CN103172668A - Monoalkyl/dialkyl phosphinate and preparation method thereof - Google Patents
Monoalkyl/dialkyl phosphinate and preparation method thereof Download PDFInfo
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- CN103172668A CN103172668A CN2013100686596A CN201310068659A CN103172668A CN 103172668 A CN103172668 A CN 103172668A CN 2013100686596 A CN2013100686596 A CN 2013100686596A CN 201310068659 A CN201310068659 A CN 201310068659A CN 103172668 A CN103172668 A CN 103172668A
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- CN
- China
- Prior art keywords
- monoalkyl
- initiator
- preparation
- dialkylphosphinic salts
- alkene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000003999 initiator Substances 0.000 claims abstract description 48
- 150000003839 salts Chemical class 0.000 claims abstract description 46
- 150000001336 alkenes Chemical class 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 239000012429 reaction media Substances 0.000 claims abstract description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 77
- -1 pentyl ester Chemical class 0.000 claims description 75
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 20
- 239000004160 Ammonium persulphate Substances 0.000 claims description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 13
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000005502 peroxidation Methods 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- MUPIEMDDBGZNRU-UHFFFAOYSA-N C(C)(C)C(=O)O.C(C)(C)(C)OO Chemical compound C(C)(C)C(=O)O.C(C)(C)(C)OO MUPIEMDDBGZNRU-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003063 flame retardant Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- VXHFNALHLRWIIU-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)OC(=O)C(C)(C)C VXHFNALHLRWIIU-UHFFFAOYSA-N 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001451 organic peroxides Chemical class 0.000 claims description 4
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 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 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- UBPJIDNMDZEGBK-UHFFFAOYSA-N benzoyl benzenecarboperoxoate formic acid Chemical group C(C1=CC=CC=C1)(=O)OOC(C1=CC=CC=C1)=O.C(=O)O UBPJIDNMDZEGBK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001941 cyclopentenes Chemical group 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 150000004978 peroxycarbonates Chemical class 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 abstract description 11
- 238000010438 heat treatment Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 238000005406 washing Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- 238000013019 agitation Methods 0.000 description 16
- 239000004411 aluminium Substances 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- 238000001816 cooling Methods 0.000 description 15
- 238000010792 warming Methods 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000012065 filter cake Substances 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 231100000987 absorbed dose Toxicity 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 239000011575 calcium Substances 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 5
- 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 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 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 description 2
- BCZXFFBUYPCTSJ-UHFFFAOYSA-L Calcium propionate Chemical compound [Ca+2].CCC([O-])=O.CCC([O-])=O BCZXFFBUYPCTSJ-UHFFFAOYSA-L 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000004330 calcium propionate Substances 0.000 description 2
- 235000010331 calcium propionate Nutrition 0.000 description 2
- JJPBKCZJVYSKGV-UHFFFAOYSA-N diethoxyphosphane Chemical compound CCOPOCC JJPBKCZJVYSKGV-UHFFFAOYSA-N 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910001381 magnesium hypophosphite Inorganic materials 0.000 description 2
- SEQVSYFEKVIYCP-UHFFFAOYSA-L magnesium hypophosphite Chemical compound [Mg+2].[O-]P=O.[O-]P=O SEQVSYFEKVIYCP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- WJSPKNSMGLBHBW-UHFFFAOYSA-N C1C2C=CCCC12 Chemical compound C1C2C=CCCC12 WJSPKNSMGLBHBW-UHFFFAOYSA-N 0.000 description 1
- 239000007977 PBT buffer Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000006886 vinylation reaction Methods 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
- 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
- C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
- C07F9/4808—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
- C07F9/4816—Acyclic saturated acids or derivatices which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention discloses monoalkyl/dialkyl phosphinate and a preparation method thereof. The method comprises the steps that: organic solvent-water is adopted as a reaction medium; under the effect of an initiator I, hypophosphite is subjected to a reaction with alkene I under a temperature of 70-90 DEG C, such that monoalkyl phosphinate is obtained; the temperature is increased to 90-110 DEG C by heating; the obtained monoalkyl phosphinate is subjected to a reaction with alkene II under the effect of an initiator II, such that dialkyl phosphinate is obtained; Or, organic solvent-water is adopted as a reaction medium; under the effect of an initiator III, hypophosphite is subjected to a reaction with alkene III under a temperature of 70-120 DEG C, such that dialkyl phosphinate is obtained. The hypophosphite is hypophosphorous acid salt of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, or Sr. According to the invention, the reaction period is short, obtained monoalkyl/dialkyl phosphinate can be precisely controlled, a total yield is high, and product purity is high. When the product is salified, the contents of other salts are low. The product is easy to wash.
Description
Technical field
The present invention relates to a kind of monoalkyl/dialkylphosphinic salts and preparation method thereof.
Background technology
Monoalkyl phosphinates and dialkylphosphinic salts, be widely used as fire retardant, can be synthesized by diverse ways.In the novel method of the research of organo phosphorous compounds-phosphorus oxide acylation reaction-synthetic dialkyl phosphonic acids and derivative thereof, (Chinese science B collects Yuan Chengye etc., 1984, 12, 1088 ~ 1092) and Lin Qiang etc. by quantitatively synthetic phospho acid (the Central South University's journal (natural science edition) of dialkyl phosphine oxide, 1987, 18(6), 697) describe the Grignard reagent method in and generated the phosphonous acid diethyl ester by phosphorus trichloride and ethanol synthesis, phosphonous acid diethyl ester and self-control Grignard reagent react and are hydrolyzed and obtain the dialkyl group phosphine oxide, can obtain dialkyl phosphinic acid after dialkyl group phosphine oxide and oxidant reaction acidifying.The product purity of this method is higher, but this method production technique is comparatively loaded down with trivial details, reaction time is long, and especially cost is high and productive rate is low, thus to making it be difficult to realize suitability for industrialized production.
Patent DE4430932 disclose two replace metal phosphinates at polyester as fire retardant, DE19910232, two patents of US6248921, disclose a kind of two preparation methods that replace metal phosphinates.U.S. Pat 6359171B1 discloses a kind of preparation method of dialkyl phosphinic acid aluminium, at first the method adopts yellow phosphorus to synthesize monoalkyl phosphonate, then utilize free radical to cause after vinylation to be hydrolyzed sour after and the aluminium reactant salt obtain dialkyl phosphinic acid aluminium fire retardant.
Chinese patent CN98811622.7, CN98811626.X, CN98811627.8 etc. disclose with a hydration sodium hypophosphite or the 50% Hypophosporous Acid, 50 aqueous solution in acetic acid medium, by azo initiator or peroxide initiator, cause it and ɑ-olefine reaction prepares dialkyl phosphinic acid and metal-salt thereof.This method is reacted in acetic acid medium, its speed of response is very fast, but solvent acetic acid and a hydration the sodium hypophosphite particularly water in 50% Hypophosporous Acid, 50 make the aftertreatment very difficulty that becomes after miscible, and because there is the existence of water to make the easy cancellation inactivation of radical initiator, make and need to add more radical initiator and just can make to have reacted, when increasing cost, make the side reaction of reaction process increase.
Chinese patent CN200410104692.0 discloses and has adopted the free radical initiation in acidic aqueous solution of a hydration sodium hypophosphite or 50wt% Hypophosporous Acid, 50 solution to prepare dialkyl phosphinic acid and metal-salt thereof with ɑ-olefine reaction.This scheme is carried out in water, and aftertreatment is few, but makes the easy cancellation inactivation of radical initiator, and reaction time is long.
Above invention, all with Hypophosporous Acid, 50 or Hypophosporous Acid, 50 an alkali metal salt, after being prepared into dialkyl phosphinic acid or dialkyl phosphinic acid an alkali metal salt, could be prepared into the throw out of dialkyl phosphinic acid alkaline earth salt or other salt in water after still needing further to be processed.And the aforesaid method gained be essentially the dialkyl phosphinic acid hydrochlorate, be difficult to obtain monoalkyl phosphinates or the Hypophosporous Acid, 50 that comparatively content is higher.
Summary of the invention
For the shortcoming and deficiency that overcome prior art, the object of the invention is to provide the preparation method of monoalkyl/dialkylphosphinic salts that a kind of technical process is simple, reaction time is short, overall yield is high, product purity is high.
The present invention is achieved by the following technical solutions:
A kind of preparation method of monoalkyl/dialkylphosphinic salts, comprise the steps:
Take organic solvent-water as reaction medium, is to react under 70 ~ 90 ℃ with alkene I in temperature by hypophosphite under initiator I effect, obtains the monoalkyl phosphinates;
Or, take organic solvent-water as reaction medium, by hypophosphite, under initiator I effect, with alkene I, in temperature, be to react under 70 ~ 90 ℃, obtain the monoalkyl phosphinates, be heated to 90 ~ 110 ℃, the monoalkyl phosphinates obtained is reacted with alkene II under initiator II effect, obtain dialkylphosphinic salts;
Or, take organic solvent-water as reaction medium, by hypophosphite, under initiator III effect, with alkene III, in temperature, be to react under 70 ~ 120 ℃, obtain dialkylphosphinic salts;
The Mg that described hypophosphite is Hypophosporous Acid, 50, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Sr salt.
Described organic solvent and water can mix also can be immiscible, with the molten organic solvent of water, is wherein methyl alcohol, ethanol, propyl alcohol, Virahol, acetone and/or tetrahydrofuran (THF); With the immiscible organic solvent of water, be wherein benzene,toluene,xylene, ether, trichloromethane and/or hexanaphthene; Phase transition wherein is water-fast organic solvent phase-water-solid-state phase of gaseous olefin phase-hypophosphite, or the water-soluble organic solvent liquid phase of mixing with water-solid-state phase of gaseous olefin phase-hypophosphite.
The mass ratio of described organic solvent and water is 0.1:1 ~ 5:1, is preferably 0.5:1 ~ 2:1.
Described initiator I, initiator II are identical with initiator III;
Described initiator I, initiator II are different with initiator III;
The mol ratio of described initiator I, initiator II and initiator III and hypophosphite is 0.001 ~ 0.1:1.
Described initiator I, initiator II and initiator III are azo-initiator, organic peroxide evocating agent or inorganic peroxide initiator.
Described azo-initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile);
Described organic peroxide evocating agent is benzoyl peroxide formic acid, peroxidation lauric acid, ditertiary butyl peroxide, peroxycarbonates, mistake oxalic acid, tert-butyl hydroperoxide isobutyrate, the peroxidation trimethylacetic acid tert-butyl ester or the special pentyl ester of peroxidation;
Described inorganic peroxide initiator is ammonium persulphate, Sodium Persulfate or Potassium Persulphate.
Described alkene I, alkene II and alkene III are identical or different, are naphthenic alkene or the carbonatoms ɑ-alkene that is 2 ~ 20.
Described ɑ-alkene is selected from one or more the mixture in ethene, propylene, butylene, iso-butylene or amylene.
Described naphthenic alkene is cyclopentenes or tetrahydrobenzene.
The mol ratio of described hypophosphite and alkene I, for being less than 1:1, is preferably 1:1.01 ~ 1.5;
The mol ratio of described hypophosphite and alkene II, for being less than 1:1, is preferably 1:1.01 ~ 1.5;
The mol ratio of described hypophosphite and alkene III, for being less than 1:2, is preferably 1:2.01 ~ 2.5;
The mass ratio of described hypophosphite and water is 1:1 ~ 50, is preferably 1:2 ~ 10, more preferably 1:2.5 ~ 5; Reaction pressure is 0.5MPa ~ 6MPa, is preferably 0.6MPa ~ 2.5MPa.
Monoalkyl/dialkylphosphinic salts that above-mentioned preparation method obtains separates from mixture by filtration or centrifugal treating.
The invention also discloses the purposes of a kind of monoalkyl/dialkylphosphinic salts prepared by above-mentioned preparation method as fire retardant.
The invention also discloses a kind of flame-proofed polymer material that above-mentioned preparation method prepares, comprise 5 ~ 20wt% monoalkyl/dialkylphosphinic salts, 50 ~ 70wt% polymkeric substance or its mixture, 0 ~ 30wt% glass fibre, other auxiliary agents of 0 ~ 5wt%;
Wherein, R
1, R
2identical or different, be expressed as H, ethyl, propyl group, butyl, amyl group, cyclopentyl, cyclohexyl or octyl group, condition is that both can not be H simultaneously;
M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr or Sr;
M is 2 ~ 4; Described polymer materials can be PBT, PET, PC, PA, PS etc.
The present invention compared with prior art, has following beneficial effect:
1) the present invention directly be take the target hypophosphite and is reacted as raw material, and single stage method obtains corresponding monoalkyl phosphinates and dialkylphosphinic salts flame retardant products.
2) reaction time of the present invention extremely short, the shortlyest can obtain at 3 ~ 5 hours monoalkyl phosphinates product, the shortlyest can obtain at 8 ~ 9 hours the dialkylphosphinic salts product.
3) the present invention prepares the monoalkyl phosphinates of gained, and productive rate is the highest approaches 95%; Simultaneously the dialkylphosphinic salts productive rate is high, the highlyest approaches 97%.
4) technical process of the present invention is simple, and after the product salify, other salts contgs are few, is easy to washing.
Embodiment
Further illustrate the present invention below by embodiment, following examples are preferably embodiment of the present invention, but embodiments of the present invention are not subject to the restriction of following embodiment.
Wherein, in embodiment, the products obtained therefrom productive rate is all calculated by following formula:
The calculation of yield formula:
Wherein, w is productive rate, and m is product gained quality, and n is the hypophosphite mole number, and M is molecular weight product.
embodiment 1: structure and the preparation thereof of ethyl phospho acid aluminium
By hypo-aluminum orthophosphate 444.1g(2mol), 500mL water, 500mL ethanol and 10.0g, 0.044mol ammonium persulphate adds in high-pressure reactor, airtight, under agitation use nitrogen (0.5MPa) to replace 5 times, after ethene is adjusted to 2.5MPa and is filled with by voltate regulator, be heated to 72 ℃, evenly be warming up to 75 ℃ and squeeze into 5.0g with volume pump in 4h, 0.022mol the solution that ammonium persulphate and 30mL water are mixed with, be incubated 1 hour again under 75 ℃, cooling emptying, obtain mixed system 1559.6g, be equivalent to the ethene absorbed dose and be the 175.5g(theoretical amount 104.5%),
The gained mixed system filters, and with 1000mL water washing 2 times, the gained filter cake obtains ethyl phospho acid aluminium: 583.7g in 5 hours 130 ℃ of lower vacuum-dryings, productive rate 95.37%, and wherein, the structural formula of ethyl phospho acid aluminium is:
31p-NMR analyzes (in the sample vitriolization):
Ethyl phospho acid mol content: 95.6%
Diethyl phospho acid mol content: 3.1%
Other mol content: 1.3%.
embodiment 2: structure and the preparation thereof of diethyl phospho acid aluminium
By hypo-aluminum orthophosphate 444g(2mol), 300mL water, 700mL ethanol and 10.0g, 0.044mol ammonium persulphate adds in high-pressure reactor, airtight, under agitation use nitrogen (0.5MPa) to replace 5 times, after ethene is adjusted to 2.5MPa and is filled with by voltate regulator, be heated to 72 ℃, evenly be warming up to 75 ℃ and squeeze into continuously 5.0g with volume pump, the solution that 0.022mol ammonium persulphate and 30mL water are mixed with in 4 hours; 4.5 after hour, be heated to 95 ℃, evenly be warming up to 110 ℃ and squeeze into continuously with volume pump the solution that 15.0g ammonium persulphate and 90mL water are mixed with in 4 hours, be incubated 1 hour again under 110 ℃, cooling emptying, obtain mixed system 1794.1g, be equivalent to the ethene absorbed dose and be the 347.1g(theoretical amount 103.3%);
The gained mixed system filters, with 1000mL water washing 2 times, filter cake within 5 hours, obtain diethyl phospho acid aluminium: 755.2g 130 ℃ of lower vacuum-dryings, productive rate 96.82%, wherein, the structural formula of diethyl phospho acid aluminium is:
31p-NMR analyzes (in the sample vitriolization):
Diethyl phospho acid mol content: 98.5%
Ethyl phospho acid mol content: 0.3%
Ethyl-butyl Hypophosporous Acid, 50 mol content: 0.8%
Other mol content: 0.4%.
embodiment 3: structure and the preparation thereof of diethyl phospho acid aluminium
By hypo-aluminum orthophosphate 444.0g(2.00mol), 500mL water and 500mL methyl alcohol adds in high-pressure reactor, airtight, under agitation use nitrogen (0.5MPa) to replace 5 times, after ethene is adjusted to 2.5MPa and is filled with by voltate regulator, be heated to 95 ℃, evenly with volume pump, squeezed into 20.0g in 9 hours, 0.088mol the solution that ammonium persulphate and 120mL water are mixed with, and evenly be warming up to 110 ℃, be incubated 1 hour again under 110 ℃, cooling emptying, obtain mixed system 1832.1g, be equivalent to the ethene absorbed dose and be the 353.1g(theoretical amount 105.1%);
The gained mixed system filters, and with 1000mL water washing 2 times, the gained filter cake obtains diethyl phospho acid aluminium: 751.0g in 5 hours 130 ℃ of lower vacuum-dryings, productive rate 96.27%, and wherein, the structural formula of diethyl phospho acid aluminium is:
31p-NMR analyzes (in the sample vitriolization):
Diethyl phospho acid mol content: 93.9 %
Ethyl phospho acid mol content: 0.4%
Ethyl-butyl Hypophosporous Acid, 50 mol content: 5.2%
Other mol content: 0.5%.
embodiment 4: structure and the preparation thereof of ethyl-butyl phospho acid aluminium
By hypo-aluminum orthophosphate 444.0g(2.00mol), 500mL water, 700mL Virahol and 10.0g, 0.044mol ammonium persulphate adds in high-pressure reactor, airtight, under agitation use nitrogen (0.5MPa) to replace 5 times, after ethene is adjusted to 2.5MPa and is filled with by voltate regulator, be heated to 72 ℃, evenly be warming up to 75 ℃ and squeeze into 5.0g with volume pump in 4h, 0.022mol the solution that ammonium persulphate and 30mL water are mixed with, then be incubated 1 hour, cooling emptying under 75 ℃; Reheat to 105 ℃, in high-pressure reactor, be filled with n-butene, maintain pressure at 2.5MPa, in 4h, evenly volume pump is squeezed into 10g, 0.044mol the solution that ammonium persulphate and 60mL water are mixed with, after 110 ℃ the insulation 2 hours, cooling emptying, the mixed system obtained is filtered, with 1000mL water washing 1 time, the gained filter cake obtains ethyl-butyl phospho acid aluminium: 904.7g, productive rate 95.43% in 5 hours 130 ℃ of lower vacuum-dryings, wherein, the structural formula of ethyl-butyl phospho acid aluminium is:
31p-NMR analyzes (in the sample vitriolization):
Ethyl-butyl phospho acid mol content: 96.0 %
Diethyl phospho acid mol content: 2.5%
Ethyl phospho acid mol content: 0.5%
Other mol content: 1.0%.
embodiment 5: structure and the preparation thereof of butyl phospho acid iron
By ferric hypophosphite 502.0g(2.00mol), 500mL water, 500mL hexanaphthene and 12.8g, 0.04mol, 50% tert-butyl hydroperoxide isobutyrate adds in high-pressure reactor, airtight, under agitation use nitrogen (0.5MPa) to replace 5 times, after butylene 350g is filled with, be heated to 80 ℃, evenly be warming up to 85 ℃ and squeeze into 6.4g with volume pump in 4h, 0.02mol, the solution that 50% tert-butyl hydroperoxide isobutyrate and 50mL hexanaphthene are mixed with, be incubated 1 hour again under 85 ℃, cooling emptying, the mixed system obtained is filtered, by 1000mL washing with alcohol 1 time, use again the 1000mL water washing 2 times, the gained filter cake obtains butyl phospho acid iron: 730.6g in 5 hours 130 ℃ of lower vacuum-dryings, productive rate 86.57%, wherein, the structural formula of butyl phospho acid iron is:
31p-NMR analyzes (in the sample vitriolization):
Butyl phospho acid mol content: 93.1%
Dibutyl phospho acid mol content: 5.3%
Other mol content: 1.6%.
embodiment 6: structure and the preparation thereof of dibutyl phospho acid iron
By ferric hypophosphite 502.0g(2.00mol), 500mL water and 500mL toluene add in high-pressure reactor, airtight, under agitation use nitrogen (0.5MPa) to replace 5 times, after butylene 700g is filled with, be heated to 95 ℃, evenly with volume pump, squeezed into 19.2g in 7 hours, 0.06mol, the solution that 50% tert-butyl hydroperoxide isobutyrate and 100mL toluene are mixed with, and evenly be warming up to 110 ℃, be incubated 1 hour again under 110 ℃, cooling emptying, the mixed system obtained is filtered, by 1000mL washing with alcohol 1 time, use again the 1000mL water washing 2 times, the gained filter cake obtains dibutyl phospho acid iron: 1034.2g in 5 hours 130 ℃ of lower vacuum-dryings, productive rate 87.64%, wherein, the structural formula of dibutyl phospho acid iron is:
31p-NMR analyzes (in the sample vitriolization):
Dibutyl phospho acid mol content: 97.5%
Butyl phospho acid mol content: 1.2%
Other mol content: 1.3%.
embodiment 7: structure and the preparation thereof of n-propyl phospho acid magnesium
By magnesium hypophosphite 465.0g(3.00mol), 500mL water, 500mL benzene and 12.8g, 0.04mol, 50% tert-butyl hydroperoxide isobutyrate adds in high-pressure reactor, airtight, under agitation use nitrogen (0.5MPa) to replace 5 times, after propylene is adjusted to 1.5MPa and is filled with by voltate regulator, be heated to 80 ℃, evenly be warming up to 85 ℃ and squeeze into 6.4g with volume pump in 4h, 0.02mol, the solution that 50% tert-butyl hydroperoxide isobutyrate and 50mL benzene are mixed with, be incubated 1 hour again under 85 ℃, cooling emptying, obtain mixed system 1729.8g, be equivalent to positive propylene absorbed dose and be the 261.6g(theoretical amount 103.8%),
The gained mixed system filters, and uses 1000mL washing with alcohol 1 time, then uses the 1000mL water washing 2 times, and the gained filter cake obtains n-propyl phospho acid magnesium: 492.6g in 5 hours 130 ℃ of lower vacuum-dryings, productive rate 68.47%, and wherein, the structural formula of n-propyl phospho acid magnesium is:
31p-NMR analyzes (in the sample vitriolization):
N-propyl phospho acid mol content: 94.3%
Dipropyl phospho acid mol content: 3.8%
Other mol content: 1.9%.
embodiment 8: structure and the preparation thereof of dipropyl phospho acid magnesium
Magnesium hypophosphite 465.0g (3.00mol), 200mL water and 800mL ether are added in high-pressure reactor, airtight, under agitation use nitrogen (0.5MPa) to replace 5 times, after propylene is adjusted to 1.5MPa and is filled with by voltate regulator, be heated to 95 ℃, evenly with volume pump, squeezed into 13.0g in 7 hours, 0.089mol the solution of ditertiary butyl peroxide and the configuration of 100mL ether, and evenly be warming up to 110 ℃, be incubated 1 hour again under 110 ℃, cooling emptying, obtain mixed system 1834.8g, be equivalent to the ethene absorbed dose and be the 515.1g(theoretical amount 102.2%);
The mixed system of gained filters, and uses 1000mL washing with alcohol 1 time, then uses the 1000mL water washing 2 times, and the gained filter cake obtains dipropyl phospho acid magnesium: 847.6g in 5 hours 130 ℃ of lower vacuum-dryings, productive rate 87.21%, and wherein the structural formula of dipropyl phospho acid magnesium is:
31p-NMR analyzes (in the sample vitriolization):
Dipropyl phospho acid mol content: 93.6 %
Propyl group phospho acid mol content: 3.7%
Other mol content: 2.7%.
embodiment 9: structure and the preparation thereof of ethyl phospho acid calcium
By calcium propionate 510.0g(3.00mol), 200mL water, 800mL ethanol and 10.0g, 0.044mol ammonium persulphate adds in high-pressure reactor, airtight, under agitation use nitrogen (0.5MPa) to replace 5 times, after ethene is adjusted to 2.5MPa and is filled with by voltate regulator, be heated to 72 ℃, evenly be warming up to 75 ℃ and squeeze into 5.0g with volume pump in 4h, 0.022mol the solution that ammonium persulphate and 30mL water are mixed with, be incubated 1 hour again under 75 ℃, cooling emptying, obtain mixed system 1564.6g, be equivalent to the ethene absorbed dose and be the 177.6g(theoretical amount 105.7%),
The gained mixed system filters, and with 1000mL water washing 2 times, the gained filter cake obtains ethyl phospho acid calcium: 408.7g in 5 hours 130 ℃ of lower vacuum-dryings, productive rate 60.29%, and wherein, the structural formula of ethyl phospho acid calcium is:
31p-NMR analyzes (in the sample vitriolization):
Ethyl phospho acid mol content: 91.7%
Diethyl phospho acid mol content: 6.0%
Other mol content: 2.3%.
embodiment 10: structure and the preparation thereof of diethyl phospho acid calcium
By calcium propionate 510g(3mol), 800mL water and 200mL propyl alcohol add in high-pressure reactor, airtight, under agitation use nitrogen (0.5MPa) to replace 5 times, after ethene is adjusted to 2.5MPa and is filled with by voltate regulator, be heated to 95 ℃, evenly with volume pump, squeezed into 19.2g in 7 hours, 0.02mol, the solution that 50% tert-butyl hydroperoxide isobutyrate and 100mL propyl alcohol are mixed with, and evenly be warming up to 110 ℃, be incubated 1 hour again under 110 ℃, cooling emptying, obtain mixed system 1920.7g, be equivalent to the ethene absorbed dose and be the 351.5g(theoretical amount 104.6%),
The gained mixed system filters, and with 1000mL water washing 2 times, the gained filter cake obtains diethyl phospho acid calcium: 721.4g in 5 hours 130 ℃ of lower vacuum-dryings, productive rate 85.28%, and wherein, the structural formula of diethyl phospho acid calcium is:
31p-NMR analyzes (in the sample vitriolization):
Diethyl phospho acid mol content: 97.8%
Ethyl phospho acid mol content: 1.2%
Other mol content: 1.0%
embodiment 11: structure and the preparation thereof of ethyl phospho acid zinc
By zinc hypophosphite 585g(3mol), 500mL water, 500mL dimethylbenzene and 7.7g, 0.044mol the peroxidation trimethylacetic acid tert-butyl ester adds in high-pressure reactor, airtight, under agitation use nitrogen (0.5MPa) to replace 5 times, after ethene is adjusted to 2.5MPa and is filled with by voltate regulator, be heated to 72 ℃, evenly be warming up to 75 ℃ and squeeze into volume pump the solution that the 3.8g peroxidation trimethylacetic acid tert-butyl ester and 30mL dimethylbenzene are mixed with in 4h, be incubated 1 hour again under 75 ℃, cooling emptying, obtain mixed system 1724.9g, be equivalent to the ethene absorbed dose and be the 172.9g(theoretical amount 102.9%),
The gained mixed system filters, and uses 1000mL washing with alcohol 1 time, then uses the 1000mL water washing 2 times, and the gained filter cake obtains ethyl phospho acid zinc: 694.5g in 5 hours 130 ℃ of lower vacuum-dryings, productive rate 91.39%, and wherein, the structural formula of ethyl phospho acid zinc is:
31p-NMR analyzes (in the sample vitriolization):
Ethyl phospho acid mol content: 93.9%
Diethyl phospho acid mol content: 4.8%
Other mol content: 1.3%.
embodiment 12: structural formula and the preparation thereof of diethyl phospho acid zinc
By zinc hypophosphite 585g(3mol), 500mL water and 500mL trichloromethane add in high-pressure reactor, airtight, under agitation use nitrogen (0.5MPa) to replace 5 times, after ethene is adjusted to 2.5MPa and is filled with by voltate regulator, be heated to 95 ℃, evenly with volume pump, squeezed into 15.3g in 7 hours, 0.088mol the solution that the peroxidation trimethylacetic acid tert-butyl ester and 100mL trichloromethane are mixed with, and evenly be warming up to 110 ℃, be incubated 1 hour again under 110 ℃, cooling emptying, obtain mixed system 2352.1g, be equivalent to the ethene absorbed dose and be 351.8 g(theoretical amount 104.7%),
The gained mixed system filters, and uses 1000mL washing with alcohol 1 time, then uses the 1000mL water washing 2 times, and the gained filter cake obtains diethyl zinc hypophosphite: 857.5g in 5 hours 130 ℃ of lower vacuum-dryings, productive rate 93.11%, and wherein, the structural formula of diethyl phospho acid zinc is:
31p-NMR analyzes (in the sample vitriolization):
Diethyl phospho acid mol content: 97.5%
Ethyl phospho acid mol content: 1.4%
Other mol content: 1.1%.
comparative Examples 1
Get 360.6g50wt% Hypophosporous Acid, 50 (2.732mol) and 4.7g(0.027mol, 1.0%mol) the peroxidation trimethylacetic acid tert-butyl ester adds in autoclave together, the enclosed high pressure still, under agitation use nitrogen (0.5MPa) to replace 5 times, after ethene is adjusted to 2.5MPa and is filled with by voltate regulator, under agitation be heated to 72 ℃, evenly add 9.4g(0.054mol in 14h, 2.0%mol) the peroxidation trimethylacetic acid tert-butyl ester, and evenly be warming up to 85 ℃, cooling and the emptying by this reactor, obtain product water solution 508.9g;
31p-NMR analyzes diethyl phospho acid mol content: 74.1%
Ethyl phospho acid mol content: 23.8%
Other mol content: 2.1%
300g water and high density alkyl phosphinic acid 557.9g obtained above are added in reactor and stir, with the neutralization of 30%wt aqueous sodium hydroxide solution, obtain, post-heating to 95 ℃, by 303.3g(0.455mol) Tai-Ace S 150 is dissolved in the 700mL aqueous solution and in 1 hour and splashes into, and after dripping off, insulation 1 hour under 90 ~ 95 ℃, be cooled to room temperature, the gained solid is leached, and, with 700mL water washing three times, at 150 ℃, be dried to constant weight, obtain 295.7g alkyl phosphinic acid aluminium.
comparative Examples 2
Get 289.6g mono-hydration sodium hypophosphite (2.732mol), 500g acetic acid and 4.4g(0.027mol, 1.0%mol) Diisopropyl azodicarboxylate adds in autoclave together, the enclosed high pressure still, under agitation use nitrogen (0.5MPa) to replace 5 times, after ethene is adjusted to 2.5MPa and is filled with by voltate regulator, under agitation be heated to 75 ℃, evenly added 6.7(0.041mol in 10 hours, 1.5%mol) Diisopropyl azodicarboxylate, and evenly be warming up to 85 ℃, cooling and the emptying by this reactor, obtain solution 926.3g, 130 ℃ of underpressure distillation 2 hours, obtain the 453.1g dope,
31p-NMR analyzes (in the sample vitriolization):
Diethyl phospho acid mol content: 91.3%
Ethyl-butyl phospho acid mol content: 2.1%
Ethyl phospho acid mol content: 3.1
Other mol content: 3.5%
To be dissolved in the 750mL water of 80 ℃ and add in reactor with 453.1g dope obtained above, be heated with stirring to 95 ℃, by 303.3g(0.455mol) Tai-Ace S 150 is dissolved in the 700mL aqueous solution and in 1 hour and splashes into, be incubated 1 hour after dripping off under 90 ~ 95 ℃, be cooled to room temperature, the gained solid is leached, and with 700mL water washing three times, be dried to constant weight at 150 ℃, obtain the 338.9g white powder, overall yield 95.41%.
Monoalkyl/the dialkylphosphinic salts of embodiment 1 ~ 14 and Comparative Examples 1 ~ 2 gained is mixed by weight 10:60:25:5 with PBT, glass, auxiliary agent at 230 ~ 260 ℃, from Bitruder, extrude, make flame-proofed thermoplastic polymer in-mold moulding material, its combustionproperty and mechanical property are tested in sample preparation, record result and see table 1:
The moulding material combustionproperty that table 1 monoalkyl/dialkylphosphinic salts makes and mechanical property parameters table
Each performance test is undertaken by following standard:
Tensile strength: GB1040-1992 plastic tensile method for testing performance;
Flexural strength: GB9341-2000 Plastics-Oetermination of flexural properties method;
Amount of deflection: GB9341-2000 Plastics-Oetermination of flexural properties method;
Combustionproperty: UL94 Plastics Combustion performance test;
From table 1 known, moulding material stretching, bending and flame retardant properties that monoalkyl/dialkylphosphinic salts prepared by preparation method of the present invention makes are superior, are applicable to make the polymer in-mold moulding material.
Claims (18)
1. the preparation method of a monoalkyl/dialkylphosphinic salts, is characterized in that, comprises the steps:
Take organic solvent-water as reaction medium, is to react under 70 ~ 90 ℃ with alkene I in temperature by hypophosphite under initiator I effect, obtains the monoalkyl phosphinates;
Or, take organic solvent-water as reaction medium, by hypophosphite, under initiator I effect, with alkene I, in temperature, be to react under 70 ~ 90 ℃, obtain the monoalkyl phosphinates, be heated to 90 ~ 110 ℃, the monoalkyl phosphinates obtained is reacted with alkene II under initiator II effect, obtain dialkylphosphinic salts;
Or, take organic solvent-water as reaction medium, by hypophosphite, under initiator III effect, with alkene III, in temperature, be to react under 70 ~ 120 ℃, obtain dialkylphosphinic salts;
Wherein, Mg, the Ca that described hypophosphite is Hypophosporous Acid, 50, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Sr salt.
2. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, it is characterized in that, described organic solvent is selected from one or more mixtures of methyl alcohol, ethanol, propyl alcohol, Virahol, acetone, tetrahydrofuran (THF), benzene,toluene,xylene, ether, trichloromethane, hexanaphthene.
3. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, described organic solvent and water are molten.
4. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, described organic solvent and water are immiscible.
5. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, the mass ratio of described organic solvent and water is 0.1:1 ~ 5:1, is preferably 0.5:1 ~ 2:1.
6. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, described initiator I, initiator II are identical with initiator III.
7. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, described initiator I, initiator II are different with initiator III.
8. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, the mol ratio of described initiator I, initiator II and initiator III and hypophosphite is 0.001 ~ 0.1:1.
9. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, described initiator I, initiator II and initiator III are azo-initiator, organic peroxide evocating agent or inorganic peroxide initiator.
10. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 9, is characterized in that, described azo-initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile); Described organic peroxide evocating agent is benzoyl peroxide formic acid, peroxidation lauric acid, ditertiary butyl peroxide, peroxycarbonates, mistake oxalic acid, tert-butyl hydroperoxide isobutyrate, the peroxidation trimethylacetic acid tert-butyl ester or the special pentyl ester of peroxidation; Described inorganic peroxide initiator is ammonium persulphate, Sodium Persulfate or Potassium Persulphate.
11. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, described alkene I, alkene II and alkene III are identical or different, are naphthenic alkene or the carbonatoms ɑ-alkene that is 2 ~ 20.
12. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 11, is characterized in that, described ɑ-alkene is selected from one or more the mixture in ethene, propylene, butylene, iso-butylene or amylene; Described naphthenic alkene is cyclopentenes or tetrahydrobenzene.
13. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, the mol ratio of described hypophosphite and alkene I, for being less than 1:1, is preferably 1:1.01 ~ 1.5; The mol ratio of described monoalkyl phosphinates and alkene II, for being less than 1:1, is preferably 1:1.01 ~ 1.5; The mol ratio of described hypophosphite and alkene III, for being less than 1:2, is preferably 1:2.01 ~ 2.5.
14. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, the mass ratio of described hypophosphite and water is 1:1 ~ 50, is preferably 1:2 ~ 10, more preferably 1:2.5 ~ 5.
15. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, described reaction pressure is 0.5MPa ~ 6MPa, is preferably 0.6MPa ~ 2.5MPa.
16. the monoalkyl/dialkylphosphinic salts prepared by the described preparation method of claim 1 ~ 15 any one, have following structure formula I,
Wherein, R
1, R
2identical or different, be expressed as H, ethyl, propyl group, butyl, amyl group, cyclopentyl, cyclohexyl or octyl group, condition is that both can not be H simultaneously;
M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr or Sr;
M is 2 ~ 4.
17. monoalkyl/dialkylphosphinic salts that the preparation method of monoalkyl/dialkylphosphinic salts as claimed in claim 16 prepares is as the purposes of fire retardant.
18. a kind of flame-proofed polymer material that the preparation method of monoalkyl/dialkylphosphinic salts as claimed in claim 16 prepares, comprise 5 ~ 20wt% monoalkyl/dialkylphosphinic salts, 50 ~ 70wt% polymkeric substance or its mixture, 0 ~ 30wt% glass fibre, other auxiliary agents of 0 ~ 5wt%; Wherein, monoalkyl/dialkylphosphinic salts has following structure formula I,
Wherein, R
1, R
2identical or different, be expressed as H, ethyl, propyl group, butyl, amyl group, cyclopentyl, cyclohexyl or octyl group, condition is that both can not be H simultaneously; M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr or Sr; M is 2 ~ 4.
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| PCT/CN2013/075743 WO2014134874A1 (en) | 2013-03-04 | 2013-05-16 | Monoalkyl/dialkyl phosphinates and preparation method therefor |
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