CN101048344A - Process for the preparation of highly purified, dialkyl phosphinic acids - Google Patents
Process for the preparation of highly purified, dialkyl phosphinic acids Download PDFInfo
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- CN101048344A CN101048344A CN 200580036551 CN200580036551A CN101048344A CN 101048344 A CN101048344 A CN 101048344A CN 200580036551 CN200580036551 CN 200580036551 CN 200580036551 A CN200580036551 A CN 200580036551A CN 101048344 A CN101048344 A CN 101048344A
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- 239000002253 acid Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 53
- 150000007513 acids Chemical class 0.000 title claims abstract description 39
- 230000008569 process Effects 0.000 title abstract description 8
- 238000002360 preparation method Methods 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 150000001336 alkenes Chemical class 0.000 claims abstract description 16
- 239000004711 α-olefin Substances 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000012074 organic phase Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000008346 aqueous phase Substances 0.000 claims abstract description 4
- 230000006872 improvement Effects 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000000460 chlorine 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- 238000007614 solvation Methods 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- 150000007522 mineralic acids Chemical class 0.000 claims 2
- 230000020477 pH reduction Effects 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 239000012264 purified product Substances 0.000 abstract 1
- -1 acids compound Chemical class 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 229910052761 rare earth metal Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 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 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000003203 everyday effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 2
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- CWPKTBMRVATCBL-UHFFFAOYSA-N 3-[1-[1-[(2-methylphenyl)methyl]piperidin-4-yl]piperidin-4-yl]-1h-benzimidazol-2-one Chemical compound CC1=CC=CC=C1CN1CCC(N2CCC(CC2)N2C(NC3=CC=CC=C32)=O)CC1 CWPKTBMRVATCBL-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 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
- 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 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- JHQYNYXQKSKNAK-UHFFFAOYSA-N OP(O)O.OP(O)O Chemical compound OP(O)O.OP(O)O JHQYNYXQKSKNAK-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- KOXDJHNIAMEYHX-UHFFFAOYSA-N [PH2](O)=O.P(O)O Chemical compound [PH2](O)=O.P(O)O KOXDJHNIAMEYHX-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- JSYGRUBHOCKMGQ-UHFFFAOYSA-N dichloramine Chemical compound ClNCl JSYGRUBHOCKMGQ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000003845 household chemical Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical group 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000007082 phosphination reaction Methods 0.000 description 1
- UXBZSSBXGPYSIL-UHFFFAOYSA-N phosphoric acid;yttrium(3+) Chemical compound [Y+3].OP(O)(O)=O UXBZSSBXGPYSIL-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 206010039073 rheumatoid arthritis Diseases 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KDNCILYKSYKEFJ-UHFFFAOYSA-N sodium;benzenesulfonyl(chloro)azanide Chemical compound [Na+].Cl[N-]S(=O)(=O)C1=CC=CC=C1 KDNCILYKSYKEFJ-UHFFFAOYSA-N 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- WBJSMHDYLOJVKC-UHFFFAOYSA-N tetraphenyllead Chemical compound C1=CC=CC=C1[Pb](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WBJSMHDYLOJVKC-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Abstract
In a process for the production of dialkylphosphinic acids, especially branched, dialkylphosphinic acids in high purity via the reaction of an alpha olefin with a hypophosphorous acid or a salt thereof, the improvement comprising conducting the reaction in the presence of a stoichiometric excess of the olefin and isolating and purifying the desired dialkylphosphinic acid product by neutralizing the monoalkylphosphinic acid by-product with an aqueous base; removing the aqueous phase in which the neutralized monoalkylphosphinic acid is preferentially solubilized; acidifying the dialkyl product in the organic phase; and isolating the purified product.
Description
The right of priority that present patent application requires is that on October 25th, 2004 submitted to, application number is 60/621,972 temporary patent application.
Technical field
The present invention relates in general to the method for a kind of improved economization production dialkylphosphinic acids (dialkylphosphinic acid) compound (being preferably the dialkylphosphinic acids compound of branching).This method can be implemented single phase separation, thereby obtains the highly purified, dialkyl phosphinic acids product.
Background technology
The known multiple derivative that has organic phosphonous acid (phosphinic Acid), these derivatives have sizable commercial value, and have multiple useful application.For example, organic phosphinate (or ester) (phosphinate) and acid be: effectively wetting agent and washing composition; The softening agent of multiple plastics and resin; The tamanori of pitch and similar mixtures thereof; The laking agent of grease and lubricating oil and oxidation retarder (United States Patent (USP) 3,001,938); Inhibiter; Flame-proofness; Flotation aid; The metal extraction agent; Calcium sulphate retarder; And the textile auxiliary agent such as fiber stabilizer (United States Patent (USP) 3,374,288).
It is very important and in demand precursor, intermediate product and final product that highly purified highly branched dialkylphosphinic acids is known as in many special-purpose fields especially.For example, the dialkylphosphinic acids of branching has been served as: complex compound forms agent; The medical active material particularly is suitable for treating the degeneration (for example rheumatoid arthritis) in inflammation and joint those (United States Patent (USP) 4,524,211); General agricultural and household chemical product comprise plant-growth regulator, sterilant, weedicide; And static inhibitor.Even if be not in all these are used, at least also be in multiple these are used, because the thermolability of the reactivity of the phosphorus-hydrogen partial in the monoalkylphosphinic acid by-product and this compounds makes that the existence of monoalkylphosphinic acid by-product is deleterious.
Because above listed multiple feasible practical application, thus to the synthetic needs that produced of simple industrial of the dialkylphosphinic acids of producing these highly purified states.Because aforesaid huge commercial value makes people develop the several different methods of organic phosphonous acid of preparation and phosphinate (or ester) thereof.Although the difference of independent step is all very big in these methods, considerable method all uses the reaction of phosphorus-halogen compounds to obtain C.Can be by making the reaction of haloalkane and phosphuret-(t)ed hydrogen although be well known that all the time, or use Ge Shi (Grignard) reagent to form this key, these methods are for being unpractical with commercial-scale operation.
People such as Stiles have disclosed a kind of utilization and have contained the compound of olefinic double bonds and a class is preferably produced phosphinate (or ester) by the reaction between the compound shown in the formula (I) method (United States Patent (USP) 2,724,718), and formula (I) is:
Wherein Z represents the monovalence alkyl of not fatty family Multiple Bonds, or represents the univalent inorganic cation;
Y represent hydrogen atom, not fatty family Multiple Bonds the monovalence alkyl or-the OZ group, wherein Z is defined as above.The hydrocarbyl carbonate of Hypophosporous Acid, 50 (hypophosphorous acid) salt, the hydrocarbyl carbonate of Hypophosporous Acid, 50, organic phosphonous acid and the list of phosphorous acid (phosphorous acid) or dialkyl ester are all within the scope as the Phosphorus and phosphorus compound of reactant that people such as Stiles propose.A particularly preferred subclass comprises an alkali metal salt of Hypophosporous Acid, 50, sodium hypophosphite for example, people such as Stiles find to make this material and contain at the most the alkene direct addition of 14 carbon atoms and " but produce water soluble detergent with basal ration ground in the operation steps in a single step.”
People such as Stiles are also noted that 1-alkene demonstrates higher slightly speed of reaction than other alkene in these methods.The described addition reaction of people such as Stiles is by causing in the presence of the free radical that contacts closely with reactant.According to people's such as Stiles instruction, temperature of reaction and reaction pressure are all inessential.
People such as Stiles instruction, need be with mole: the calculating of mole be carried out under the situation of addition, preferably makes reactant for waiting mol ratio approximately or making phosphorus compound excessive usually; (for example) institute's bonded olefin(e) compound in the product is exceeded under one mole the situation, preferably making the excessive olefin compound and the ratio of phosphorus compound is 1 mole of about 2 to 3 mol ratio.
A.J.Robertson (United States Patent (USP) 4,374,780) alkene that has disclosed by two moles (is specially 2,4,4 '-2,4,4-Trimethyl-1-pentene-1), with two moles hydrogen peroxide the reaction product of phosphuret-(t)ed hydrogen is oxidized to phosphonous acid subsequently with phosphine gas generation free radical addition, produce highly branched dialkylphosphinic acids, promptly two-2,4,4 '-tri-methyl-amyl phosphonous acid.Yet, must realize phosphuret-(t)ed hydrogen and alkene at high proportion with high phosphuret-(t)ed hydrogen pressure (promptly up to about 1000psig) according to disclosing, and thereby reduce unnecessary three-2,4,4 '-tri-methyl-amyl phosphonous acid by product is because the formation of any this by product all is that overall yield is suffered a loss.In addition, it is believed that temperature is extremely important for the exothermic oxidation stage, because if temperature surpasses about 120 ℃, extra monoalkyl-phosphinous acid is just sloughed and formed to alkyl group; If temperature is lower than about 50 ℃, will cause the reaction times long.It is said the dialkylphosphinic acids productive rate that simple distillation can realize.
Certainly, monoalkyl and dialkylphosphinic acids can also be by using the hydrolysis required at least one quantitative water of stoichiometry under about 160 ℃ to 300 ℃ temperature, make its separately the alkyl ester hydrolytic scission and form, the phosphorus-to-carbon bonds of wherein said alkyl ester at first forms by alternate manner.The alkanol that forms one of hydrolysate is removed (United States Patent (USP) 4,069,247) by distillation usually from reaction mixture.
Phostonic acid also is used to extracting rare-earth element (United States Patent (USP) 5,639,433).Be used for from the conventional process of rare earth element solution (the particularly acidic solution of rare earth element) separation of rare earth elements, material solution is usually to the ore that contains rare earth element (monazite for example, hamartite, xenotime, bauxite and similar raw ore) treating processes.The extract that will contain the rare earth element after the extraction is usually sent into the washer dilute acid wash, then the rare earth element that obtains is sent into securing device (stopper) so that carry out stripping with denseer acid, with separation of rare earth elements.In the prior art, hydrochloric acid is the preferred acid of washing and stripping extract.It is said that two-(2,4, the 4-tri-methyl-amyl) phosphonous acid are preferred extraction agents, are preferred for separation of cobalt from nickel especially.
In addition, end-use about dialkylphosphinic acids and ester thereof, United States Patent (USP) 6,165,427 have disclosed and have used the mixture precipitation and reclaim soluble heavy metal, for example lead, cadmium, zinc class and their mixture from waste water stream that contains two-(n-octyl) phosphonous acid sodium and two-(dodecyl) phosphonous acid sodium.According to instruction, advantageously, make its dissolving by handling throw out with dense hydroxide aqueous solution, in (for example) separatory funnel, contact resulting solution then organophosphorated salt is regenerated from throw out with diethyl ether.Stir and being separated subsequently after, present two-phase.One is the concentration of metal water higher than feedstock solution that it comprised mutually.Another is the ethereal solution of precipitation agent mutually.After the ether evaporation, dialkylphosphinic acids sodium is regenerated.
Usually by adding the organic materials (United States Patent (USP) 4,434,108) such as Di Iso Propyl Ether or sherwood oil, the purifying of evaporate repeatedly subsequently, phostonic acid and its ester being finished in crystallization and filtration (United States Patent (USP) 4,524,211).
Inherent subject matter is extremely difficult dialkylphosphinic acids to be separated with the monoalkyl reaction product that forms together in the aforementioned art methods, and this is because they have very close water-soluble.By being applicable to that practical reaction method production of high purity in the next life dialkylphosphinic acids of producing the compound with multiple structure (particularly highly branched dialkyl group structure) is art-recognized problem, this problem is not resolved so far yet.
Therefore, the objective of the invention is by providing some conditions that a kind of practical and effective treatment process that solves this technical problem is provided, wherein by the condition that is provided in the simple free radical reaction of alpha-olefin one Hypophosporous Acid, 50 or its salt, by simple neutralization/be separated, from dialkylphosphinic acid product, remove any monoalkyl-phosphinous acid and other water-soluble impurity of existence, and need not organic solvent additive as the 3rd component.
From follow-up specification sheets and appended claims, other purpose is conspicuous.
Summary of the invention
The present invention relates to a kind of method, wherein can use the reaction process and the device (promptly need not High Temperature High Pressure) of standard, and need not extra organic solvent interpolation step and additional removal process and device (this recovery for extra solvent is necessary), simple water extraction/separating technology, come easily dialkylphosphinic acids of synthesis of high purity (the particularly dialkylphosphinic acids of branching) and salt (or ester) thereof.
Can produce highly purified dialkylphosphinic acids by following steps through improved this method: make alpha-olefin and some phosphorus compound generation free radical reaction, wherein use excessive olefin so that provide solvent medium, separate dialkylphosphinic acids by all monoalkylphosphinic acid by-product of preferential neutralization subsequently as reaction product; Wash with water and extract dialkylphosphinic acids; By the dialkylphosphinic acids that the technology well known in the art such as acidifying, filtration and distillation is separated from the excessive olefin reactant solvents and purifying is required.
Described method realizes by following process: at first, use excessive alpha-olefin, it has played the effect of the optimum solvation medium phase of dialkylphosphinic acids subsequently; Next recognizes, by producing a kind of environment of alkaline pH, makes the alkali of monoalkyl-phosphinous acid or alkaline earth ester be dissolved in aqueous phase more significantly than the ester products of dialkylphosphinic acids, rather than in the organic phase (being excessive olefin reactant phase).
Detailed Description Of The Invention
Theme of the present invention is a kind of dialkylphosphinic acids through improved preparation purifying as described below, is preferably the method for the dialkylphosphinic acids shown in the formula (I) that formula (I) is:
R wherein
1And R
2Independent separately alkyl of representing to have 2 to 22 carbon atoms (promptly being same to each other or different to each other), these groups can randomly be replaced by chlorine, bromine, alkyl or alkoxyl group or their mixing, and preferably replaced or more high-grade replacement by above-mentioned group two, wherein alkyl or alkoxyl group have 1 to 4 carbon atom independently of one another; Described method is for passing through the free radical intensified response of the excessive alpha-olefin of Hypophosporous Acid, 50 or its salt and stoichiometry, separate and purifying dialkylphosphinic acids reaction product by the aqueous solution that adds alkali, the aqueous solution of wherein said alkali is found any monoalkylphosphinic acid by-product that can preferentially neutralize and be formed by reaction.Because monoalkyl-phosphinous acid is dissolved in aqueous phase better in the organic phase, dialkylphosphinic acids then optimum solvation in organic phase, so monoalkyl-phosphinous acid is separated with dialkylphosphinic acid product.Optionally be, can use other purification step as well known to those skilled in the art, for example acidifying subsequently and distillation for purifying dialkylphosphinic acids more to heavens.
By this way, can easily from dialkyl product, remove unnecessary impurity such as unreacted alkene, water or other volatile matter.
R
1And R
2Preferably identical.
The alpha-olefin of Shi Yonging contains 2 to 22 carbon atoms, is preferably 2 to 12 carbon atoms, most preferably is 2 to 9 carbon atoms in the method for the invention.In the method for the invention, although can use straight chain alpha-monoolefine, the branched α-monoolefine of preferred use most preferably is highly branched α-monoolefine.The example of these alkene is: ethene, third rare, butylene-(1), hexene-(1), octene-(1), laurylene-(1), tetradecene-(1), hexadecylene-(1), octadecylene-(1), heneicosene-(1), two dodecylenes-(1), 2-methylpentene-(1), 2-ethyl hexene-(1) and diisobutylene-(1).Can also use the mixture of these alkene.
The alpha-olefin that is used as the initial compounds of the present invention's reaction can obtain by means commonly known in the art, and this method comprises the cracking of petroleum distillate or wax, cancellation spirit of salt from the alkane of end band chlorine atom, or make end have the dehydration of alcohols of hydroxyl.
Reaction initiator/propellant compound can be easy dissociated any compound under the influence of temperature (preferably between about 24 ℃ and 200 ℃) and/or actinic light.Form agent as the free radical in the inventive method, can use all known free radicals to form material, for example: the positively charged ion halogen compounds such as Losantin, N-chloro-Chloramine, N-chlorobenzene sulfonamide sodium; Metal alkyl compound such as tetraethyllead and tetraphenyl-lead; Carbonyl compound such as acetone, methylethylketone and phenyl aldehyde; And such as ditertiary butyl peroxide, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, TBPB tertiary butyl perbenzoate, 2,5-dimethyl-two-2,5-peroxy benzoate, 2, the organo-peroxide of 2-bis(t-butylperoxy) butane and benzoyl peroxide and so on.Advantageously use ditertiary butyl peroxide.
Use the free radical of catalytically effective amount to form agent, and this catalytically effective amount depend on the character of concrete initiator and change in the limited range of broad.In general, reaction initiator be the about 0.5 mole of % of phosphorus reaction thing to the amount of about 10 moles of % is suitable.
For the free radical generating agent in the solubilizing reaction mixture, must add a kind of inert solvent as solvating agent.Yet, preferably, select free radical generating agent, it can be dissolved at least a reactant (being alpha-olefin or Hypophosporous Acid, 50 or its salt).All free radical generating agent-reaction-ure mixtures when beginning, can be added in reaction or join in the reactor afterwards in batches.
When reaction causes by ultraviolet radiation, reaction soln must be exposed under the direct radiation of ultraviolet lamp.
Adding any suitable transition-metal catalyst may be favourable for further raising speed of reaction.Suitable transition-metal catalyst includes, but is not limited to the salt of nickel, cobalt, iron and chromium.
Can advantageously carry out with following process according to reaction of the present invention: can be randomly form agent blended alpha-olefin and add lentamente in Hypophosporous Acid, 50 or its salt with the free radical of catalytic amount.
Reaction of the present invention should be carried out in the presence of excessive alpha-olefin, that is to say that the ratio of alkene and Hypophosporous Acid, 50 or its salt should be higher than 2: 1, preferably is higher than 2.5: 1.
Find that the productive rate of the dialkylphosphinic acids that generates in phosphonous acidization (phosphination) reaction of the existence of acid to alkene has positive influence.Theory points out, acid catalysis help to form the decomposition of the organic peroxide evocating agent of dialkylphosphinic acids, theoretically point out that also acid is converted into its sour form to microcosmic salt.Therefore, preferably, be reflected at output and increase under the existence of one or more acid that the aspect is a significant quantity and carry out.Suitable acid is the mineral acid and the organic acid that can not decompose or can not cause disadvantageous side reaction under the main reaction condition.Suitable example is hydrochloric acid, sulfuric acid and/or most preferred acetate.
Reaction can also be carried out in the presence of the inert solvent such as alcohol, ester or hydrocarbon (for example benzene).Yet, it is most preferred that do not have additional solvent composition in the presence of carry out this reaction.
After initial reaction finishes, can add the viscosity that product mixtures is regulated in entry, be beneficial to the carrying out of subsequent technique.
In order to strengthen dialkylphosphinic acids and monoalkylphosphinic acid by-product and other unwanted separate impurities and purifying, organic phase is with thoroughly washing of alkaline solution (preferred caustic solution) because this alkaline solution preferential in and monoalkyl-phosphinous acid.But remove the water layer of resulting high dissolution monoalkyl-phosphinous acid.By such as fractionation, change the film evaporation/or conventional washing technology the known technology of this area approval come from reaction mixture, to separate and the purifying dialkylphosphinic acid product.Preferably, in order to be further purified the needed dialkylphosphinic acid product that is dissolved in the organic medium phase (this organic medium mainly is the excessive alpha-olefin reactant that joins at first in the reaction vessel mutually), organic phase is carried out pickling, preferably use mineral acid (for example sulfuric acid) washing.Remove water once more, organic phase is filtered and distilled to remove all final impurity and volatile matter.
The example of the particular compound that can prepare comprises: two-(2,4, the 4-tri-methyl-amyl) phosphonous acid and two-(2-ethylhexyl) phosphonous acid.
The temperature of using in the method for the present invention can change according to factor known to those of skill in the art.Reaction generally can be carried out under about 24 ℃ of temperature in about 200 ℃ of scopes, particularly preferably is, and temperature of reaction is about 100 ℃ to about 150 ℃.In the most preferred embodiment of the present invention, reaction is to carry out under about 140 ℃ temperature at about 110 ℃.
This reaction can under atmospheric pressure or in being in the closed container that is higher than under the atmospheric pressure state be carried out.
Method of the present invention has carried out being enough to producing the time of the required compound of capacity.Reaction times is subjected to the selection of temperature of reaction, concentration of reactants and reactant and the influence of other factors known to those of skill in the art to a great extent.In general, the reaction times can change in 8 hours to several days or longer time.
If initial use is the pure form alpha-olefin, those then excessive alpha-olefins can recycle.
Method of the present invention is preferably carried out with batch processing or semicontinuous mode.Described reaction can in the single reaction district or multi-reaction-area carries out or described reaction can intermittently be carried out in a long tube district or in a series of such zone.The material of used structure should be an inert for reactant during reaction, and equipment should manufacture and can make it bear temperature of reaction and pressure.
Followingly describe the present invention with reference to specific embodiment, these embodiment only should be as the exemplary illustration of the inventive method and mixture, and can not limit the scope of the invention.
Embodiment 1
Synthetic
For synthetic two (2,4, the 4-tri-methyl-amyl) phosphonous acid, the tert-butyl peroxide initiator of the 40g that in 1.5 liters autoclave, packs into (0.377 mole) sodium hypophosphite, 40g acetate, 132.3g (0.943 mole) diisobutylene (80%) and 2.8g (0.019 mole).Then mixture is heated under 8 hours the condition heating about four days (promptly totally 30 hours) in about 135 ℃ in every day, and when begin to heat every day, add the 1.4g initiator.Reaction mixture is used
31P NMR detects, and obtains the component that following table 1 is confirmed.Original mixture contains 75.3% needed dialkylphosphinic acid product and 12.1% unwanted monoalkylphosphinic acid by-product.
Purifying
(220g) is transferred in the erlenmeyer flask with whole reaction mixtures, and about 70 ℃ to about 80 ℃ scope internal heating to reduce the viscosity of described mixture.Slowly add 38g water till observing two-phase.Remove water, its pH value that measures is about 5.Caustic solution with 75g 4% washs organic phase then, and removes the water layer (89.2g) that obtains.With the sulphuric acid soln acidifying of 50g 10% and wash organic layer, remove the water that obtains then.
Organic phase through acidifying and washing is passed through the PS filter paper filtering, removes volatile matter by vacuum distilling.Recovery obtains the 95g dialkylphosphinic acids that purity is 93.7% (obtaining by phosphorus NMR detection); Yield is 86.9% thus.The component of final product is determined as following table 1.
Table 1
| Component | Initial mixture of reaction products (%) | Mixture of reaction products behind the purifying (%) |
| Unreacted Hypophosporous Acid, 50 | 1.6 | 0 |
| Monoalkyl-phosphinous acid | 12.1 | 0 |
| Dialkylphosphinic acids | 75.3 | 93.7 |
| Other impurity | 11.0 | 6.3 |
From the foregoing description and specification sheets to the detailed description of this method, can find out easily that method of the present invention can prepare highly purified dialkylphosphinic acids with very high yield with simple mode, therefore particularly highly branched dialkylphosphinic acids has represented the marked improvement in this industrial technology field.
Although described the present invention in detail with reference to the preferred embodiments of the invention especially, should be appreciated that within the mentioned above and appended the spirit and scope of the present invention that claim limited and to carry out variations and modifications.
Claims (17)
1. one kind through improved method, excessive alpha-olefin reaction generates the mixture of reaction products that comprises monoalkyl-phosphinous acid and dialkylphosphinic acids to this method by make Hypophosporous Acid, 50 or its salt and stoichiometry in the presence of radical initiator and optional transition-metal catalyst, thus production high yield and highly purified described dialkylphosphinic acids; The improvement of this method comprises:
A) in described mixture of reaction products, add the aqueous solution of enough alkali with i) generate the salt of described phosphonous acid and ii) form water and organic phase, wherein said monoalkyl-phosphinous acid optimum solvation is in described aqueous phase;
B) described water is separated with described organic phase;
C) the described organic phase of acidifying; And
D) from described organic phase, remove described alkene, and
E) separate purified dialkylphosphinic acid product.
2. the described method of claim 1, wherein said dialkylphosphinic acids meets following formula:
R wherein
1And R
2Expression independently of one another has the alkyl of 2 to 22 carbon atoms.
3. the described method of claim 2, wherein said R
1And R
2Be alkyl independently of one another with replacement of 2 to 12 carbon atoms.
4. the described method of claim 3, wherein said R
1And R
2Be alkyl independently of one another with replacement of 2 to 9 carbon atoms.
5. the described method of claim 2, wherein said alkyl are replaced by two or more groups that are selected from chlorine, bromine, alkyl, alkoxyl group or their combination independently of one another.
6. the described method of claim 3, wherein said alkyl are replaced by two or more groups that are selected from chlorine, bromine, alkyl, alkoxyl group or their combination independently of one another.
7. the described method of claim 4, wherein said alkyl are replaced by two or more groups that are selected from chlorine, bromine, alkyl, alkoxyl group or their combination independently of one another.
8. the described method of claim 1, the reaction of wherein said formation mixture of reaction products is carried out in the presence of acid solution.
9. the described method of claim 8, wherein said acid solution is selected from hydrochloric acid, sulfuric acid, acetate and their mixture.
10. the described method of claim 9, wherein said acid solution is an acetic acid solution.
11. the described method of claim 1, wherein said hypophosphite are the sodium hypophosphite monohydrates.
12. the described method of claim 1, the mol ratio of wherein said alpha-olefin and described Hypophosporous Acid, 50 or its salt was greater than 2: 1.
13. the described method of claim 12, the mol ratio of wherein said alpha-olefin and described Hypophosporous Acid, 50 or its salt was greater than 2.5: 1.
14. the described method of claim 1, the aqueous solution that wherein adds the described alkali in the described mixture of reaction products are aqueous sodium hydroxide solution and aqueous sodium carbonate.
15. the described method of claim 1, the acid of using in the wherein said acidification step comprises inorganic acid solution.
16. the described method of claim 15, wherein said inorganic acid solution is a sulphuric acid soln.
17. the described method of claim 1, the described alkene that wherein is removed can be recovered utilization.
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| CN101891762A (en) * | 2010-06-30 | 2010-11-24 | 南开大学 | Preparation method and application of diethyl phosphinates |
| CN102020673A (en) * | 2010-12-07 | 2011-04-20 | 江西科技师范学院 | Method for synthesizing bis(2,4,4-trimethylpentyl) phosphinic acid under normal pressure |
| CN101475588B (en) * | 2008-12-25 | 2012-01-04 | 清华大学 | Method for synthesizing dialkyl hypophosphorous acid |
| CN102372740A (en) * | 2011-12-06 | 2012-03-14 | 南开大学 | Preparation method for di(2,4,4-trimethyl pentyl) hypophosphorous acid |
| CN102617638A (en) * | 2012-03-02 | 2012-08-01 | 山东兄弟科技股份有限公司 | Normal pressure two-phase phase-transfer catalysis synthesizing process of dialkyl phosphinate |
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| CN103694273B (en) * | 2013-01-10 | 2017-04-12 | 中国科学院上海有机化学研究所 | Preparation method and application of dialkyl phosphinate compounds and salts thereof |
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| CN103804412B (en) * | 2013-12-04 | 2017-01-18 | 南开大学 | Preparation method of top-grade ultrafine particle diethyl aluminum phosphinate |
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