CN117534702A - Dialkyl-monoalkyl composite phosphinate and rapid preparation method thereof - Google Patents
Dialkyl-monoalkyl composite phosphinate and rapid preparation method thereof Download PDFInfo
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- CN117534702A CN117534702A CN202410034641.2A CN202410034641A CN117534702A CN 117534702 A CN117534702 A CN 117534702A CN 202410034641 A CN202410034641 A CN 202410034641A CN 117534702 A CN117534702 A CN 117534702A
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- China
- Prior art keywords
- phosphinate
- monoalkyl
- composite
- dialkyl
- reaction
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- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 title claims abstract description 94
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 157
- 239000000243 solution Substances 0.000 claims abstract description 114
- 239000003999 initiator Substances 0.000 claims abstract description 87
- 150000001336 alkenes Chemical class 0.000 claims abstract description 35
- -1 hypophosphite alkali metal salt Chemical class 0.000 claims abstract description 34
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 21
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 3
- 239000005077 polysulfide Substances 0.000 claims description 3
- 150000008117 polysulfides Polymers 0.000 claims description 3
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010985 leather Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 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 abstract description 22
- 239000003063 flame retardant Substances 0.000 abstract description 22
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 65
- 239000005977 Ethylene Substances 0.000 description 65
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 45
- 229910052698 phosphorus Inorganic materials 0.000 description 45
- 239000011574 phosphorus Substances 0.000 description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 19
- 238000001556 precipitation Methods 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 238000005481 NMR spectroscopy Methods 0.000 description 18
- 229910000831 Steel Inorganic materials 0.000 description 18
- 239000010959 steel Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 230000001105 regulatory effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- ZJOKNSFTHAWVKK-UHFFFAOYSA-K aluminum octadecanoate sulfate Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Al+3].S(=O)(=O)([O-])[O-] ZJOKNSFTHAWVKK-UHFFFAOYSA-K 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 238000010183 spectrum analysis Methods 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 8
- ACBPPDYBJZVCTL-UHFFFAOYSA-N CCP(O)=O Chemical compound CCP(O)=O ACBPPDYBJZVCTL-UHFFFAOYSA-N 0.000 description 7
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical compound CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 description 7
- 238000004364 calculation method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005457 optimization Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KTLIMPGQZDZPSB-UHFFFAOYSA-M diethylphosphinate Chemical compound CCP([O-])(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-M 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229910001376 inorganic hypophosphite Inorganic materials 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- REBHQKBZDKXDMN-UHFFFAOYSA-M [PH2]([O-])=O.C(C)[Al+]CC Chemical compound [PH2]([O-])=O.C(C)[Al+]CC REBHQKBZDKXDMN-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- HOCOIDRZLNGZMV-UHFFFAOYSA-N ethoxy(oxido)phosphanium Chemical compound CCO[PH2]=O HOCOIDRZLNGZMV-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 238000007342 radical addition reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ZJKCITHLCNCAHA-UHFFFAOYSA-K aluminum dioxidophosphanium Chemical compound [Al+3].[O-][PH2]=O.[O-][PH2]=O.[O-][PH2]=O ZJKCITHLCNCAHA-UHFFFAOYSA-K 0.000 description 1
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- SIGUVTURIMRFDD-UHFFFAOYSA-M sodium dioxidophosphanium Chemical compound [Na+].[O-][PH2]=O SIGUVTURIMRFDD-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention relates to a rapid preparation method of dialkyl-monoalkyl composite phosphinate, which comprises the following steps: dissolving soluble hypophosphite alkali metal salt in water, dropwise adding initiator solution with concentration of 5-20% into a reaction container, introducing olefin at the same time, and keeping the temperature of the reaction container at 110-130 ℃ and the pressure at 5-10MPa; cooling the reaction vessel to 100-110 ℃ until the molar ratio of the olefin to the hypophosphite is 1.2-1.4:1, stopping introducing the olefin when the molar ratio of the olefin to the hypophosphite is 1.6-1.9:1, continuously dropwise adding the initiator, and carrying out constant-temperature reaction until the reaction is finished to obtain an intermediate solution; and (3) dripping a soluble metal salt solution into the intermediate solution, and precipitating, filtering and washing to obtain the dialkyl-monoalkyl composite phosphinate. The concentration of olefin, the reaction temperature and the reaction pressure are controlled in the middle and later stages of the reaction, inorganic hypophosphorous acid is completely converted into organic phosphinic acid as much as possible, the extremely low residue of hypophosphite is realized, the component ratio of monoalkylphosphinate is controlled to be 5-20%, and better flame retardant property is realized.
Description
Technical Field
The invention belongs to the technical field of flame retardant materials, and particularly relates to dialkyl-monoalkyl composite phosphinate and a rapid preparation method thereof.
Background
The dialkyl phosphinate is widely applied to flame retardance of materials such as polyamide, polyester, epoxy resin, polyurethane and the like due to good heat stability and high-efficiency flame retardance, wherein the dialkyl phosphinate has high requirements on heat stability and purity of the alkyl phosphinate due to high processing temperature of a base material in engineering plastics such as polyamide, polyester and the like, and the dialkyl phosphinate with high purity is required to be prepared or removed in the preparation process.
However, in epoxy resin, polyurethane and other thermosetting coating materials, when the thermal stability of the flame retardant has no high requirement in engineering plastics, the higher phosphorus content of the monoalkyl phosphinate and the high-efficiency flame-retardant synergistic performance reflected in the composite use process of the monoalkyl phosphinate and the diethyl phosphinate have obvious advantages.
The Chinese patent publication No. CN103172670B discloses a monoalkyl/dialkyl phosphinate and a preparation method thereof, wherein water is used as a reaction medium, hypophosphite reacts with olefin under the action of an initiator, the reaction is firstly carried out at the temperature of 70-90 ℃ to obtain the monoalkyl phosphinate, then the monoalkyl phosphinate reacts with olefin under the action of the initiator, and the reaction is carried out at the temperature of 90-110 ℃ to obtain the dialkyl phosphinate; however, aluminum hypophosphite is adopted as a raw material, is insoluble, and needs to undergo a gas-solid reaction when contacting ethylene gas, so that the reaction difficulty of free radical addition reaction with higher addition activity difficulty is further increased, and the problems of longer reaction time, lower reaction yield and incomplete reaction progress are caused.
Thus, there is a need for a process for preparing dialkyl-monoalkyl complex phosphinates with higher reaction yields and more thorough reactions.
Disclosure of Invention
The invention provides dialkyl-monoalkyl composite phosphinate and a rapid preparation method thereof, which are used for solving the problems of long reaction time, low reaction yield and incomplete reaction due to the fact that aluminum hypophosphite serving as a raw material is difficult to dissolve in water and needs to carry out gas-solid reaction with olefin in the existing preparation method.
The invention is realized by the following technical scheme:
a rapid preparation method of dialkyl-monoalkyl composite phosphinate, comprising the following steps:
dissolving soluble hypophosphite alkali metal salt in water, dropwise adding initiator solution with concentration of 5-20% into a reaction container, introducing olefin at the same time, and keeping the temperature of the reaction container at 110-130 ℃ and the pressure at 5-10MPa;
cooling the reaction vessel to 100-110 ℃ until the molar ratio of the olefin to the hypophosphite is 1.2-1.4:1, stopping introducing the olefin when the molar ratio of the olefin to the hypophosphite is 1.6-1.9:1, continuously dropwise adding the initiator, and carrying out constant-temperature reaction until the reaction is finished to obtain a dialkyl-monoalkyl composite phosphinate solution serving as an intermediate solution;
and (3) dripping a soluble metal salt solution into the intermediate solution, and precipitating, filtering and washing to obtain the dialkyl-monoalkyl composite phosphinate.
In order to better practice the present invention, further optimization is made in the above method, wherein the soluble alkali metal hypophosphite is sodium hypophosphite or potassium hypophosphite.
For better practice of the invention, further optimization is made in the above process, wherein the olefin is one or more of ethylene, propylene, butene, isobutylene or pentene.
For better practice of the invention, further optimization is made in the above method, and when the initiator is 0.01mol% to 2mol% of hypophosphite alkali metal salt, the initiator is stopped to be added dropwise.
For better implementation of the present invention, a further optimization is made in the above method, wherein the initiator is one or more of azo, peroxide and polysulfide initiators.
For better realizing the invention, the method is further optimized, and the initiator is one or more of azodiisobutyronitrile, azodiisovaleronitrile, hydrogen peroxide, di-tert-butyl peroxide, sodium persulfate, ammonium persulfate and potassium persulfate.
For better implementation of the invention, the method is further optimized, and the metal salt solution is one or more of magnesium, calcium, aluminum, iron metal sulfate, chloride, nitrate and acetate solution.
In order to better carry out the invention, a further optimization is made in the above-mentioned process, the reaction vessel being replaced at least 3 times by inert gas before the initiator solution is added dropwise.
In order to better realize the invention, the method is further optimized, and the molar ratio of the metal salt ions to the organic phosphonate ions is 1:2.1-3.1.
The dialkyl-monoalkyl composite phosphinate is prepared by the preparation method, and the proportion of the components of the monoalkyl phosphinate in the dialkyl-monoalkyl composite phosphinate is 5-20%.
The dialkyl-monoalkyl composite phosphinate is prepared by the preparation method and is used in a composite PU leather material.
Compared with the prior art, the invention has the following beneficial effects:
1. the method has the advantages that the soluble hypophosphite alkali metal salt is used as the raw material, and compared with the gas-liquid reaction, the reaction difficulty and the reaction efficiency of the gas-solid reaction are obviously improved, so that the yield can be further improved;
2. the reaction temperature and pressure are regulated while the concentration of olefin is controlled in the middle and later stages of the reaction, so that the reaction is converted into organic phosphinic acid as much as possible, the extremely low residue of phosphinate is realized, the component ratio of the monoalkylphosphinate in the dialkyl-monoalkyl composite phosphinate is controlled to be 5-20%, and the dialkyl-monoalkyl composite phosphinate with the component ratio of 5-20% can realize better flame retardant performance in polyurethane coating materials compared with single dialkyl phosphinate or single monoalkylphosphinate.
Drawings
FIG. 1 is a schematic illustration of the reaction process of a rapid preparation method of a dialkyl-monoalkyl complex phosphinate salt according to the present invention;
FIG. 2 is a nuclear magnetic resonance P spectrum of example 1 of the present invention;
FIG. 3 is a nuclear magnetic resonance P-spectrum of example 2 of the present invention;
FIG. 4 is a nuclear magnetic resonance P-spectrum of example 3 of the present invention;
FIG. 5 is a nuclear magnetic resonance P-spectrum of example 4 of the present invention;
FIG. 6 is a nuclear magnetic resonance P-spectrum of example 5 of the present invention;
FIG. 7 is a nuclear magnetic resonance P-spectrum of example 6 in the present invention;
FIG. 8 is a nuclear magnetic resonance P-spectrum of example 7 of the present invention;
FIG. 9 is a nuclear magnetic resonance P-spectrum of comparative example 1 in the present invention;
FIG. 10 is a nuclear magnetic resonance P-spectrum of comparative example 2 in the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
The invention provides a rapid preparation method of dialkyl-monoalkyl composite phosphinate, which comprises the following steps:
step S1, dissolving soluble hypophosphite alkali metal salt in water, preparing hypophosphite solution with concentration of 20-30%, and adding the hypophosphite solution into a high-pressure reaction kettle;
specifically, sodium hypophosphite or potassium hypophosphite is used as the soluble alkali metal hypophosphite.
S2, preparing an initiator solution with the concentration of 5-20%;
specifically, the initiator is one or more of azo, peroxide and polysulfide initiators;
more specifically, the initiator is one or more of azodiisobutyronitrile, azodiisovaleronitrile, hydrogen peroxide, di-tert-butyl peroxide, sodium persulfate, ammonium persulfate and potassium persulfate.
Step S3, replacing the high-pressure reaction kettle with inert gas for more than 3 times, and switching the reaction kettle from a vacuum state to olefin feeding;
specifically, the olefin is one or more of ethylene, propylene, butylene, isobutylene or pentene.
Step S4, heating the reaction kettle to 110-130 ℃ and preparing for reaction;
step S5, slowly dripping the initiator solution prepared in the step S2 into a reaction kettle, gradually increasing the olefin inlet amount, controlling the pressure in the reaction kettle to be 5-10MPa, starting stirring, initiating the addition reaction of hypophosphite and olefin under the initiation action of the initiator, maintaining the reaction at 110-130 ℃ until the molar ratio of olefin to hypophosphite is 1.2-1.4:1, cooling the reaction container to 100-110 ℃, stopping introducing olefin when the molar ratio of olefin to hypophosphite is 1.6-1.9:1, continuing dripping the initiator until the initiator is 0.01-2 mol% of hypophosphite alkali metal salt, stopping dripping the initiator, and performing constant-temperature reaction until the reaction is finished to obtain dialkyl-monoalkyl compound phosphinic acid soluble salt solution as an intermediate solution;
step S6, dripping a soluble metal salt solution into the intermediate solution, and washing and purifying for multiple times to obtain a finished dialkyl-monoalkyl composite phosphinate;
it should be noted that the molar ratio of the metal salt ion to the organic phosphonate ion is 1:2.1-3.1;
specifically, the metal salt solution is one or a mixture of magnesium, calcium, aluminum and iron metal sulfate, chloride, nitrate and acetate solutions.
Referring to fig. 1, the reaction process of the preparation method of dialkyl-monoalkyl composite phosphinate of the present invention is completed in two steps: the first step of reaction is that hypophosphite alkali metal salt and alkene complete free radical addition reaction under the action of an initiator to prepare dialkyl-monoalkyl composite phosphinic acid soluble salt solution which is used as intermediate solution, then metal salt solution is dripped into the intermediate solution to carry out the second step of reaction, and sediment obtained by double decomposition reaction is washed and dried to obtain the finished dialkyl-monoalkyl composite phosphinate.
The reaction mechanism of the invention: the free radical generated by the initiator firstly attacks active P-H bond to form hypophosphorous acid free radical and hydrogen free radical, the unsaturated bond of the olefin dissolved into water under high pressure can be attacked by the free radical, and both the hypophosphorous acid free radical and the hydrogen free radical can attack the double bond of the olefin to form monoalkylphosphinic acid free radical or alkyl free radical; at this time, the solution system contains four or more free radicals, the direct bonding between the free radicals can end the chain reaction to finish the addition, the free radicals can continuously attack active P-H bonds, both inorganic hypophosphite and monoalkylphosphinate P-H bonds can be attacked, and at this time, the differences of the attack of the inorganic hypophosphite and the monoalkylphosphinate P-H bonds can be caused by the differences of the olefin concentration, the reaction temperature or the pressure conditions. If the reaction conditions such as the concentration of olefin, the temperature and the pressure are high enough, no obvious difference exists, but the concentration of olefin and the temperature and the pressure are controlled and regulated, the monoalkylphosphinic acid part can be reserved, and the inorganic hypophosphite is attacked preferentially.
Based on the object of the invention, the control of the olefin concentration in the middle and later stages of the reaction is considered, and the reaction temperature and pressure are regulated, so that the reaction conversion is as far as possible to convert all inorganic phosphinic acid into organic phosphinic acid, the extremely low residue of phosphinate is realized, the component proportion of the monoalkyl phosphinate in the dialkyl-monoalkyl composite phosphinate is controlled to be 5-20%, and the test shows that the dialkyl-monoalkyl composite phosphinate with the component proportion of the monoalkyl phosphinate in the range of 5-20% can realize better flame retardant performance in the polyurethane coating material compared with the dialkyl phosphinate alone or the monoalkyl phosphinate alone.
Example 1:
step S1, 1060g (10 mol) of sodium hypophosphite monohydrate is dissolved in 2500 g distilled water to prepare a phosphorus source solution, and then the phosphorus source solution is transferred into a high-pressure reaction kettle;
step S2, preparing azodiisobutyronitrile into 5% ethanol solution serving as an initiator solution;
step S3, after the high-pressure reaction kettle is replaced by nitrogen for 3 times, switching the reaction kettle from a vacuum state to an ethylene steel bottle connection and introducing ethylene;
step S4, heating the reaction kettle to 110 ℃ and preparing for reaction;
step S5, slowly dripping the initiator solution prepared in the step S2 into a reaction kettle, gradually increasing the ethylene flow, starting stirring, and keeping the constant temperature at 110 ℃; after dropwise adding an initiator for 5min, lifting the flow rate of an ethylene steel bottle, regulating the pressure to 5MPa, starting to react, reducing the reaction temperature to 100 ℃ when the ethylene feeding amount reaches 336.6g (12 mol), stopping feeding ethylene when the ethylene is continuously fed to 448.8 g (16 mol), continuously dropwise adding the initiator until the initiator is 0.1mol% of sodium hypophosphite, stopping dropwise adding the initiator, and reacting at constant temperature until the reaction is finished to obtain diethyl-monoethyl compound sodium phosphinate solution serving as an intermediate solution;
and S6, transferring the intermediate solution into a double decomposition precipitation reaction kettle, starting stirring, heating to 80 ℃, dripping the solution of aluminum sulfate octadecanoate (1165 g,1.75 mol) prepared in advance into the precipitation reaction kettle, reacting at constant temperature for 1h after 2 h is dripped, filtering the precipitate while the solution is hot, and washing and purifying for multiple times to obtain 1128g of finished diethyl-monoethyl composite phosphinate with the yield of 94.9%.
Referring to fig. 2, nuclear magnetic resonance P-spectrum analysis of the composite phosphinate composition gave a diethyl phosphinate molar content of 79.34%, a monoethyl phosphinate molar content of 20.06% and an inorganic phosphinate molar content of 0.60%.
Example 2:
step S1, 1060g (10 mol) of sodium hypophosphite monohydrate is dissolved in 2500 g distilled water to prepare a phosphorus source solution, and then the phosphorus source solution is transferred into a high-pressure reaction kettle;
s2, preparing ammonium persulfate into a 20% concentration aqueous solution serving as an initiator solution;
step S3, after the high-pressure reaction kettle is replaced by nitrogen for 3 times, switching the reaction kettle from a vacuum state to an ethylene steel bottle connection and introducing ethylene;
step S4, heating the reaction kettle to 115 ℃ and preparing for reaction;
step S5, slowly dripping the initiator solution prepared in the step S2 into a reaction kettle, gradually increasing the ethylene flow, starting stirring, and keeping the constant temperature at 115 ℃; after dropwise adding an initiator for 5min, lifting the flow rate of an ethylene steel bottle, regulating the pressure to 8MPa, starting to react, reducing the reaction temperature to 105 ℃ when the ethylene feeding amount reaches 392.7g (14 mol), stopping feeding ethylene when the ethylene is continuously fed to 490.9 g (17.5 mol), continuously dropwise adding the initiator until the initiator is 1mol% of sodium hypophosphite, stopping dropwise adding the initiator, and reacting at constant temperature until the reaction is finished to obtain diethyl-monoethyl compound sodium phosphinate solution serving as an intermediate solution;
and S6, transferring the intermediate solution into a double decomposition precipitation reaction kettle, starting stirring, heating to 80 ℃, dripping the solution of the aluminum sulfate octadecanoate (1165 g,1.75 mol) prepared in advance into the precipitation reaction kettle, reacting at constant temperature for 1h after 2 h is dripped, filtering the precipitate while the solution is hot, and washing and purifying for multiple times to obtain the finished diethyl-monoethyl composite phosphinate 1171 g with the yield of 95.2%.
Referring to fig. 3, nuclear magnetic resonance P-spectrum analysis of the composite phosphinate composition gave a diethylphosphinic acid molar content of 84.05%, a monoethylphosphinic acid molar content of 14.98%, and an inorganic phosphinic acid molar content of 0.97%.
Example 3:
step S1, 1060g (10 mol) of sodium hypophosphite monohydrate is dissolved in 2500 g distilled water to prepare a phosphorus source solution, and then the phosphorus source solution is transferred into a high-pressure reaction kettle;
step S2, preparing ammonium persulfate into a 15% concentration aqueous solution serving as an initiator solution;
step S3, after the high-pressure reaction kettle is replaced by nitrogen for 3 times, switching the reaction kettle from a vacuum state to an ethylene steel bottle connection and introducing ethylene;
step S4, heating the reaction kettle to 120 ℃ and preparing for reaction;
step S5, slowly dripping the initiator solution prepared in the step S2 into a reaction kettle, gradually increasing the ethylene flow, starting stirring, and keeping the constant temperature of 120 ℃; after dropwise adding an initiator for 5min, lifting the flow of an ethylene steel bottle, regulating the pressure to 9.5MPa, starting to react, reducing the reaction temperature to 110 ℃ when the ethylene inlet amount reaches 392.7g (14 mol), stopping introducing ethylene when the ethylene is continuously introduced to 505g (18 mol), continuously dropwise adding the initiator until the initiator is 1mol% of sodium hypophosphite, stopping dropwise adding the initiator, and reacting at constant temperature until the reaction is finished to obtain diethyl-monoethyl composite sodium phosphinate solution serving as an intermediate solution;
and S6, transferring the intermediate solution into a double decomposition precipitation reaction kettle, starting stirring, heating to 80 ℃, dripping the solution of the aluminum sulfate octadecanoate (1165 g,1.75 mol) prepared in advance into the precipitation reaction kettle, reacting at constant temperature for 1h after 2 h is dripped, filtering the precipitate while the solution is hot, and washing and purifying for multiple times to obtain the finished product diethyl-monoethyl composite phosphinate 1195 g, wherein the yield is 96.0%.
Referring to fig. 4, nuclear magnetic resonance P-spectrum analysis of the composite phosphinate composition gave a diethylphosphinic acid molar content of 84.49%, a monoethylphosphinic acid molar content of 15.17%, and an inorganic phosphinic acid molar content of 0.34%.
Example 4:
step S1, 1060g (10 mol) of sodium hypophosphite monohydrate is dissolved in 2500 g distilled water to prepare a phosphorus source solution, and then the phosphorus source solution is transferred into a high-pressure reaction kettle;
step S2, preparing sodium sulfate into 15% concentration water solution serving as an initiator solution;
step S3, after the high-pressure reaction kettle is replaced by nitrogen for 3 times, switching the reaction kettle from a vacuum state to an ethylene steel bottle connection and introducing ethylene;
step S4, heating the reaction kettle to 120 ℃ and preparing for reaction;
step S5, slowly dripping the initiator solution prepared in the step S2 into a reaction kettle, gradually increasing the ethylene flow, starting stirring, and keeping the constant temperature of 120 ℃; after the initiator is dropwise added for 5min, the flow of an ethylene steel bottle is increased, the pressure is regulated to 9.5MPa, the reaction is started, when the ethylene inflow amount reaches 392.7g (14 mol), the reaction temperature is reduced to 110 ℃, when the ethylene is continuously introduced to 519 g (18.5 mol), the ethylene is stopped, the initiator is continuously dropwise added until the initiator is 1mol% of sodium hypophosphite, the initiator is stopped, the reaction is stopped at constant temperature until the reaction is finished, and diethyl-monoethyl compound sodium phosphinate solution is obtained as an intermediate solution;
and S6, transferring the intermediate solution into a double decomposition precipitation reaction kettle, starting stirring, heating to 80 ℃, dripping the solution of aluminum sulfate octadecanoate (1165 g,1.75 mol) prepared in advance into the precipitation reaction kettle, reacting at constant temperature for 1h after 2 h is dripped, filtering the precipitate while the solution is hot, and washing and purifying for multiple times to obtain the finished diethyl-monoethyl composite phosphinate 1200 g with the yield of 95.3%.
Referring to fig. 5, nuclear magnetic resonance P-spectrum analysis of the composite phosphinate composition gave a diethylphosphinic acid molar content of 89.78%, a monoethylphosphinic acid molar content of 10.12%, and an inorganic phosphinic acid molar content of 0.10%.
Example 5:
step S1, 1060g (10 mol) of sodium hypophosphite monohydrate is dissolved in 2500 g distilled water to prepare a phosphorus source solution, and then the phosphorus source solution is transferred into a high-pressure reaction kettle;
step S2, preparing ammonium persulfate into a 15% concentration aqueous solution serving as an initiator solution;
step S3, after the high-pressure reaction kettle is replaced by nitrogen for 3 times, switching the reaction kettle from a vacuum state to an ethylene steel bottle connection and introducing ethylene;
step S4, heating the reaction kettle to 120 ℃ and preparing for reaction;
step S5, slowly dripping the initiator solution prepared in the step S2 into a reaction kettle, gradually increasing the ethylene flow, starting stirring, and keeping the constant temperature of 120 ℃; after the initiator is dropwise added for 5min, the flow of an ethylene steel bottle is increased, the pressure is regulated to 9.5MPa, the reaction is started, when the ethylene inflow amount reaches 392.7g (14 mol), the reaction temperature is reduced to 110 ℃, when ethylene is continuously introduced to 525 g (18.7 mol), the ethylene is stopped, the initiator is continuously dropwise added until the initiator is 1mol% of sodium hypophosphite, the initiator is stopped, the reaction is stopped at constant temperature until the reaction is finished, and diethyl-monoethyl compound sodium phosphinate solution is obtained as an intermediate solution;
and S6, transferring the intermediate solution into a double decomposition precipitation reaction kettle, starting stirring, heating to 80 ℃, dripping the solution of the aluminum sulfate octadecanoate (1165 g,1.75 mol) prepared in advance into the precipitation reaction kettle, reacting at constant temperature for 1h after 2 h is dripped, filtering the precipitate while the solution is hot, and washing and purifying for multiple times to obtain the finished diethyl-monoethyl composite phosphinate 1209 g with the yield of 95.6%.
Referring to FIG. 6, nuclear magnetic resonance P-spectrum analysis of the composite phosphinate composition gave a diethylphosphinic acid molar content of 91.53%, a monoethylphosphinic acid molar content of 8.19%, and an inorganic phosphinic acid molar content of 0.28%.
Example 6:
step S1, 1060g (10 mol) of sodium hypophosphite monohydrate is dissolved in 2500 g distilled water to prepare a phosphorus source solution, and then the phosphorus source solution is transferred into a high-pressure reaction kettle;
step S2, preparing potassium sulfate into 15% concentration aqueous solution serving as an initiator solution;
step S3, after the high-pressure reaction kettle is replaced by nitrogen for 3 times, switching the reaction kettle from a vacuum state to an ethylene steel bottle connection and introducing ethylene;
step S4, heating the reaction kettle to 130 ℃ and preparing for reaction;
step S5, slowly dripping the initiator solution prepared in the step S2 into a reaction kettle, gradually increasing the ethylene flow, starting stirring, and keeping the constant temperature at 130 ℃; after dropwise adding an initiator for 5min, lifting the flow rate of an ethylene steel bottle, regulating the pressure to 10MPa, starting to react, reducing the reaction temperature to 110 ℃ when the ethylene feeding amount reaches 392.7g (14 mol), stopping feeding ethylene when the ethylene is continuously fed to 533 g (19 mol), continuously dropwise adding the initiator until the initiator is 2mol% of sodium hypophosphite, stopping dropwise adding the initiator, and performing constant-temperature reaction until the reaction is finished to obtain diethyl-monoethyl compound sodium phosphinate solution serving as an intermediate solution;
and S6, transferring the intermediate solution into a double decomposition precipitation reaction kettle, starting stirring, heating to 80 ℃, dripping the aluminum sulfate octadecanoate (1165 g,1.75 mol) solution prepared in advance into the precipitation reaction kettle, reacting at constant temperature for 1h after 2 h is dripped, filtering the precipitate while the solution is hot, and washing and purifying for multiple times to obtain the finished diethyl-monoethyl composite phosphinate 1203 g with the yield of 94.5%.
Referring to fig. 7, nuclear magnetic resonance P-spectrum analysis of the composite phosphinate composition gave a diethylphosphinic acid molar content of 92.28%, a monoethylphosphinic acid molar content of 7.61%, and an inorganic phosphinic acid molar content of 0.11%.
Example 7:
step S1, 1060g (10 mol) of sodium hypophosphite monohydrate is dissolved in 2500 g distilled water to prepare a phosphorus source solution, and then the phosphorus source solution is transferred into a high-pressure reaction kettle;
step S2, preparing potassium sulfate into 15% concentration aqueous solution serving as an initiator solution;
step S3, after the high-pressure reaction kettle is replaced by nitrogen for 3 times, switching the reaction kettle from a vacuum state to an ethylene steel bottle connection and introducing ethylene;
step S4, heating the reaction kettle to 120 ℃ and preparing for reaction;
step S5, slowly dripping the initiator solution prepared in the step S2 into a reaction kettle, gradually increasing the ethylene flow, starting stirring, and keeping the constant temperature of 120 ℃; after dropwise adding an initiator for 5min, lifting the flow of an ethylene steel bottle, regulating the pressure to 9.5MPa, starting to react, reducing the reaction temperature to 110 ℃ when the ethylene inlet amount reaches 392.7g (14 mol), stopping introducing ethylene when the ethylene is continuously introduced to 533 g (19 mol), continuously dropwise adding the initiator until the initiator is 1mol% of sodium hypophosphite, stopping dropwise adding the initiator, and reacting at constant temperature until the reaction is finished to obtain diethyl-monoethyl compound sodium phosphinate solution serving as an intermediate solution;
and S6, transferring the intermediate solution into a double decomposition precipitation reaction kettle, starting stirring, heating to 80 ℃, dripping the solution of the aluminum sulfate octadecanoate (1165 g,1.75 mol) prepared in advance into the precipitation reaction kettle, reacting at constant temperature for 1h after 2 h is dripped, filtering the precipitate while the solution is hot, and washing and purifying for multiple times to obtain the finished diethyl-monoethyl composite phosphinate 1217 g with the yield of 95%.
Referring to fig. 8, nuclear magnetic resonance P-spectrum analysis of the composite phosphinate composition gave a diethylphosphinic acid molar content of 94.55%, a monoethylphosphinic acid molar content of 5.04%, and an inorganic phosphinic acid molar content of 0.41%.
Comparative example 1:
step S1, 1060g (10 mol) of sodium hypophosphite monohydrate is dissolved in 2500 g distilled water to prepare a phosphorus source solution, and then the phosphorus source solution is transferred into a high-pressure reaction kettle;
step S2, preparing sodium sulfate into 15% concentration water solution serving as an initiator solution;
step S3, after the high-pressure reaction kettle is replaced by nitrogen for 3 times, switching the reaction kettle from a vacuum state to an ethylene steel bottle connection and introducing ethylene;
step S4, heating the reaction kettle to 120 ℃ and preparing for reaction;
step S5, slowly dripping the initiator solution prepared in the step S2 into a reaction kettle, gradually increasing the ethylene flow, starting stirring, and keeping the constant temperature of 120 ℃; after dropwise adding an initiator for 5min, lifting the flow of an ethylene steel bottle, regulating the pressure to 9.5MPa, starting to react, reducing the reaction temperature to 110 ℃ when the ethylene feeding amount reaches 392.7g (14 mol), stopping feeding ethylene when the ethylene is continuously fed to 421 g (15.5 mol), continuously dropwise adding the initiator until the initiator is 2mol% of sodium hypophosphite, stopping dropwise adding the initiator, and reacting at constant temperature until the reaction is finished to obtain diethyl-monoethyl compound sodium phosphinate solution serving as an intermediate solution;
and S6, transferring the intermediate solution into a double decomposition precipitation reaction kettle, starting stirring, heating to 80 ℃, dripping the aluminum sulfate octadecanoate (1165 g,1.75 mol) solution prepared in advance into the precipitation reaction kettle, reacting at constant temperature for 1h after 2 h is dripped, filtering the precipitate while the solution is hot, and washing and purifying for multiple times to obtain the finished diethyl-monoethyl composite phosphinate 1104 g with the yield of 94%.
Referring to fig. 9, nuclear magnetic resonance P-spectrum analysis of the composite phosphinate composition gave a diethylphosphinic acid molar content of 70.54%, a monoethyl phosphinic acid molar content of 27.68%, and an inorganic phosphinic acid molar content of 1.78%.
Comparative example 2:
step S1, 1060g (10 mol) of sodium hypophosphite monohydrate is dissolved in 2500 g distilled water to prepare a phosphorus source solution, and then the phosphorus source solution is transferred into a high-pressure reaction kettle;
step S2, preparing sodium sulfate into 15% concentration water solution serving as an initiator solution;
step S3, after the high-pressure reaction kettle is replaced by nitrogen for 3 times, switching the reaction kettle from a vacuum state to an ethylene steel bottle connection and introducing ethylene;
step S4, heating the reaction kettle to 120 ℃ and preparing for reaction;
step S5, slowly dripping the initiator solution prepared in the step S2 into a reaction kettle, gradually increasing the ethylene flow, starting stirring, and keeping the constant temperature of 120 ℃; after the initiator is dropwise added for 5min, the flow of an ethylene steel bottle is increased, the pressure is regulated to 9.5MPa, the reaction is started, when the ethylene inflow amount reaches 392.7g (14 mol), the reaction temperature is reduced to 110 ℃, when ethylene is continuously introduced to 575 g (20.5 mol), the ethylene is stopped, the initiator is continuously dropwise added until the initiator is 2mol% of sodium hypophosphite, the initiator is stopped, the reaction is stopped at constant temperature until the reaction is finished, and diethyl-monoethyl compound sodium phosphinate solution is obtained as an intermediate solution;
and S6, transferring the intermediate solution into a double decomposition precipitation reaction kettle, starting stirring, heating to 80 ℃, dripping the solution of the aluminum sulfate octadecanoate (1165 g,1.75 mol) prepared in advance into the precipitation reaction kettle, reacting at constant temperature for 1h after 2 h is dripped, filtering the precipitate while the solution is hot, and washing and purifying for multiple times to obtain the finished product diethyl-monoethyl composite phosphinate 1256 g, wherein the yield is 95.5%.
Referring to fig. 10, nuclear magnetic resonance P-spectrum analysis of the composite phosphinate composition gave a diethyl phosphinate mole content of 99.26%, a monoethyl phosphinate mole content of 0.48% and an inorganic phosphinate mole content of 0.26%.
The diethyl-monoethyl composite phosphinate prepared in examples 1 to 7 and comparative examples 1 to 2 were subjected to theoretical calculation and test of phosphorus content, respectively, and the test method and specific data are as follows:
theoretical phosphorus content calculation: taking the compound salt prepared by using ethylene as an olefin and aluminum sulfate as a metal salt as an example, the theoretical phosphorus content of pure diethyl aluminum phosphinate, pure diethyl aluminum phosphinate and pure inorganic aluminum phosphinate is 23.5%,30.6% and 41.86%, the corresponding proportion of each component is set to w1%, w2% and w3%, the proportion of each component is multiplied by the respective phosphorus content, and the theoretical phosphorus content P% of the compound phosphinate is obtained by adding the following formulas:
theoretical phosphorus content P% = w1% ×23.5% + w2% ×30.6% + w3% × 41.86%.
Actual phosphorus content test calculation: according to GB/T1871.1-1995 (weight and volume method for determination of phosphorus pentoxide in phosphate Ores and phosphate concentrates) the method comprises the following steps: firstly preparing an orthophosphoric acid radical solution by a high-temperature alkali fusion method, then precipitating the phosphomolybdic acid quinoline by using a quinolylmethylene citrate precipitant, determining the precipitation amount by weighing and deducting blank, measuring the phosphorus content in a sample by multiplying a conversion coefficient, dividing the calculation formula into two steps, calculating the following formula 1 to obtain the phosphorus pentoxide mass fraction, and multiplying the phosphorus pentoxide mass fraction by (30.97 x 3/141.95 (phosphorus molecular weight/phosphorus pentoxide molecular weight)), thus obtaining the phosphorus content of the sample.
Actual phosphorus content test calculation formula:
P%=30.97*3*X/141.95
the detailed steps can be seen in national standard detailed documents.
The actual test process data of phosphorus content are recorded as follows: each sample is tested for three groups of repetition, actual phosphorus content data and average values are calculated according to the above formula, the table is shown below, wherein m1, m2, m3 and m4 are all the direct weighing mass of the analytical balance, m is the weighing mass of the sample, a certain percentage is taken after the solution is prepared, and the indirect weighing result is obtained.
Table 1:
table 1, below
The theoretical phosphorus content and the actual phosphorus content of the composite phosphinate are compared with the data as follows:
table 2:
| numbering device | Flame retardant | Theoretical calculation of phosphorus content P% | Actual test of phosphorus content P% |
| 1 | Example 1 | 25.03 | 24.95 |
| 2 | Example 2 | 24.74 | 24.88 |
| 3 | Example 3 | 24.64 | 24.54 |
| 4 | Example 4 | 24.24 | 24.33 |
| 5 | Example 5 | 24.13 | 24.10 |
| 6 | Example 6 | 24.06 | 24.02 |
| 7 | Example 7 | 23.93 | 23.95 |
| 8 | Comparative example 1 | 25.79 | 25.58 |
| 9 | Comparative example 2 | 23.58 | 23.48 |
According to the table 2, the calculated result of the theoretical phosphorus content is similar to the test result of the actual phosphorus content, and the integral area ratio of the nuclear magnetic characterization diethyl component and the monoethyl component is determined to be consistent with the ratio of the actual preparation product, so that the component ratio of the composite organic phosphinate is further characterized to be in the set range.
The diethyl-monoethyl composite phosphinate prepared in examples 1 to 7 and comparative examples 1 to 2 were respectively subjected to flame retardant property test, and the test procedure was as follows:
(1) Preparing polyurethane resin as a surface middle layer coating for standby, adding 18% of the flame retardant prepared in the examples 1-7 and the comparative examples 1-2 into the bottom layer resin, and preparing for standby;
(2) Sequentially scraping and coating surface middle layer resin on release paper, drying, then scraping and coating bottom layer resin, drying 50-200 s, then semi-drying and pasting polyester base fabric, finishing after post-curing, and finishing preparation of a flame retardant material sample after pasting the base fabric firmly;
(3) Placing the prepared flame-retardant sample in the atmosphere with the temperature of 10-30 ℃ and the relative humidity of 30-80% for humidifying treatment of 12-24 h, cutting the flame-retardant sample into standard flame-retardant sample strips, and measuring;
(4) According to the requirements of GB8410-2006 combustion characteristics of automotive interior materials, the horizontal combustion evaluation flame retardant level of the fabric is tested, an object to be tested is exposed in flame for 15 s, if the object to be tested is extinguished in a first marking line, the object to be tested is A-0 mm/min, and the flame retardant level is optimal; if the fire goes out by self at 60 s and the burning distance is less than or equal to 50 mm, the fire is B grade; otherwise, the combustion speed is C-combustion speed, D-combustion speed or E;
(5) According to the requirements of GB/T5454-1997 'textile combustion performance test, oxygen index method', placing the object to be tested in vertical test condition, in the mixed gas flow of oxygen and nitrogen, measuring the minimum oxygen concentration (also called limiting oxygen index) required by the sample to maintain combustion; after the upper ignition of the material, whether the oxygen concentration is higher or lower is judged according to whether the sample is self-extinguished after ignition, whether the continuous combustion time and the smoldering time are more than 2 minutes, or whether the destroying length is more than 40 mm, and the ultimate oxygen concentration value is finally determined as a test result.
The results of the tests for horizontal burn rating and oxygen index are as follows:
table 3:
| numbering device | Flame retardant | GB8410 horizontal combustion rating | GB/T5454-1997 oxygen index/% |
| 1 | Is not added with | D or direct burn-through | 23 |
| 2 | Example 1 | A-0（Extinguishing when leaving fire | 28 |
| 3 | Example 2 | A-0 (off fire extinguishing) | 28.5 |
| 4 | Example 3 | A-0 (off fire extinguishing) | 29 |
| 5 | Example 4 | A-0 (off fire extinguishing) | 28.5 |
| 6 | Example 5 | A-0 (off fire extinguishing) | 29 |
| 7 | Example 6 | A-0 (off fire extinguishing) | 29 |
| 8 | Example 7 | A-0 (off fire extinguishing) | 28.5 |
| 9 | Comparative example 1 | A-0 (10-20 s put out) | 26.5 |
| 10 | Comparative example 2 | A-0 (5-10 s put out) | 27 |
As can be seen from table 3, after the flame retardant is added, the flame retardant performance is obviously improved; and comparing comparative example 1 and comparative example 2 with examples 1 to 7, respectively, it is known that the dialkyl-monoalkyl composite phosphinate having the molar ratio of olefin to alkyl in the range of 1.6 to 1.9:1 and the monoalkylphosphinate component in the range of 5 to 20% has more excellent flame retardant property.
The theoretical phosphorus content of pure aluminum diethylphosphinate is 23.5%, the theoretical phosphorus content of pure aluminum monoethyl phosphinate is 30.6%, and the more monoethyl components are introduced into the composite component, the higher the phosphorus content of the composite component. Comparing the flame retardant results of example 1 and comparative example 1 in table 3, it can be found that the phosphorus content of comparative example 1 is higher than that of example 1, but the flame retardant effect of comparative example 1 is rather deteriorated. It is understood that the higher the phosphorus content of the composite component is, the better the flame retardant effect is not represented.
Therefore, the synergistic effect between the dialkyl component and the monoalkyl component and the contribution of the overall phosphorus content to flame retardance are comprehensively considered, and according to the test result, the synergistic effect and the contribution of the overall phosphorus content to flame retardance are in a certain proportion range, namely the overall proportion of the monoethyl component is 5-20%, so that the purposes of high oxygen index and high-efficiency flame retardance can be realized.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A rapid preparation method of dialkyl-monoalkyl composite phosphinate, which is characterized by comprising the following steps:
dissolving soluble hypophosphite alkali metal salt in water, dropwise adding initiator solution with concentration of 5-20% into a reaction container, introducing olefin at the same time, and keeping the temperature of the reaction container at 110-130 ℃ and the pressure at 5-10MPa;
cooling the reaction vessel to 100-110 ℃ until the molar ratio of the olefin to the hypophosphite is 1.2-1.4:1, stopping introducing the olefin when the molar ratio of the olefin to the hypophosphite is 1.6-1.9:1, continuously dropwise adding the initiator, and carrying out constant-temperature reaction until the reaction is finished to obtain a dialkyl-monoalkyl composite phosphinate solution serving as an intermediate solution;
and (3) dripping a soluble metal salt solution into the intermediate solution, and precipitating, filtering and washing to obtain the dialkyl-monoalkyl composite phosphinate.
2. The rapid preparation method of dialkyl-monoalkyl composite phosphinate according to claim 1, characterized by: the soluble hypophosphite alkali metal salt adopts sodium hypophosphite or potassium hypophosphite.
3. The rapid preparation method of dialkyl-monoalkyl composite phosphinate according to claim 1, characterized by: the olefin is one or more of ethylene, propylene, butylene, isobutylene or pentene.
4. A rapid preparation method of a dialkyl-monoalkyl complex phosphinate according to any of claims 1-3, characterized in that: and stopping dripping the initiator when the initiator is 0.01-2 mol% of the hypophosphite alkali metal salt.
5. The rapid preparation method of dialkyl-monoalkyl composite phosphinate according to claim 4, characterized by comprising the following steps: the initiator is one or a mixture of more of azo initiators, peroxide initiators and polysulfide initiators.
6. The rapid preparation method of dialkyl-monoalkyl composite phosphinate according to claim 5, characterized by comprising the following steps: the initiator is one or more of azodiisobutyronitrile, azodiisovaleronitrile, hydrogen peroxide, di-tert-butyl peroxide, sodium persulfate, ammonium persulfate and potassium persulfate.
7. The rapid preparation method of dialkyl-monoalkyl composite phosphinate according to claim 1, characterized by: the metal salt solution is one or more of magnesium, calcium, aluminum, iron metal sulfate, chloride, nitrate and acetate solution.
8. The rapid preparation method of dialkyl-monoalkyl composite phosphinate according to claim 1, characterized by: the reaction vessel was replaced at least 3 times with inert gas before the initiator solution was added dropwise.
9. A dialkyl-monoalkyl complex phosphinate characterized by: the dialkyl-monoalkyl composite phosphinate obtained by the production process according to any one of claims 1 to 8, wherein the proportion of the monoalkyl phosphinate component in the dialkyl-monoalkyl composite phosphinate is 5 to 20%.
10. The application of dialkyl-monoalkyl composite phosphinate is characterized in that: a dialkyl-monoalkyl composite phosphinate obtained from the preparation process of any one of claims 1-8, which is used in a composite PU leather material.
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