal Chemical class 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 4
- 101000653680 Hordeum vulgare Translationally-controlled tumor protein homolog Proteins 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920000388 Polyphosphate Polymers 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 150000003512 tertiary amines Chemical group 0.000 description 2
- 235000011178 triphosphate Nutrition 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 2
- JQTUEJIDFLIUEH-UHFFFAOYSA-N (2,4,6-trioxo-3,5-diphosphono-1,3,5-triazinan-1-yl)phosphonic acid Chemical compound C1(=O)N(C(=O)N(C(=O)N1P(=O)(O)O)P(=O)(O)O)P(=O)(O)O JQTUEJIDFLIUEH-UHFFFAOYSA-N 0.000 description 1
- IJKLPURZPYBADG-UHFFFAOYSA-N 3-chloropropyl 2-(2-hydroxyethoxy)ethyl hydrogen phosphate Chemical compound P(=O)(OCCCCl)(O)OCCOCCO IJKLPURZPYBADG-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
- C07F9/6521—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
-
- 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
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
Abstract
The invention relates to a preparation method of a high-performance fire retardant compounded by isocyanuric acid triphosphoric acid and derivatives thereof, which is prepared from 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate (TTPE), 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate (TTP) and 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate (MTTP, M ═ Ca)2+,Mg2+,Fe2+Transition metal ions, rare earth ions and the like) and the compound is used as a reactive polyurethane flame retardant. The flame retardant is mainly characterized by gas phase and condensed phase synergistic flame retardance depending on the contained nitrogen element and phosphorus element, can be used as a reactive flame retardant, and has simple synthesis method and good flame retardant effect. The flame retardant can be used for various polyurethane materials, and can also be used in the fields of decorative materials, textiles, wood, paper and the like.
Description
Technical Field
The invention relates to a high-performance fire retardant compounded by isocyanuric acid triphosphoric acid and derivatives thereof, which can be used in the fields of various polyurethane materials, decorative materials, textiles, wood, paper and the like.
Technical Field
The polyurethane has excellent mechanical property, high strength, good elasticity and wear resistance, and is widely applied to rubber, fiber, adhesive, elastomer, soft (or hard) foam plastic and the like. However, polyurethane materials (especially polyurethane foam materials) are flammable, and a large amount of toxic gases such as HCN, CO and the like can be generated in the combustion process, so that the health of human bodies is seriously harmed. Therefore, the development of polyurethane flame retardant materials is receiving extensive attention.
The traditional halogen flame retardant brings environmental pollution problem, therefore, halogen-free environment-friendly polyurethane flame retardant needs to be developed. At present, nitrogen-phosphorus flame retardants are researched more and certain research progress is made. The nitrogen-containing flame retardant can generate nitrogen at high temperature, reduce oxygen concentration and play a role in gas-phase flame retardance. The phosphorus-containing flame retardant can generate phosphoric acid and dehydration oligomer thereof at high temperature, and mainly plays a role in condensed phase flame retardance. If the flame retardant material containing nitrogen element and phosphorus element is designed and synthesized, the synergistic flame retardant effect of gas phase and condensed phase can be achieved.
C.H.wavelet Weill et al reported (CN201280013371.2) the preparation of diester diols of brominated aromatic compounds as reactive flame retardants for flexible polyurethane foams. The flame retardant contains halogen and hydroxyl, and the hydroxyl can perform reactive flame retardance. Wanokwei et al reported (cn201811105197.x) a complex of tris (2-chloropropyl) phosphate and a diethylene glycol chloropropyl phosphate oligomer as a polyurethane foam flame retardant containing halogen and phosphorus. Wadeleki et al reported (CN201910587907.5) polydiallyldimethylammonium and polyphosphate polyelectrolyte complex flame retardants that react to form ammonium chloride when acted upon, resulting in halogen emissions. Niudan et al reported (CN201710875352.5) a low triphenyl phosphate halogen-free flame retardant material, belonging to phosphorus flame retardant.
The invention prepares 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphonic acid (TTP) and metal salt MTTP and ester TTPE thereof, and compounds the three to obtain the polyurethane flame retardant material with gas phase and condensed phase synergistic action. The obtained samples are respectively subjected to flame retardant performance such as limited oxygen index and vertical burning test according to standards GB/T2406-1993 and GB/T2408-2008, and are prepared according to standard QB/T4197-2011, and the mechanical properties such as tensile strength and elongation at break are measured. The flame-retardant material has good flame-retardant performance and mechanical performance.
The invention content is as follows:
the invention utilizes the reaction of high-activity N-Cl bond in trichloroisocyanuric acid molecule and phosphite ester to obtain 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate, hydrolyzes the 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate in concentrated hydrochloric acid, and reacts with water-soluble high-valence transition metal ions to obtain insoluble 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate. The specific operation steps and reaction process are as follows:
(1) preparation of flame retardant components
60mL of triethyl phosphite (TEP,0.34mol) was charged into a 200mL three-necked round bottom flask. Under the magnetic stirring, 13.94g of trichloroisocyanuric acid (TCCA,0.06mol) is divided into three batches, and slowly added into triethyl phosphite within 1 hour at room temperature, the TCCA is gradually dissolved, the reaction releases heat, and chloroethane gas is released, so that a yellow transparent solution is obtained. After the TCCA is added, the temperature is raised to 100-105 ℃ for reaction for 8h, the reaction is cooled to 50 ℃, 35mL of petroleum ether (boiling range is 60-90 ℃) is slowly added, the mixture is continuously stirred and cooled to room temperature, the mixture is stirred overnight, a large amount of colorless crystals are separated out, the mixture is filtered, the mixture is washed for 3 times by 20mL of petroleum ether, and unreacted TEP and TCCA are removed, so that 25.15g of colorless crystals, namely 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-ethyl triphosphate (HTP, yield: 78%) are obtained.
21.5g HTP (0.04mol) were added to 130mL concentrated HCl, refluxed for 36h with magnetic stirring, cooled to 50 deg.C, evaporated to HCl under reduced pressure, concentrated to 40mL, extracted three times with 90mL ethyl acetate to remove unhydrolyzed HTP. The aqueous phase was concentrated to near dryness and dried in a vacuum oven at 120 ℃ for 12h to give 14.18 g of a white solid, i.e., 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate (TTPA, yield: 96%).
11.08g of TTPA (0.03mol) was added to 20mL of deionized water, and the mixture was stirred at room temperature for 30min to dissolve it sufficiently. 4.05g of ferric chloride hexahydrate (0.015mol) was dissolved in 30mL of 0.1mol L-1Dilute hydrochloric acid (to avoid hydrolysis to form insoluble ferric hydroxide). Dropwise adding hydrochloric acid solution of ferric trichloride into aqueous solution of TTPA, stirring at room temperature for 12h to enable phosphonic acid groups on TTPA to react with Fe3+The polymerization reaction was sufficiently carried out to obtain a yellow suspension. It was filtered with suction and washed with deionized water to a filtrate pH of 7 to sufficiently remove unreacted starting materials, and dried at 120 ℃ for 12 hours to give 6.9g of a yellow solid (yield 51%) which was 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-ferric triphosphate with a molar ratio of iron to TTPA of 1:2, and thus the product was designated FeTTP (1: 2). FeTTP with different molar ratios of iron and TTPA can be obtained by the method. According to this method, MTTP of different metals can be prepared by replacing ferric trichloride hexahydrate with water-soluble salts of other metals.
The reaction equations for synthesizing HTP, TTPA and MTTP are as follows.
Synthesis of MTTP
Wherein M isn+＝Mg2+、Ca2+Transition metal ion or rare earth ion
(2) Research on compounding process of flame retardant
Compounding HTP, TTPA and MTTP according to a certain proportion to obtain a reactive polyurethane flame retardant, and compounding 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate, 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate and 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate, wherein the mass ratio of the HTP to the TTPA to the MTTP is 6:1: 1-1: 3: 4; the compounding process comprises the following steps: firstly, 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate is added for 1-2 h, then 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate is added according to the proportion and continuously ground for 0.5-2 h, and after the grinding is uniform, 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate and a proper solvent are added and ground for 0.5-2 h.
(3) Reaction of reactive flame retardants with isocyanates
(a) Reaction of TTPA with isocyanate
In the process of preparing polyurethane by mixing A, B two raw materials of polyurethane, phosphoric acid groups in TTPA and isocyanate can react to obtain the polyurethane with the participation of TTPA, and the flame retardant component and the polyurethane can be fully mixed and exist in the polyurethane, so that the combustion of the polyurethane can be effectively prevented, and the flame retardant property of the polyurethane can be optimal. The reaction equation is as follows:
(b) reaction of MTTP with isocyanate
In the process of preparing polyurethane by mixing A, B two raw materials of polyurethane, phosphate groups which do not react with metal ions in MTTP or hydroxyl groups in the residual phosphate groups can react with isocyanate to obtain the polyurethane with the participation of MTTP, and the flame retardant component and the polyurethane can be fully mixed and exist in the polyurethane to effectively prevent the combustion of the polyurethane, so the flame retardant property of the polyurethane can reach the best. The reaction equation is as follows:
(c) because the HTP is a hydrophobic compound, the HTP has good intersolubility with polyurethane, and can be directly doped into the polyurethane to play a role in flame retardance.
(4) Method for Using flame retardant
The flame retardant compound is added into the A ingredient of the polyurethane according to the formula and different dosage of the polyurethane. The polyurethane is prepared from A, B components in parts by mass: component A (combined polyether component): 50-100 parts of polyether polyol; 0-50 parts of polymer polyol; 0.2-5 parts of a catalyst; 1-8 parts of a foaming agent; 0.2-3 parts of foam stabilizer; 0.2-6 parts of a crosslinking agent; 0-10 parts of a pore-forming agent; 0.1-20 parts of a reactive flame retardant (related to the invention); component B (isocyanate component): polyisocyanates, which may be TDI, MDI, polymeric MDI or modified MDI and mixtures thereof;
the mass ratio of A to B is 100: 30-100: 80.
Wherein the polyether polyol in the formula of the polyurethane has the functionality of 3, the relative molecular weight of 4000-9000 and the primary hydroxyl content in the terminal hydroxyl groups of more than 65 percent; the polymer polyol is a graft copolymer of polyether polyol and styrene acrylonitrile; the catalyst is tertiary amine or secondary amine; the foaming agent is one or a mixture of more of deionized water, polybasic primary amine and quaternary ammonium carbonate; the foam stabilizer is polysiloxane polyether copolymer; the cross-linking agent is an alcohol amine compound; the cell opener is polyether polyol with EO content more than or equal to 50%.
(5) Flame retardant performance study of flame retardant
The flame retardant is added into polyurethane, the flame retardant performance detection of the worthy product is respectively according to standards GB/T2406-1993 and GB/T2408-2008, samples are prepared and the flame retardant performance such as limiting oxygen index and vertical burning test are determined, and according to standard QB/T4197-2011, samples are prepared and the mechanical properties such as tensile strength and elongation at break are determined.
The flame retardant has the characteristics analysis and innovation points that:
1) the flame retardant compound contains flame-retardant isocyanuric acid groups and phosphoric acid groups in the molecule and polymerized polyphosphate flame-retardant components.
2) The flame retardant has the advantages that the flame retardant contains two flame-retardant elements of nitrogen and phosphorus, can generate the synergistic flame-retardant effect of gas phase and condensed phase, and has better flame retardant property.
3) The polyphosphate group in TTPA and unreacted phosphate group or unreacted hydroxyl group in phosphate group in MTTP salt in the component can react with isocyanate, so that the flame retardant group of the flame retardant is connected into polyurethane, and the flame retardant can be uniformly mixed and can be subjected to flame retardance at the unburned moment. Can achieve good flame retardant effect.
4) The HTP phosphate component of the flame retardant can be mixed into the polyurethane material to play a role in flame retardance.
5) The flame retardant prepared by the HTP, the TTPA and the MTTP according to a certain mass ratio and a compounding process has more flame retardant groups and flame retardant components and can have better flame retardant effect.
Detailed Description
[ example 1 ]: preparation of ethyl 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate (HTP)
60mL of triethyl phosphite (TEP,0.34mol) was charged into a 200mL three-necked round bottom flask. Under the magnetic stirring, 13.94g of trichloroisocyanuric acid (TCCA,0.06mol) is divided into three batches, and slowly added into triethyl phosphite within 1 hour at room temperature, the TCCA is gradually dissolved, the reaction releases heat, and chloroethane gas is released, so that a yellow transparent solution is obtained. After the TCCA is added, the temperature is raised to 100-105 ℃ for reaction for 8h, the reaction is cooled to 50 ℃, 35mL of petroleum ether (boiling range is 60-90 ℃) is slowly added, the mixture is continuously stirred and cooled to room temperature, the mixture is stirred overnight, a large amount of colorless crystals are separated out, the mixture is filtered, the mixture is washed for 3 times by 20mL of petroleum ether, and unreacted TEP and TCCA are removed, so that 25.15g of colorless crystals, namely ethyl 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate (yield: 78%) are obtained.
The method is adopted, and the product can be obtained only by replacing triethyl phosphite with other phosphite esters (trimethyl phosphite, tripropyl phosphite and triisopropyl phosphite) and also by controlling the temperature at 85-120 ℃.
[ example 2 ]: preparation of 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphoric acid (TTPA)
21.5g HTP (0.04mol) were added to 130mL concentrated HCl, refluxed for 36h with magnetic stirring, cooled to 50 deg.C, evaporated to HCl under reduced pressure, concentrated to 40mL, extracted three times with 90mL ethyl acetate to remove unhydrolyzed HTP. The aqueous phase was concentrated to near dryness and dried in a vacuum oven at 120 ℃ for 12h to give 14.18 g of a white solid, i.e., 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate (TTPA, yield: 96%).
The yields of the reactions carried out with different phosphites or under different conditions using the same reaction procedure are summarized in table 1:
TABLE 1 reaction conditions and yields for the preparation of TTPA from different phosphite reactions
[ example 3 ]: preparation of 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate (MTTP)
11.08g of TTPA (0.03mol) was added to 20mL of deionized water, and the mixture was stirred at room temperature for 30min to dissolve it sufficiently. 4.05g of ferric chloride hexahydrate (0.015mol) was dissolved in 30mL of 0.1mol L-1Dilute hydrochloric acid (to avoid hydrolysis to form insoluble ferric hydroxide). Dropwise adding hydrochloric acid solution of ferric trichloride into aqueous solution of TTPA, stirring at room temperature for 12h to enable phosphonic acid groups on TTPA to react with Fe3+The polymerization reaction was sufficiently carried out to obtain a yellow suspension. It was filtered with suction and washed with deionized water to a filtrate pH of 7 to sufficiently remove unreacted starting materials, and dried at 120 ℃ for 12 hours to give 6.9g of a yellow solid (yield 51%) which was 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-ferric triphosphate with a molar ratio of iron to TTPA of 1:2, and thus the product was designated FeTTP (1: 2). FeTTP with different molar ratios of iron and TTPA can be obtained by the method. According to this method, MTTP of different metals can be prepared by replacing ferric trichloride hexahydrate with water-soluble salts of other metals.
The results of the same reaction procedure but with different metal ions or different molar ratios (metal: TTPA) are shown in Table 2.
TABLE 2 yield of different metal ion or different molar ratio (metal: TTPA) reactions
[ example 4 ]: compounding process of flame retardant
Compounding HTP, TTPA and MTTP according to a certain proportion to obtain a reactive polyurethane flame retardant, and compounding 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate, 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate and 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate, wherein the mass ratio of the HTP to the TTPA to the MTTP is 6:1: 1-1: 3: 4; the compounding process comprises the following steps: firstly, 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate is added for 1-2 h, then 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate is added according to the proportion and continuously ground for 0.5-2 h, and after the grinding is uniform, 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate and a proper solvent are added and ground for 0.5-2 h.
[ example 5 ]: method for using flame retardant in polyurethane and preparation process of polyurethane product
The flame retardant of example 4 was added in the proportions of the polyurethane formulation A already prepared. The polyurethane is prepared from A, B components in parts by mass: component A (combined polyether component): 50-100 parts of polyether polyol; 0-50 parts of polymer polyol; 0.2-5 parts of a catalyst; 1-8 parts of a foaming agent; 0.2-3 parts of foam stabilizer; 0.2-6 parts of a crosslinking agent; 0-10 parts of a pore-forming agent; 0.1-20 parts of a reactive flame retardant (related to the invention); component B (isocyanate component): polyisocyanates, which may be TDI, MDI, polymeric MDI or modified MDI and mixtures thereof; the mass ratio of A to B is 100: 30-100: 80.
Wherein the polyether polyol in the formula of the polyurethane has the functionality of 3, the relative molecular weight of 4000-9000 and the primary hydroxyl content in the terminal hydroxyl groups of more than 65 percent; the polymer polyol is a graft copolymer of polyether polyol and styrene acrylonitrile; the catalyst is tertiary amine or secondary amine; the foaming agent is one or a mixture of more of deionized water, polybasic primary amine and quaternary ammonium carbonate; the foam stabilizer is polysiloxane polyether copolymer; the cross-linking agent is an alcohol amine compound; the cell opener is polyether polyol with EO content more than or equal to 50%.
According to the prepared polyurethane product added with the novel flame retardant, samples are prepared and the flame retardant performance such as limited oxygen index and vertical burning test are determined according to the standards GB/T2406-1993 and GB/T2408-2008, and the samples are prepared and the mechanical performance such as tensile strength and elongation at break are determined according to the standard QB/T4197-2011. The results are shown in Table 3.
TABLE 3 flame retardancy of HTP, TTPA and MTTP compounded flame retardants for polyurethanes
Note: RHTP: esters, Me-methyl; et-ethyl; pr-propyl, and the like.
Claims (6)
1. A preparation method of a high-performance reactive flame retardant compounded by isocyanuric acid triphosphate and derivatives thereof is characterized by comprising the following steps: the flame retardant is prepared by compounding 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate (HTP), 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate (TTPA) and 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate (MTTP); the flame retardant contains various flame retardant groups such as isocyanuric groups, phosphoric groups and phosphates, and various flame retardant elements such as nitrogen, phosphorus and magnesium, and has good flame retardant property; phosphoric acid groups in TTPA in the compound, unreacted phosphoric acid groups in MTTP and unreacted hydroxyl groups in the phosphoric acid groups react with isocyanate, and the flame retardant is uniformly distributed in the polyurethane material, so that the flame retardant effect is better; the preparation method comprises the following steps:
(1) trichloroisocyanuric acid and phosphite ester are used as raw materials to react to obtain 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-ethyl triphosphate (HTP); hydrolyzing HTP in concentrated hydrochloric acid to obtain 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate (TTPA); polymerizing one or more of TTPA and metal ions in an aqueous phase to obtain 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate (MTTP);
(2) the HTP, the TTPA and the MTTP are compounded according to a certain proportion to obtain the reactive polyurethane flame retardant, and the flame retardant is used for various types of polyurethane.
2. The preparation method of the high-performance reactive flame retardant compounded by the isocyanuric acid triphosphoric acid and the derivatives thereof according to claim 1, wherein the phosphite ester is selected from the following components: one or a mixture of more of trimethyl phosphite, triethyl phosphite, tripropyl phosphite or triisopropyl phosphite, and is characterized in that: the alcohol produced by the hydrolysis reaction has a low boiling point and is easily removed by evaporation.
3. The isocyanate triphosphoric acid and its derivative compounded high-purity compound of claim 1The preparation method of the performance reaction type flame retardant comprises the following steps of: mg (magnesium)2+、Ca2+One or more of transition metal ions or rare earth ions, characterized in that: the salt is soluble in water, can ionize metal ions in the solution, and is selected from one or more of acetate, hydrochloride and nitrate.
4. The preparation method of the high-performance reactive flame retardant compounded by the isocyanuric acid triphosphate and the derivatives thereof according to claim 1 is characterized by comprising the following steps: in the preparation process of MTTP, the mass ratio of metal ions to 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphoric acid is 2: 5-3: 2.
5. The preparation method of the high-performance reactive flame retardant compounded by the isocyanuric acid triphosphate and the derivatives thereof as claimed in claim 1, is characterized in that: 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate, 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate and 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate are compounded, wherein the mass ratio of the three is 6:1: 1-1: 3: 4; the compounding process comprises the following steps: firstly, 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate is added for 1-2 h, then 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate is added according to the proportion and continuously ground for 0.5-2 h, and after the grinding is uniform, 2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triphosphate and a proper solvent are added and ground for 0.5-2 h.
6. The preparation method of the high-performance reactive flame retardant compounded by the isocyanuric acid triphosphate and the derivatives thereof as claimed in claim 1, is characterized in that: the polyurethane raw material consists of A, B two components, the flame retardant obtained by compounding is added into the component A according to different mass ratios, and the component A contains: the flame retardant comprises polyether polyol, polymer polyol, a catalyst, a foaming agent, a foam stabilizer, a crosslinking agent, a cell opening agent and a reactive flame retardant (related by the invention), wherein the flame retardant accounts for 1-20 parts by mass; component B (isocyanate component): a polyisocyanate comprising: TDI, MDI, polymeric MDI or modified MDI and mixtures thereof; the mass ratio of A to B is 100: 30-100: 80.
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