CN1976941B - 含磷化合物的烷基化方法 - Google Patents
含磷化合物的烷基化方法 Download PDFInfo
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- CN1976941B CN1976941B CN2005800128165A CN200580012816A CN1976941B CN 1976941 B CN1976941 B CN 1976941B CN 2005800128165 A CN2005800128165 A CN 2005800128165A CN 200580012816 A CN200580012816 A CN 200580012816A CN 1976941 B CN1976941 B CN 1976941B
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- Prior art keywords
- acid
- methyl
- tert
- butyl ester
- azo
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 150000001875 compounds Chemical class 0.000 title claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 15
- 239000011574 phosphorus Substances 0.000 title claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 230000029936 alkylation Effects 0.000 title claims description 18
- 238000005804 alkylation reaction Methods 0.000 title claims description 18
- 150000001336 alkenes Chemical class 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 230000002152 alkylating effect Effects 0.000 claims abstract description 10
- 150000001925 cycloalkenes Chemical class 0.000 claims abstract description 10
- 239000000376 reactant Substances 0.000 claims abstract description 10
- 239000002168 alkylating agent Substances 0.000 claims abstract description 8
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims description 44
- -1 phospho Chemical class 0.000 claims description 37
- DRDKFCAHTAHYER-UHFFFAOYSA-N bis(2-methylpropyl)phosphinic acid Chemical compound CC(C)CP(O)(=O)CC(C)C DRDKFCAHTAHYER-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 8
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 8
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 claims description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 4
- VZOUAJWESDEYMF-UHFFFAOYSA-N CC(C)(C)OP(O)=O Chemical compound CC(C)(C)OP(O)=O VZOUAJWESDEYMF-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 4
- 150000003009 phosphonic acids Chemical class 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 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 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- XFFKAYOHINCUNU-UHFFFAOYSA-N 1-methylcycloheptan-1-ol Chemical compound CC1(O)CCCCCC1 XFFKAYOHINCUNU-UHFFFAOYSA-N 0.000 claims description 2
- CAKWRXVKWGUISE-UHFFFAOYSA-N 1-methylcyclopentan-1-ol Chemical compound CC1(O)CCCC1 CAKWRXVKWGUISE-UHFFFAOYSA-N 0.000 claims description 2
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 claims description 2
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- BCZXFFBUYPCTSJ-UHFFFAOYSA-L Calcium propionate Chemical compound [Ca+2].CCC([O-])=O.CCC([O-])=O BCZXFFBUYPCTSJ-UHFFFAOYSA-L 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- NXOIWSPUTXWQSM-UHFFFAOYSA-N [Na].C1(=CC=CC=C1)P(O)=O Chemical compound [Na].C1(=CC=CC=C1)P(O)=O NXOIWSPUTXWQSM-UHFFFAOYSA-N 0.000 claims description 2
- VPQOWWNEYGVVJQ-UHFFFAOYSA-N [oxido(phenoxy)phosphaniumyl]benzene Chemical compound C=1C=CC=CC=1P(=O)OC1=CC=CC=C1 VPQOWWNEYGVVJQ-UHFFFAOYSA-N 0.000 claims description 2
- HJJOHHHEKFECQI-UHFFFAOYSA-N aluminum;phosphite Chemical compound [Al+3].[O-]P([O-])[O-] HJJOHHHEKFECQI-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004330 calcium propionate Substances 0.000 claims description 2
- 235000010331 calcium propionate Nutrition 0.000 claims description 2
- BZWGENDDUSTHIR-UHFFFAOYSA-N iron phosphorous acid Chemical compound [Fe].P(O)(O)O BZWGENDDUSTHIR-UHFFFAOYSA-N 0.000 claims description 2
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 claims description 2
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 claims description 2
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- RYIOLWQRQXDECZ-UHFFFAOYSA-N phosphinous acid Chemical compound PO RYIOLWQRQXDECZ-UHFFFAOYSA-N 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
- SDQCGKJCBWXRMK-UHFFFAOYSA-N propan-2-yl 4-methylbenzenesulfonate Chemical group CC(C)OS(=O)(=O)C1=CC=C(C)C=C1 SDQCGKJCBWXRMK-UHFFFAOYSA-N 0.000 claims description 2
- SWWHCQCMVCPLEQ-UHFFFAOYSA-N propan-2-yl methanesulfonate Chemical group CC(C)OS(C)(=O)=O SWWHCQCMVCPLEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 claims description 2
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 claims description 2
- IRDFFAPCSABAGK-UHFFFAOYSA-N tert-butyl dihydrogen phosphate Chemical compound CC(C)(C)OP(O)(O)=O IRDFFAPCSABAGK-UHFFFAOYSA-N 0.000 claims description 2
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 claims description 2
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 2
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 150000003017 phosphorus Chemical class 0.000 abstract 2
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 125000002993 cycloalkylene group Chemical group 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 8
- 150000001721 carbon Chemical group 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- HAEFDDOAYBQRGK-UHFFFAOYSA-N 2-methylpropylphosphonic acid Chemical class CC(C)CP(O)(O)=O HAEFDDOAYBQRGK-UHFFFAOYSA-N 0.000 description 4
- 238000004679 31P NMR spectroscopy Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 3
- HLMXUWAUCZMWOG-UHFFFAOYSA-N 2-methyl-2-[(2-methylpropan-2-yl)oxyphosphonoyloxy]propane Chemical compound CC(C)(C)OP(=O)OC(C)(C)C HLMXUWAUCZMWOG-UHFFFAOYSA-N 0.000 description 2
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- FQFILJKFZCVHNH-UHFFFAOYSA-N tert-butyl n-[3-[(5-bromo-2-chloropyrimidin-4-yl)amino]propyl]carbamate Chemical compound CC(C)(C)OC(=O)NCCCNC1=NC(Cl)=NC=C1Br FQFILJKFZCVHNH-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- JHNJGLVSPIMBLD-UHFFFAOYSA-N dichloro(ethyl)phosphane Chemical compound CCP(Cl)Cl JHNJGLVSPIMBLD-UHFFFAOYSA-N 0.000 description 1
- CDPKWOKGVUHZFR-UHFFFAOYSA-N dichloro(methyl)phosphane Chemical compound CP(Cl)Cl CDPKWOKGVUHZFR-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
一种烷基化含磷化合物提供烷基化的含磷化合物的方法,所述的方法包括用可在引发剂存在下,原位产生链烯烃和/或环烯烃烷基化剂的反应物,烷基化具有至少一个磷氢可烃化位的含磷化合物,亚烷基和/或环亚烷基烷基化剂,烷基化含磷化合物以提供烷基化的含磷产品。
Description
相关申请的相互对照
本发明要求2004年4月23日美国临时申请序号60/564,801的优先权,其全部内容引入本发明作为参考。
发明背景
本发明涉及含磷化合物烷基化的方法。更特别,本发明涉及具有至少一个磷氢可烃化
部位的含磷化合物烷基化的方法,以提供烷基化的含磷产品,例如,单或者二烷基次膦酸或者其金属盐,烷基芳基次膦酸或者其金属盐,烷基烷基膦酸或者其金属盐,烷基或者芳基二烷基亚磷酸酯酯,烷基或者芳基烷基烷基次膦酸酯,烷基或者芳基烷基磷酸或者其金属盐,或者二烷基或者二芳基烷基磷酸酯。
为制备二烷基次膦酸衍生物,使用复杂的合成途径,包括水解乙基二氯膦以提供甲基次膦酸,随后酯化该酸以提供烷基甲基次膦酸酯。在自由基引发剂存在下,第二磷氢键也可以被烷基化。
使用二烷基次膦酸衍生物作为聚酯(聚(对苯二甲酸乙二酯)和聚(对苯二甲酸丁二酯))的阻燃剂描述于欧洲专利出版物699,708中。这些产品通过使用可水解为甲基次膦酸的甲基二氯膦的复杂过程合成;已经制备出该酸的酯并分离出来作为中间体。为制备二烷基次膦酸或者其衍生物,在自由基催化条件下,在高温下烷基次膦酸酯可以被α-烯烃烷基化。在相同的条件,在烷基次膦酸反应的情况下,仅得到歧化产品,即即烷基膦和烷基膦酸,而在温和条件下没有观察到反应。
US4,632,741描述了使用紫外线在光引发剂存在下,通过使烯烃与次磷酸盐反应制备烷基次膦酸和二烷基次膦酸盐的混合物的方法。US4,590,014描述了类似的方法,其中烯烃与次磷酸碱金属盐在自由基引发剂存在下起反应。然而,占优势的产品是单烷基次膦酸。
US6,300,516描述了通过使烯烃,特别是乙烯与烷基次膦酸或者次磷酸,在偶氮自由基引发剂存在下制备二烷基次膦酸和/或其碱金属盐的方法。该方法在具有要求专门安全性能的复杂加料***的加压反应器中进行。在大气压力下仅高沸点的烯烃可与次磷酸起反应。
次磷酸与异丁烯的反应报导在文献(S.Deprele and J-L.Montchamp,J.Org Chem.2001,66,6745)中。所述反应在化学计量的三乙基硼烷作为引发剂存在下进行。单取代的异丁基次膦酸的产率仅为38%。
发明内容
本发明的目的是提供一种具有至少一个磷氢可烃化部位的含磷化合物的烷基化的方法。
本发明一个特别的目的是提供这样一种方法,使用短链烷基作为烷基化剂,导致在较短时间内得到高产率希望的烷基化产品,同时避免与以上讨论的已知方法有关的上述缺点。
本发明的这些及其他目的通过本发明烷基化
的方法实现,所述的方法包括用可在自由基引发剂存在下,原位产生链烯烃和/或环烯烃烷基化剂的反应物,烷基化具有至少一个磷氢可烃化位的含磷化合物,所述链烯烃和/或环烯烃烷基化剂烷基化含磷化合物以提供烷基化的含磷产品。
不意欲被束缚,认为原位产生链烯烃或者环烯烃的反应物,在烷基化条件下可产生足够浓度的这些化合物,导致起始的含有机磷化合物中含有的至少一个磷氢可烃化位烷基化,随着在烷基化反应中链烯烃/环烯烃消耗,平衡向产生额外的链烯烃/环烯烃方向移动。
本发明的详细说明
本发明中用作起始反应物之一的含磷化合物必须包括至少一个磷氢可烃化位,而
在烷基化含磷产品可以是部分或者完全烷基化这样情况下,可以包括多于一个这样的位。
在本发明一个实施方式中,所述含磷起始反应物由通式(I)表示:
其中:
X1,如果存在,是
和x2,如果存在,是
其中,R1是H,高达30个碳原子的烷基,3-12个碳原子的环烷基,或者6-20个碳原子的芳基;Me是化合价v为1,2,3或者4的金属;R2是H,高达30个碳原子烷基,3-12个碳原子的环烷基,或者6-20个碳原子的芳基,和,
a,b,c,d,e和f每一个独立为0或者1,
条件是:
当a=1,c=1时,b=0,
当b=1,a=0时,x1不存在,
当f=1,d=1时,e=0,和
当e=1,f=0时,x2不存在。
特别有用的含磷化合物(I)是结构式(1)-(6)的那些:
其中R1,R2,Me和v具有上述的含义。在上述结构式中,R1优选H,R2优选H(除了在结构式1的化合物中,其中仅R1可以是H)或者1-8个碳原子的烷基,Me优选是锂,钠,钾,镁,钙,钡,铝,钛,钒,铬,钼,铁,镍,钴,铜,或者锌。
本发明例证性的可烃化的含磷起始反应物是膦酸(亚磷酸);次磷酸;次膦酸;三价膦酸;上述的酯,比如膦酸叔丁基酯,膦酸二叔丁酯,膦酸甲酯,膦酸苯酯,次膦酸叔丁酯,甲基次膦酸苯酯,苯次膦酸苯酯,等等;上述的金属盐,比如次磷酸钠,次磷酸钙,次磷酸锌,次磷酸铝,亚磷酸钠,亚磷酸氢钙,亚磷酸锌,亚磷酸铝,亚磷酸铁,苯次膦酸钠,甲基次膦酸钠,等等。
在本发明另外的实施方式中,原位产生链烯烃或者环烯烃的反应物由如下通式表示:
R4-X (II)
其中:
R4是最多30个碳原子的烷基,或者3-12个碳原子的环烷基,和,X是卤素,-OH,
其中,R5和R6每一个独立为H,最多30个碳原子的烷基,3-12个碳原子的环烷基,或者6-20个碳原子的芳基,g是0或者1。
在反应物(II)中,R4优选是支链烷基,因为支链更容易提供链烯烃烷基化剂。
例证性的有用卤化物R4-X是2-氯代-2-甲基丙烷,2-溴代-2-甲基丙烷,2-氯丙烷,2-溴丙烷,叔戊基氯,叔戊基溴,等等。
有用的醇结构R4-OH包括叔丁醇,叔戊醇,异丙醇,2-丁醇,2-丁烯-1-醇,2-甲基-3-丁烯-2-醇。同样适当的是环醇,特别是,1-甲基环戊醇,1-甲基环庚醇,1-甲基环辛醇,和1-甲基环癸醇。
有用的酯结构:
包括醋酸叔丁酯,磷酸叔丁基酯,膦酸叔丁基酯,膦酸二叔丁酯,二异丁基次膦酸叔丁酯,甲苯磺酸异丙酯,甲磺酸异丙酯,等等。
作为自由基引发剂,有利的利用偶氮化合物。优选,偶氮化合物是阳离子的和/或非阳离子的偶氮化合物。优选,作为阳离子的偶氮化合物,使用2,2′-偶氮二(2-脒基丙烷)二盐酸化物,或者2,2′-偶氮二(N,N′-二亚甲基异丁基脒)二盐酸化物。优选,作为非阳离子的偶氮化合物,使用偶氮二(异丁腈)(AIBN),4,4′-偶氮二(4-氰基戊酸)或者2,2′-偶氮二(2-甲基丁腈)。
优选,作为自由基引发剂,使用无机过氧化物和/或有机过氧化物自由基引发剂。
优选,作为无机过氧化物自由基引发剂,使用过氧化氢,过二硫酸铵和/或过二硫酸钾。
优选,作为有机过氧化物自由基引发剂,使用过氧化二苯酰,二叔丁基过氧化物,过氧苯甲酸叔丁酯和/或过乙酸。
优选,使用紫外线单独引发,或者与以上提到的引发剂结合使用。
优选,所述反应在羧酸或者无机酸存在下进行。特别优选,所述羧酸是乙酸,所述无机酸是硫酸。
优选,所述反应在约25-约130℃温度下进行。特别优选,所述反应在约60℃-约120℃温度下进行。优选,所述反应在大气压力下进行。如果原位产生,那么链烯烃往往从反应容器中蒸发,之后与P-H反应,而在这样情况下,可以使用冷凝器以使链烯烃返回所述反应容器中。或者,施加约1-2个大气压的压力以阻止所述链烯烃的蒸发。
本发明同样特别是涉及一种方法,其中在偶氮自由基引发剂存在下,或者在过氧化物自由基引发剂存在下,次磷酸或者次磷酸钠与叔丁醇或者醋酸叔丁酯起反应,得到二异丁基次膦酸和/或其钠盐作为主要产品。
本发明同样涉及由上述方法获得的二烷基次膦酸和/或其碱金属盐在制备这样的金属如Mg,Ca,Al,Zn,Fe(II),Fe(III),Cu(II),Zr(IV)的盐中的用途。这些盐用作热塑性聚合物比如聚(对苯二甲酸乙二酯),聚(对苯二甲酸丁二酯),聚苯乙烯,聚酰胺,聚乙烯,聚丙烯等,热固性树脂比如环氧,酚醛或者双马来酰亚胺树脂等的阻燃剂。由上述方法获得的二烷基次膦酸和/或其碱金属盐同样用作制药工业的中间体。
本发明方法通过随后的实施例说明。
实施例1
向250ml配备有冷凝器,加料漏斗,磁性搅拌器和温度计的三颈烧瓶中,加入47.79g(0.362mol)50%的工业次磷酸,45.94g(0.395mol)醋酸叔丁酯和3.2g AIBN。反应混合物加热到61℃,搅拌3小时。其后,第二份8.7g的AIBN的乙酸溶液逐渐地加入,同时在11个小时内反应混合物的温度缓慢升高到84℃。在加入完成之后,31P NMR分析表明:形成了8%的二异丁基次膦酸,63%的异丁基次膦酸和29%的次磷酸。所述反应混合物由氢氧化钠水溶液中和,然后用含水的氢氧化铝处理,或者直接与氧化铝起反应。过滤去得到的白色沉淀,用水洗涤,在烘箱中干燥,因此得到23g异丁基次膦酸的铝盐。如果希望,所述母液可以回收用于制备另外大量的产品。
实施例2
向500ml配备有冷凝器,加料漏斗,磁性搅拌器和温度计的三颈烧瓶中加入65.80g(0.498mol)50%的工业次磷酸,和79.92g(1.08mol)的叔丁醇。所述反应混合物加热到70℃,开始加入2.06g的AIBN的35g乙酸溶液。在6小时之后,加入完成。31P NMR确定所述混合物包含50%的异丁基次膦酸和50%的次磷酸。用乙酸中的第二份5.5g的AIBN和5.7g的过氧苯甲酸叔丁酯处理所述混合物,同时温度在10小时内逐渐地增加到97℃。在加入完成之后,发现所述混合物包括75%的二异丁基次膦酸,20%的异丁基次膦酸和5%的异丁基膦酸。所述混合物在旋转蒸发仪真空75℃下干燥,除去水和溶剂,用温水洗涤三次。分离上层油相,在旋转蒸发仪真空75℃下干燥。收集到57.5g含油物质,在室温下结晶。基于次磷酸的产率为65%,不回收利用母液。如果希望,所述母液可以回收用于制备另外的大量产品。
实施例3
向配备有冷凝器,加料漏斗,机械搅拌器和温度计的2L四颈烧瓶中,加入321.35g(3.03mol)的次磷酸钠一水化物和637g乙酸。在溶液变清澈之后,逐渐地向所述混合物中加入149.33g硫酸,观察到淤浆。在104-110℃温度下,在14.5小时内缓慢加入由458.18g(6.186mol)叔丁醇,107.85g乙酸和18.63g(0.13mol)二叔丁基过氧化物组成的溶液。由31P核磁共振分析混合物显示出它包含58mol%的二异丁基次膦酸和42mol%的单异丁基次膦酸。由31P核磁共振分析确定存在不可测量的次磷酸。然后除去一部分溶剂。在103-111℃温度下,在7小时内,向所述反应混合物中加入包括98.80g(1.33mol)叔丁醇,5.87g(0.040mol)二叔丁基过氧化物和23.7g乙酸的另外的溶液。31P核磁共振分析表明混合物为73%的二异丁基次膦酸和25%的单异丁基次膦酸,残余物由单异丁基膦酸和亚磷酸组成。
实施例4
过滤上述实施例3中获得的烷基化产品混合物,在旋转蒸发仪真空下洗提去溶剂。然后液体混合物连续地用200ml水,200ml 2.7%碳酸钠洗涤三次,和200ml水洗涤两次。分离上层,在真空下旋转蒸发仪中干燥。在室温下一经放置所述材料就结晶,得到350g纯二异丁基次膦酸。产率是65%。
实施例5
一部分上述纯二异丁基次膦酸(135.01g,0.758mol)与水混合,用稀氢氧化钠水溶液中和。所述中和产品然后与61.83g(0.256mol)的AlCl3·6H2O的2L的水溶液混合。观察到大量的白色沉淀。过滤所述沉淀,在烘箱中105℃下干燥至恒重。获得139.43g的白色二异丁基次膦酸铝盐粉末。产率是98.9%。
实施例6
向配备有冷凝器,加料漏斗,机械搅拌器和温度计的1L四颈烧瓶中,加入187.52g(1.77mol)次磷酸钠一水化物和294乙酸。在所述溶液变清澈之后,向其中逐渐地加入88.18g的硫酸,观察到淤浆。在111-118℃温度下,在6小时内,缓慢加入由150.81g(2.03mol)叔丁醇,16.97g乙酸和6.35g(0.043mol)二叔丁基过氧化物组成的溶液。31P核磁共振分析混合物显示出混合物由13mol%的二异丁基次膦酸,72mol%的单异丁基次膦酸和13%的次磷酸组成。在104-111℃温度下,在14.5小时内,向反应混合物中加入包括156.577g(2.11mol)叔丁醇,11.86g二叔丁基过氧化物(0.081mol)和160.29g乙酸酐的另外的溶液,同时从第二个漏斗加入13.71g硫酸。得到87.5%的二异丁基次膦酸,9.5%的单异丁基次膦酸,1.6%的单异丁基膦酸和1.4%亚磷酸的混合物。
实施例7
首先过滤上述实施例6中获得的烷基化产品混合物,然后在旋转蒸发仪中在100℃浴温下洗提。得到302g溶液。该溶液的一部分(233g,总的1.37mol P)用稀氢氧化钠中和,加入到2.5L 4%氯化铝水溶液(0.435mol,AlCl3·6H2O)中。过滤得到的白色沉淀,在75℃烘箱中干燥过夜。获得214g的白色二异丁基次膦酸,单异丁基次膦酸和单异丁基膦酸铝盐粉末。
实施例8
向配备有冷凝器,加料漏斗,机械搅拌器和温度计的2L四颈烧瓶中,加入211.76g(2.00mol)的次磷酸钠一水化物和317g乙酸。在所述溶液变清澈之后,向混合物中逐渐地加入106.97g硫酸,观察到淤浆。然后所述混合物加热到120℃。在115-120℃温度下,在5小时内,缓慢加入由243.19g(2.09mol)的醋酸叔丁酯和7.35g(0.050mol)的二叔丁基过氧化物组成的溶液。31P核磁共振分析所述混合物显示出所述混合物包含11mol%的二异丁基次膦酸,72mol%的单异丁基次膦酸和17mol%的次磷酸。加入另外的20.12g硫酸。在114-120℃温度下,在10小时内,向所述反应混合物中加入包括310.73g(2.68mol)的醋酸叔丁酯,和13.10g(0.090mol)的二叔丁基过氧化物的另外的溶液。31P核磁共振分析表明所述混合物包含88%的二异丁基次膦酸,10%单异丁基次膦酸,残余物由单异丁基膦酸和亚磷酸组成。
实施例9
过滤上述实施例8中获得的烷基化产品混合物,在真空下旋转蒸发仪中洗提溶剂。液体与100ml甲苯混合,连续地分别用200ml水,150ml 3.8%的碳酸钠洗涤三次,100ml水洗涤两次。分离上层,在真空下旋转蒸发仪中干燥。在室温下一经放置层就结晶,得到288g纯二异丁基次膦酸。产率是81%。
尽管参考特定实施方式描述了本发明的方法,但本领域的普通技术人员可以理解:在不背离本发明范围的前提下,可以进行不同的变化,而且等同物可以取代本发明的要素。另外,在不背离本发明实质范围的前提下,根据本发明的教导,可以进行许多改变以适应特定的情形或者材料。因此,意欲本发明并不被限制于公开的作为实施本发明方法预期最佳方式的特定实施方式,而是本发明将包括所有的在附加权利要求范围内的实施方式。
Claims (3)
1.一种烷基化含磷化合物提供烷基化的含磷化合物的方法,所述方法包括在引发剂存在下,用原位产生链烯烃和/或环烯烃烷基化剂的反应物,烷基化含磷化合物,所述链烯烃和/或环烯烃烷基化剂烷基化含磷组分以提供烷基化的含磷产品,
其中所述引发剂是至少一种自由基引发剂,紫外线或者其组合,
其中所述含磷化合物是如下的至少一员:膦酸,次磷酸,次膦酸,三价膦酸,膦酸叔丁基酯,膦酸二叔丁基酯,膦酸甲酯,膦酸苯酯,次膦酸叔丁基酯,甲基次膦酸苯酯,苯次膦酸苯酯,次磷酸钠,次磷酸钙,次磷酸锌,次磷酸铝,亚磷酸钠,亚磷酸氢钙,亚磷酸锌,亚磷酸铝,亚磷酸铁,苯次膦酸钠和甲基次膦酸钠,
其中原位产生链烯烃和/或环烯烃的反应物是如下的至少一员:2-氯代-2-甲基丙烷,2-溴代-2-甲基丙烷,2-氯丙烷,2-溴丙烷,叔戊基氯,叔戊基溴,叔丁醇,叔戊醇,异丙醇,2-丁醇,2-丁烯-1-醇,2-甲基-3-丁烯-2-醇,1-甲基环戊醇,1-甲基环庚醇,1-甲基环辛醇,1-甲基环癸醇,醋酸叔丁酯,磷酸叔丁基酯,膦酸叔丁基酯,膦酸二叔丁基酯,二异丁基次膦酸叔丁基酯,甲苯磺酸异丙酯和甲磺酸异丙酯,和
其中所述自由基引发剂是选自如下的至少一种:2,2′-偶氮二(2-脒基丙烷)二盐酸化物,2,2′-偶氮二(N,N′-二亚甲基异丁基脒)二盐酸化物,偶氮二(异丁腈),4,4′-偶氮二(4-氰基戊酸),2,2′-偶氮二(2-甲基丁腈),过氧化氢,过二硫酸铵,过二硫酸钾,过氧化二苯酰,二叔丁基过氧化物和过乙酸。
2.权利要求1所述的方法,在羧酸和/或无机酸存在下进行。
3.权利要求1所述的方法,其中所述烷基化反应在25℃-130℃温度和在大气压到最高达2大气压的压力下进行。
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CN101891762A (zh) * | 2010-06-30 | 2010-11-24 | 南开大学 | 二乙基次膦酸盐的制备方法及应用 |
DE102010047790A1 (de) * | 2010-09-14 | 2012-03-15 | Clariant International Ltd. | Phosphorhaltige Mischungen, Verfahren zu deren Herstellung und ihre Verwendung |
DE102011121591A1 (de) | 2011-12-16 | 2013-06-20 | Clariant International Ltd. | Gemische aus Dialkylphosphinsäuren und Alkylphosphonsäuren, ein Verfahren zu deren Herstellung und ihre Verwendung |
DE102014001222A1 (de) * | 2014-01-29 | 2015-07-30 | Clariant lnternational Ltd | Halogenfreie feste Flammschutzmittelmischung und ihre Verwendung |
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KR101213544B1 (ko) | 2012-12-18 |
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US8097747B2 (en) | 2012-01-17 |
CN1976941A (zh) | 2007-06-06 |
US20090054675A1 (en) | 2009-02-26 |
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TWI371454B (en) | 2012-09-01 |
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