CN104710475B - A kind of preparation method of quaternary salt - Google Patents
A kind of preparation method of quaternary salt Download PDFInfo
- Publication number
- CN104710475B CN104710475B CN201310684970.3A CN201310684970A CN104710475B CN 104710475 B CN104710475 B CN 104710475B CN 201310684970 A CN201310684970 A CN 201310684970A CN 104710475 B CN104710475 B CN 104710475B
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- China
- Prior art keywords
- acid
- preparation
- reaction
- phosphine
- quaternary
- Prior art date
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- 239000011780 sodium chloride Substances 0.000 title claims abstract description 127
- 150000003839 salts Chemical group 0.000 title claims abstract description 123
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 111
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 60
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 239000000376 reactant Substances 0.000 claims abstract description 23
- 239000007848 Bronsted acid Substances 0.000 claims abstract description 20
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 230000000875 corresponding Effects 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims description 39
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 32
- -1 phenyl-carbonic acid methyl ester Chemical class 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 13
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N Triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N Boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- ODGCEQLVLXJUCC-UHFFFAOYSA-O tetrafluoroboric acid Chemical compound [H+].F[B-](F)(F)F ODGCEQLVLXJUCC-UHFFFAOYSA-O 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N HF Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 5
- TUQOTMZNTHZOKS-UHFFFAOYSA-N Tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 5
- 235000011054 acetic acid Nutrition 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-N hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 5
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- GPAYUJZHTULNBE-UHFFFAOYSA-N Diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- GQZXNSPRSGFJLY-UHFFFAOYSA-N Hypophosphorous acid Chemical compound OP=O GQZXNSPRSGFJLY-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N Oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-N Pyrophosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N Stearic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- QAIPRVGONGVQAS-DUXPYHPUSA-N caffeic acid Natural products OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- DWYMPOCYEZONEA-UHFFFAOYSA-N fluorophosphoric acid Chemical compound OP(O)(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-N 0.000 claims description 4
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 4
- OQWOLAMXNGPSQY-UHFFFAOYSA-N pentafluoro-$l^{5}-phosphane;hydrofluoride Chemical compound F.FP(F)(F)(F)F OQWOLAMXNGPSQY-UHFFFAOYSA-N 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 229910004039 HBF4 Inorganic materials 0.000 claims description 3
- 229910004713 HPF6 Inorganic materials 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N Silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 229960004365 benzoic acid Drugs 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- LVTCZSBUROAWTE-UHFFFAOYSA-N diethyl(phenyl)phosphane Chemical compound CCP(CC)C1=CC=CC=C1 LVTCZSBUROAWTE-UHFFFAOYSA-N 0.000 claims description 3
- YOTZYFSGUCFUKA-UHFFFAOYSA-N dimethylphosphine Chemical compound CPC YOTZYFSGUCFUKA-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 229940071870 hydroiodic acid Drugs 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- BFASWJXWTSCDRR-UHFFFAOYSA-M prop-2-enyl carbonate Chemical compound [O-]C(=O)OC[C]=C BFASWJXWTSCDRR-UHFFFAOYSA-M 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 3
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-Dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-Naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-Aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N Benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- LPWXFIYOTKUODB-UHFFFAOYSA-N C(C)P(CCCl)CC Chemical compound C(C)P(CCCl)CC LPWXFIYOTKUODB-UHFFFAOYSA-N 0.000 claims description 2
- 229910020596 CmF2m+1SO2 Inorganic materials 0.000 claims description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N Diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 2
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 claims description 2
- 229910016850 F2n+1SO2 Inorganic materials 0.000 claims description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N Fluorosulfuric acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910003641 H2SiO3 Inorganic materials 0.000 claims description 2
- 229910004770 HSO3F Inorganic materials 0.000 claims description 2
- TYQCGQRIZGCHNB-JLAZNSOCSA-N L-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N Malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- IWYDHOAUDWTVEP-UHFFFAOYSA-N Mandelic acid Chemical compound OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-XIXRPRMCSA-N Mesotartaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-XIXRPRMCSA-N 0.000 claims description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-N Methyl bisulfate Chemical compound COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N P-Cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N P-Toluenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N Phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N Tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N Trifluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- NWZKZWNTVWMEAG-UHFFFAOYSA-N [W].OB(O)O Chemical compound [W].OB(O)O NWZKZWNTVWMEAG-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- VOTFXKJPNQELOG-UHFFFAOYSA-N arsenic acid Chemical compound O[As](=O)=O VOTFXKJPNQELOG-UHFFFAOYSA-N 0.000 claims description 2
- 229940000488 arsenic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 229950011260 betanaphthol Drugs 0.000 claims description 2
- JMXMXKRNIYCNRV-UHFFFAOYSA-N bis(hydroxymethyl)phosphanylmethanol Chemical compound OCP(CO)CO JMXMXKRNIYCNRV-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- WVQUCYVTZWVNLV-UHFFFAOYSA-N boric acid;oxalic acid Chemical compound OB(O)O.OC(=O)C(O)=O WVQUCYVTZWVNLV-UHFFFAOYSA-N 0.000 claims description 2
- WXMZPPIDLJRXNK-UHFFFAOYSA-N butyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CCCC)C1=CC=CC=C1 WXMZPPIDLJRXNK-UHFFFAOYSA-N 0.000 claims description 2
- 229940074360 caffeic acid Drugs 0.000 claims description 2
- 235000004883 caffeic acid Nutrition 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- HZXXSCOUSGLRRX-UHFFFAOYSA-N cyanoboronic acid Chemical compound OB(O)C#N HZXXSCOUSGLRRX-UHFFFAOYSA-N 0.000 claims description 2
- ZBCKWHYWPLHBOK-UHFFFAOYSA-N cyclohexylphosphane Chemical compound PC1CCCCC1 ZBCKWHYWPLHBOK-UHFFFAOYSA-N 0.000 claims description 2
- 125000006182 dimethyl benzyl group Chemical group 0.000 claims description 2
- CRHWEIDCXNDTMO-UHFFFAOYSA-N ditert-butylphosphane Chemical compound CC(C)(C)PC(C)(C)C CRHWEIDCXNDTMO-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- JLHMVTORNNQCRM-UHFFFAOYSA-N ethylphosphine Chemical compound CCP JLHMVTORNNQCRM-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N fumaric acid Chemical compound OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- CHXARDKIHSVFDK-UHFFFAOYSA-N hexylphosphane Chemical class CCCCCCP CHXARDKIHSVFDK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
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- 229940099690 malic acid Drugs 0.000 claims description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- WEYHWRWGAACKIL-UHFFFAOYSA-N pentylphosphane Chemical class CCCCCP WEYHWRWGAACKIL-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- 229910052904 quartz Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- 235000011044 succinic acid Nutrition 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 229960001367 tartaric acid Drugs 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 2
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 2
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenate Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 claims 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N Dimethylphenylphosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 claims 1
- 229910003638 H2SiF6 Inorganic materials 0.000 claims 1
- OHORFAFFMDIQRR-UHFFFAOYSA-P Hexafluorosilicic acid Chemical compound [H+].[H+].F[Si-2](F)(F)(F)(F)F OHORFAFFMDIQRR-UHFFFAOYSA-P 0.000 claims 1
- 241000219000 Populus Species 0.000 claims 1
- 150000001350 alkyl halides Chemical class 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 1
- 125000005586 carbonic acid group Chemical group 0.000 claims 1
- 229960004106 citric acid Drugs 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000005712 crystallization Effects 0.000 claims 1
- 150000001924 cycloalkanes Chemical class 0.000 claims 1
- VZZJVOCVAZHETD-UHFFFAOYSA-N diethylphosphane Chemical compound CCPCC VZZJVOCVAZHETD-UHFFFAOYSA-N 0.000 claims 1
- 229910052909 inorganic silicate Inorganic materials 0.000 claims 1
- 229910052756 noble gas Inorganic materials 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 38
- 239000000047 product Substances 0.000 description 20
- IEJIGPNLZYLLBP-UHFFFAOYSA-N Dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 18
- 239000000126 substance Substances 0.000 description 16
- 150000001450 anions Chemical class 0.000 description 14
- 238000003756 stirring Methods 0.000 description 11
- FZTWZIMSKAGPSB-UHFFFAOYSA-N phosphide(3-) Chemical compound [P-3] FZTWZIMSKAGPSB-UHFFFAOYSA-N 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 238000006073 displacement reaction Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000002829 reduced Effects 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 150000002466 imines Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 0 *S(NCS(C(F)(F)F)(=O)=O)(=O)=O Chemical compound *S(NCS(C(F)(F)F)(=O)=O)(=O)=O 0.000 description 4
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N Dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 206010020852 Hypertonia Diseases 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 150000004820 halides Chemical group 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N Chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 229910016855 F9SO2 Inorganic materials 0.000 description 2
- 229940050176 Methyl Chloride Drugs 0.000 description 2
- 230000002152 alkylating Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910021432 inorganic complex Inorganic materials 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 101710031899 moon Proteins 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing Effects 0.000 description 2
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 2
- NJFUXFRJVIXVSG-UHFFFAOYSA-M tetramethylphosphanium;chloride Chemical compound [Cl-].C[P+](C)(C)C NJFUXFRJVIXVSG-UHFFFAOYSA-M 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- NJESAXZANHETJV-UHFFFAOYSA-N 4-Methylsalicylic acid Chemical compound CC1=CC=C(C(O)=O)C(O)=C1 NJESAXZANHETJV-UHFFFAOYSA-N 0.000 description 1
- 229910017251 AsO4 Inorganic materials 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 240000004307 Citrus medica Species 0.000 description 1
- 210000003298 Dental Enamel Anatomy 0.000 description 1
- LSRGXLRLWFDKNR-UHFFFAOYSA-N FC(F)(F)[S] Chemical compound FC(F)(F)[S] LSRGXLRLWFDKNR-UHFFFAOYSA-N 0.000 description 1
- ZYCMDWDFIQDPLP-UHFFFAOYSA-N HBr bromine Chemical compound Br.Br ZYCMDWDFIQDPLP-UHFFFAOYSA-N 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N Iodic acid Chemical compound OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N Methyl iodide Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- GWLQPIZZAYEMQQ-UHFFFAOYSA-N NCPC1=CC=CC=C1 Chemical compound NCPC1=CC=CC=C1 GWLQPIZZAYEMQQ-UHFFFAOYSA-N 0.000 description 1
- GGYPIUANQNUBOE-UHFFFAOYSA-N O=S(C(F)(F)F)(NS(F)(=O)=O)=O Chemical compound O=S(C(F)(F)F)(NS(F)(=O)=O)=O GGYPIUANQNUBOE-UHFFFAOYSA-N 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-M Sodium 2-anthraquinonesulfonate Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)[O-])=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-M 0.000 description 1
- GCPXMJHSNVMWNM-UHFFFAOYSA-N Trihydroxyarsenite(Iii) Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 1
- DDJUYFRJINFTCP-UHFFFAOYSA-N [O-]=S(NS(F)(=O)=O)(F)=O Chemical compound [O-]=S(NS(F)(=O)=O)(F)=O DDJUYFRJINFTCP-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000000844 anti-bacterial Effects 0.000 description 1
- TTZGACSBMSVUOJ-UHFFFAOYSA-N benzene-1,2-diol;boric acid Chemical compound OB(O)O.OC1=CC=CC=C1O TTZGACSBMSVUOJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960002645 boric acid Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 230000003197 catalytic Effects 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 231100000078 corrosive Toxicity 0.000 description 1
- 231100001010 corrosive Toxicity 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000002349 favourable Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000002452 interceptive Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 229910052751 metal Chemical group 0.000 description 1
- 239000002184 metal Chemical group 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000002068 microbial inoculum Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- YGAMIEYKXHAVBP-UHFFFAOYSA-N molecular hydrogen;hydrochloride Chemical compound Cl.[H][H] YGAMIEYKXHAVBP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005377 tertiary alkyl halides Chemical class 0.000 description 1
- ODGCEQLVLXJUCC-UHFFFAOYSA-N tetrafluoroborate Chemical compound F[B-](F)(F)F ODGCEQLVLXJUCC-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000002588 toxic Effects 0.000 description 1
- 231100000563 toxic property Toxicity 0.000 description 1
- IFXORIIYQORRMJ-UHFFFAOYSA-N tribenzylphosphane Chemical compound C=1C=CC=CC=1CP(CC=1C=CC=CC=1)CC1=CC=CC=C1 IFXORIIYQORRMJ-UHFFFAOYSA-N 0.000 description 1
- RLZMYANQLOCZOB-UHFFFAOYSA-M tributyl(methyl)phosphanium;iodide Chemical compound [I-].CCCC[P+](C)(CCCC)CCCC RLZMYANQLOCZOB-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention provides the preparation method of a kind of quaternary salt, including: (a) phosphorus-containing compound (R1R2R3P) the corresponding salt of generation is reacted with Bronsted acid；B () salt and dialkyl carbonate react and prepare quaternary salt.The method can synthesize quaternary salt with hydrogen phosphide or organic phosphoric compound for initial reactant, and the selection degree of freedom of reaction mass is bigger；The various quaternary salts of various structures can also be obtained, and product purity is high.
Description
Technical field
The present invention relates to the preparation method of a kind of quaternary salt.
Background technology
At present, one of application that quaternary salt is maximum is water treatment agent.Quaternary salt is considered as that a new generation's cationic is killed
Microbial inoculum (prior-generation cationic antibacterial is quaternary ammonium salt), can be applicable to the circulations such as oil-field flooding, petrochemical industry, iron and steel, electric power
In water system.Such as, tetramethyl chlorination is the first generation quaternary salt product being applied to Treatment of Industrial Water, has proved to be one
Plant and there is inhibition, scale inhibition and the multipurpose agent killed livestock.Quaternary salt is also used as phase transfer catalyst, at catalytic field
There is important application.Another potential important applied field is electro-chemical systems, and the quaternary salt of low melting point is of ionic liquid
Important branch, the quaternary salt of low melting point is used as the electrochemical device such as lithium rechargeable battery, electric chemical super capacitor
Electrolyte.
The traditional processing technology of quaternary salt is the method using tertiary phosphine and alkyl halide to carry out quaternary reaction, and its reaction is such as following formula institute
Show:
R1R2R3P+R4X→[R1R2R3R4P]+X- (1)
Such as, tributyl methyl phosphonium iodide can be prepared by tributyl tertiary phosphine and iodomethane reaction:
(C4H9)3P+CH3I→[(C4H9)3PCH3]+I- (2)
Prepare at least to replace on P elements and have the quaternary salt of a methyl, it is also possible to make alkylating reagent by dimethyl sulfate, as
Shown in following formula:
R1R2R3P+(CH3)2SO4→[R1R2R3PCH3]+CH3SO4 - (3)
Tertiary phosphine and dimethyl sulfate are easier to reaction, and yield is high, use the shortcoming of dimethyl sulfate to be its severe toxicity, have carcinogenesis.
The maximum weak point of above-mentioned process route is to prepare certain several quaternary salt, such as quaternary instead according to halogenated alkane
The method answered, can only prepare anion is Cl-、Br-、I-Quaternary salt；According to the method for dimethyl sulfate quaternization reaction,
Can only prepare anion is CH3SO4 -Quaternary salt.When being the quaternary salt of other ion if desired for preparation anion, Zhi Nengtong
Cross ion-exchange reactions to realize, as shown in formula (4) and formula (5):
[R1R2R3R4P]+X-+H+A-→[R1R2R3R4P]+A-+H+X- (4)
[R1R2R3R4P]+X-+M+A-→[R1R2R3R4P]+A-+M+X- (5)
Such as, preparation anion is SO4 2-Quaternary salt [R1R2R3R4P]2 2+SO4 2-, general the most synthesizing chlorinated via formula (1)
Quaternary salt, makes chloride quaternary and sulfuric acid reaction via formula (4) the most again, utilizes the volatile feature of hydrochloric acid to remove hydrogen chlorine
Acid, makes reaction (4) balance move right, thus reaches ion exchange to greatest extent.And for example preparing anion is BF4 -
Quaternary salt [R1R2R3R4P]+BF4 -, in like manner first synthesize corresponding quaternary halide via formula (1), then via formula (5)
Make quaternary halide and metal inorganic salt such as NaBF4React in organic solvent is such as acetone, utilize metal halide organic molten
The feature that in agent, dissolubility is little makes halogen ion separate out to realize the purpose of ion exchange with precipitation form.Obviously, formula (4) and formula
(5) it is all balancing response, all there is the halfway phenomenon of reaction, inevitably residual halogens ion in final products.
Utilize silver salt such as AgBF4, reaction (5) can carry out in aqueous, and can react complete, but high cost.
On the one hand, due to halide anion such as Cl-、Br-、I-Equistability is poor, the most oxidized and discharge toxic property,
Corrosive halogen simple substance, its range of application is restricted；On the other hand, along with in-depth and the extension of research, it has been found that
(F when anion is a certain in following ion-、NO3 -、CO3 2-、PF6 -、BF4 -、C2O4 2-、SO4 2-、PO4 3-、
Al2Cl7 -、CH3COO-、CF3SO3 -、C4H9SO3 -、CF3COO-、N(CF3SO2)2 -、N(C2F5SO2)2 -、N(C4F9SO2)2 -、N[(CF3SO2)(C4F9SO2)]-、C(CF3SO2)3 -Etc.), quaternary salt generally has not available for quaternary halide
Some characteristic, such as fusing point are lower, conductivity is higher, viscosity is lower, hydrophobicity is strong etc., thus have and widely use
On the way.To this end, the new preparation process developing these special quaternary salts is particularly important.
United States Patent (USP) US4892944 describes dimethyl carbonate as a kind of method preparing quaternary salt of alkylating reagent.
The method is undertaken in two steps, and first step tertiary phosphine and dimethyl carbonate generate season methylcarbonate, second step season methyl
Carbonate and acid reaction discharge methanol and carbon dioxide prepared quaternary salt, and the anion species of quaternary salt is by the acid used
Determining, reaction equation is as follows:
R1R2R3P+Me2CO3→[R1R2R3PMe]+MeCO3 - (6)
[R1R2R3PMe]+MeCO3 -+H+A-→[R1R2R3PMe]+A-+MeOH+CO2 (7)
The feature of the method is, the anion of the quaternary salt prepared is the anion of various acid, is not limited by quaternizing agents,
The anion range of choice is big.But, still being limited to reactant must be that tertiary phosphine, only tertiary phosphine could be by dimethyl carbonate alkyl
Metaplasia becomes corresponding quaternary salt, hydrogen phosphide, primary phosphine and secondary phosphine can not by dimethyl carbonate alkylation, can not get Ji Yang from
Son.
Summary of the invention
The invention provides the preparation method of a kind of quaternary salt, including: in the first step is reacted, by phosphorus-containing compound R1R2R3P
The corresponding salt of generation is reacted with Bronsted acid；In second step reacts, the salt that first step reaction is generated and dialkyl carbonate
Reaction prepares quaternary salt；Wherein, R1、R2、R3Separately selected from H, alkyl, thiazolinyl, alkynyl, phenyl, aryl,
Or containing boron, silicon, nitrogen, phosphorus, oxygen, sulfur, fluorine, chlorine, bromine, iodine at least one of which element in above-mentioned organic group
Group；R1、R2、R3Can be independent substituted radical, it is also possible to be that adjacent group combines cyclization.Due to the inventive method not
Need to introduce halogenated hydrocarbons and make quaternizing agents, it is not necessary to be the season of appointment ion with prepared anion by anion exchange reaction
Salt, therefore, the quaternary salt purity prepared by the inventive method is high, there is not the situation of other anion residual.
Method in the present invention, the first step, phosphorus-containing compound R1R2R3P is selected from hydrogen phosphide (PH3) and organic phosphoric compound in
At least one, organic phosphoric compound be selected from primary phosphine (RPH2), secondary phosphine (R1R2And tertiary phosphine (R PH)1R2R3P) in extremely
Few one；They are with Bronsted acid (H+A-) the reaction corresponding salt (PH of generation4Or organic salt (R A)1PH3A,
R1R2PH2A, R1R2R3PHA)；In second step reacts, salt (PH4Or organic salt (R A)1PH3A, R1R2PH2A,
R1R2R3PHA) prepared quaternary salt (R is reacted with dialkyl carbonate1R2R3R4PA).To use dimethyl carbonate to make quaternary
As a example by (alkylation) reagent, with hydrogen phosphide (PH3) it is initial reactant when preparing quaternary salt, chemical equation such as formula (8)
With formula (9) Suo Shi:
With primary phosphine (R1PH2) it is initial reactant when preparing quaternary salt, chemical equation such as formula (10) and formula (11) institute
Show:
R1PH2+H+A-→R1H3P+A- (10)
With secondary phosphine (R1R2PH) it is initial reactant when preparing quaternary salt, chemical equation such as formula (12) and formula (13) institute
Show:
R1R2PH+H+A-→R1R2H2P+A- (12)
With tertiary phosphine (R1R2R3P) it is initial reactant when preparing quaternary salt, chemical equation such as formula (14) and formula (15)
Shown in:
R1R2R3P+H+A-→R1R2R3HP+A- (14)
In the preparation method of above-mentioned quaternary salt, R in chemical equation1、R2、R3Be independently selected from hydrogen, alkyl, thiazolinyl, alkynyl,
In phenyl, aryl or above-mentioned organic group containing boron, silicon, nitrogen, phosphorus, oxygen, sulfur, fluorine, chlorine, bromine, iodine the most extremely
The group of few a kind of element；R1、R2、R3Can be independent substituted radical, it is also possible to be that adjacent group combines cyclization.Enter one
Step, R1、R2、R3Separately selected from the alkyl that H, phenyl, aryl, carbon number are 1～20.
According to one embodiment of the present invention, organic phosphoric compound is selected from methylphosphine, dimethylphosphine, three methylphosphines, ethyl phosphine, diethyl
Base phosphine, triethyl phosphine, tripropyl phosphine, di-t-butyl phosphine, tri-butyl phosphine, tributylphosphine, three n-pentyl phosphines, cyclohexyl
Phosphine, dicyclohexylphosphontetrafluoroborate, tricyclohexyl phosphine, three hexyl phosphines, tri octyl phosphine, Phenylphosphine, diphenylphosphine, triphenylphosphine, two
Aminomethyl phenyl phosphine, diethyl Phenylphosphine, diphenyl butylphosphine, tribenzyl phosphine, tris hydroxymethyl phosphine, 2-chloroethyl diethyl phosphine
With at least one in three (pentafluoroethyl group) phosphine.
The quaternary cation structure of quaternary alkylphosphonium salt can be selected from following structure, but is not limited to following structure:
Bronsted acid in the inventive method refers to the most at least to provide a proton and hydrogen phosphide (PH3) or
Organic phosphoric compound (includes primary phosphine R1PH2, secondary phosphine R1R2PH, tertiary phosphine R1R2R3P) compound that the P element on combines,
Mineral acid oxyacid such as arsenic acid (H can be selected from3AsO4), arsenious acid (H3AsO3), pyroarsenic acid (H4As2O7), boron
Acid (H3BO3), 12 tungsten boric acid (H5BW12O40), phosphoric acid (H3PO4), phosphorous acid (H3PO3), hypophosphorous acid
(H3PO2), hypophosphoric acid (H4P2O6), pyrophosphoric acid (H4P2O7), sulphuric acid (H2SO4), sulfurous acid (H2SO3)、
Chlorosulfonic acid (HSO3Cl), fluosulfonic acid (HSO3F), metasilicic acid (H2SiO3Or SiO2·H2O), orthosilicic acid (H4SiO4)
At least one in Deng；Bronsted acid is also selected from inorganic oxygen-free acid such as carborane acid (H [CHB11Cl11]), hydrosulphuric acid
(H2S), fluoboric acid (HBF4), hexafluosilicic acid (H2SiF6), hexafluorophosphoric acid (HPF6), Fluohydric acid. (HF),
At least one in hydrochloric acid (HCl), hydrobromic acid (HBr) and hydroiodic acid (HI)；With organic acid such as oxalic acid, formic acid,
Acetic acid, propanoic acid, succinic acid, trifluoracetic acid, trifluoromethanesulfonic acid, methanesulfonic acid, mandelic acid, methylsulfuric acid, ethyl sulfuric acid,
Oleic acid, stearic acid, acrylic acid, maleic acid, citric acid, double (catechol) boric acid, double oxalic acid boric acid, dimalonic acid
Boric acid, three (pentafluoroethyl group) three fluorophosphoric acid, triethyl group three fluorophosphoric acid, four cyano boric acid, tartaric acid, malic acid, citron
At least one in acid, ascorbic acid, benzoic acid, benzenesulfonic acid, p-methyl benzenesulfonic acid, salicylic acid and caffeic acid etc..
The preparation method of the quaternary salt according to the present invention, above-mentioned Bronsted acid also includes that scope far surpasses the acid compounds of common meaning,
We are defined as non-acids proton compound them, this compounds active proton hydrogen, and owing to neighboring group has
The strongest electron-withdrawing and make hydrogen atom have greater activity, the most above-mentioned non-acids proton compound can discharge activity matter
Son, and and phosphorus-containing compound R1R2R3P reaction generates salt.Such as imide analog compounds, above-mentioned imide compound has
Just like the structure shown in formula 1 or formula 2:
Formula 1:HN (CmF2m+1SO2)(CnF2n+1SO2)；
Formula 2:HNCxF2x(SO2)2；
Wherein m is the integer of 0～5, and n is the integer of 0～5, and X is the integer of 1～10.
According to one embodiment of the present invention, above-mentioned imide compound is selected from
In at least one.
According to another embodiment of the invention, non-acids proton compound is also selected from three (trimethyl fluoride sulfonyl) first
At least one in alkane, phenol, p-methyl phenol, betanaphthol, 2,4 dichloro phenol and para-aminophenol etc..
The kind of acid is influential for the yield of final reacting product.According to one embodiment of the present invention, acid strong
The productivity that is favorably provided with of acid and the yield of product, such as halogen acids in hydrochloric acid (HCl), hydrobromic acid (HBr), hydrogen
Iodic acid (HI) is all strong acid, and the yield of product is the highest.It addition, same type of acid often has close reaction to produce
Thing yield, inorganic complex acid such as fluoboric acid (HBF4), hexafluosilicic acid (H2SiF6), hexafluorophosphoric acid (HPF6) there is close product
Rate and product yield.In some cases, halogen acids is typically higher than the product rate of inorganic complex acid and yield.
Quaternary (alkylation) reagent dialkyl carbonate RO-CO-OR ' in the inventive method, it is considered to substituent R, R '
To electronics/factor such as sucting electronic effect, space steric effect to the thermodynamics of quaternary reaction, kinetic effect, preferably tie
The relatively simple dimethyl carbonate of structure, Ethyl methyl carbonate, diethyl carbonate, ethylene carbonate, Allyl carbonate, phenyl carbons
At least one in acid methyl ester, diphenyl carbonate and dimethyl benzyl, particularly preferred dimethyl carbonate, Ethyl methyl carbonate and carbon
Diethyl phthalate.Particularly point out, when carbonic ester is circulus, utilize the method in the present invention can obtain multifunctional dough
Compound.Such as in second step reacts, add ethylene carbonate or Allyl carbonate makees quaternizing agents, can be at end product
Quaternary salt introduces ethoxy (-CH respectively2CH2And 2-hydroxypropyl (-CH OH)2CHOHCH3).Due to drawing of hydroxyl
Entering, the application on the one hand expanding quaternary salt (such as strengthens hydrophilic or water solublity, can apply to water-related neck
Territory)；On the other hand, provide condition for " grafting " other functional group, on the basis of hydroxyl can sense dough further,
Such as halogenation, be etherified, esterification etc., it is also possible to by being oxidized to carboxylic acid.
The preparation method of the quaternary salt according to the present invention, the first step is reacted, the most i.e. can be reacted.Phosphorous
Compound such as hydrogen phosphide (PH3) or organic phosphoric compound (include primary phosphine R1PH2, secondary phosphine R1R2PH, tertiary phosphine R1R2R3P)
Corresponding salt (the PH of generation is reacted with Bronsted acid4Or organic salt (R A)1PH3A, R1R2PH2A, R1R2R3PHA),
The mol ratio of reactant is depending on the proton number that Bronsted acid can provide.If a part Bronsted acid may only provide a proton,
So, hydrogen phosphide (PH3) or organic phosphoric compound (include primary phosphine R1PH2, secondary phosphine R1R2PH, tertiary phosphine R1R2R3P) with
The mol ratio of Bronsted acid is preferably 1:1.Boiling point reaction relatively low, lower-cost can be considered to ensure reaction to carry out completely
Thing is the most excessive.Can remove by the way of distillation of washing, distill or reduce pressure after reaction completely.Such as, hydrogen phosphide (PH3)
Prepared PH is reacted with mol ratio 1:1 with Fluohydric acid. (HF)4F, hydrogen phosphide and Fluohydric acid. are all effumability compounds, permissible
Which kind of consider to select more favourable (the economic one-tenth of material somewhat excess according to combined factors such as Material Cost height, waste recovery difficulty or ease
This low and environmental friendliness)；If a part Bronsted acid can provide two or the proton of more than two, then hydrogen phosphide (PH3)
Or organic phosphoric compound (includes primary phosphine R1PH2, secondary phosphine R1R2PH, tertiary phosphine R1R2R3P) mol ratio with Bronsted acid can be
1:1,2:1 or 3:1, such as, a part phosphoric acid at most can provide 3 protons, and triethyl phosphine can be pressed respectively with phosphoric acid
Mol ratio 1:1,2:1 or 3:1 react, and prepare triethyl group dihydric phosphate ([(C respectively2H5)3PH][H2PO4]), three
Ethyl phosphonic acid hydrogen salt ([(C2H5)3PH]2[HPO4]) or triethyl ([(C2H5)3PH]3[PO4]).In order to
Ensure reaction to carry out completely and can consider that boiling point reactant relatively low, lower-cost is the most excessive, can pass through after reaction completely
The mode distilled of washing, distill or reduce pressure removes.
According to raw material sources, hydrogen phosphide (PH3) or organic phosphoric compound (include primary phosphine R1PH2, secondary phosphine R1R2PH, tertiary phosphine
R1R2R3P) being usually pure substance, Bronsted acid can be that pure substance can also be dissolved in solvent formation solution, such as, common
Mineral acid be usually aqueous solution, sulphuric acid, nitric acid, hydrochloric acid, hydrobromic acid, Fluohydric acid., phosphoric acid, hexafluorophosphoric acid, tetrafluoro boron
Acid etc..If Bronsted acid is dissolved in the solution of solvent, first step reaction can be carried out in solution is such as aqueous solution, can be with volume
Outer interpolation solvent can also be without.If Bronsted acid is pure substance, organic acid is pure substance mostly, such as acetic acid, propanoic acid,
Benzoic acid etc., preferably interpolation solvent are beneficial to reaction and carry out completely.Molten to used in step chemical reaction each in the inventive method
Agent system does not make specific requirement, alcohols (preferably methanol), ethers, ketone, dialkyl carbonate esters (preferably dimethyl carbonate),
Nitrile, dichloro-methane, chloroform, oxolane, toluene etc. common are machine solvent and their mixed solvent all
Can consider to use.If Bronsted acid is not traditional acid, it is owing to neighboring group has the strongest electron-withdrawing
And make hydrogen atom have greater activity, and such as three (trimethyl fluoride sulfonyl) methane, two (trimethyl fluoride sulfonyl) imines etc.,
Single step reaction should select suitable solvent to avoid introducing side reaction.
Usually, in the present invention first step reaction be easier to carry out, generally-20 DEG C～80 DEG C relatively be beneficial to reaction, preferably 0～
60 DEG C, if exothermic heat of reaction is obvious, preferably slow down another kind of reactant addition, or lowers the temperature.Reaction pressure is usual
Being 0.05～2MPa absolute pressure, preferably 0.09～0.5MPa absolute pressure, particularly preferred 0.095～0.12MPa is absolute
Pressure.This reaction required time is usually a few minutes to a few hours, preferably 0.1～12 hour, particularly preferred 0.5～8 hour.
After reaction completely, can by the modes such as distillation, decompression distillation, recrystallization, washing remove unreacted reactant and
Solvent；On the premise of not affecting second step reaction (introducing side reaction), it is also possible to be left intact and then carry out second
Step reaction.
According to the preparation method in the present invention, in second step reacts, the first step reaction salt (PH prepared4Or have A)
Machine salt (R1PH3A, R1R2PH2A, R1R2R3PHA) prepared quaternary salt (R is reacted with dialkyl carbonate4PA).?
Salt (PH4Or organic salt (R A)1PH3A, R1R2PH2A, R1R2R3PHA) mol ratio with dialkyl carbonate regards hydrogen
Depending on the number of proton, such as salt PH4A is 1:4 with the mol ratio of dialkyl carbonate, organic salt RPH3A、R2PH2A、
R3PHA is respectively 1:3,1:2,1:1 with the mol ratio of dialkyl carbonate.Certainly, carry out completely in order to ensure reaction, typically
Ground, selects dialkyl carbonate the most excessive；Dialkyl carbonate can also be selected the most excessive, and the dialkyl carbonate of excess is permissible
Serve as solvent.This reaction is generally carried out at a temperature of 60～280 DEG C, preferably 100～200 DEG C, reaction pressure be usually 0.1～
3MPa absolute pressure, preferably 0.8～2.0MPa absolute pressure.Before reaction starts, the most first use inert atmosphere displacement reaction
Air in container or take the air in reaction vessel away to avoid because reaction is adversely affected by air with vacuum pump.Should
Reaction required time is usually a few hours, preferably 0.5～24 hour, particularly preferred 2～15 hours.After reaction completely,
Unnecessary reactant and solvent can be removed, in order to ensure end product quaternary salt by the way of distillation or decompression distillation
Purity, can pass through the Methods For Purification product such as recrystallization, extraction.From reaction equation, wherein the one of second step reaction
Planting by-product is CO2.Along with constantly carrying out of reaction, CO2Amount be continuously increased, in causing reaction vessel, pressure is continuous
Rise.Consider safety in production and reduce equipment manufacturing cost (pressure vessel by bear pressure graduation, pressure is the highest, consumption
Material is the most, the highest to bubble-tight requirement), a certain reactant (control reaction rate) limit can be slowly added into limit and pass through
Air valve release CO2So that the pressure stability in reaction vessel is in certain level.And use limit conveying material limit release CO2
Method be also beneficial to improve the production capacity of reactor in actual production.Such as according to practical experience, if discharging CO not in time2,
The pressure reaction still of general 10L produces the quaternary salt of about 1kg, and under the reaction condition of 160 DEG C, pressure in still is it is possible to reach
To 1.6MPa；If using conveying reaction raw materials (carbonic ester) limit, limit to discharge CO in right amount2Method, make reactor intrinsic pressure
Power is in an equilibrium valve, such as, be still 1.6MPa, then the pressure reaction still of 10L can produce 5kg even more season
Salt.Test result indicate that, adopt yield and the purity not interfering with final products in this way.
As consersion unit used by the inventive method, however, it would be possible to use all be applicable to liquid reactive container and pressure
Container, especially first step reaction can also be carried out in the consersion unit of mixes liquid raw material such as stirring container.The material of container
Matter need to select according to the physico-chemical property of reactant, preferably with having the material of characteristic acidproof, alkaline-resisting, and such as first step reaction
Can carry out in enamel reaction vessel, second step reaction can at rustless steel (such as 316L rustless steel) pressure vessel or
Person's titanium material pressure vessel is carried out.
The inventive method can in batches, semicontinuous or be carried out continuously.When being conducted batch-wise, after first step reaction terminates, logical
Cross distillation, the decompression mode such as distillation, recrystallization, washing removes unreacted reactant and solvent to obtain purity higher
Salt (PH4Or organic salt (R A)1PH3A, R1R2PH2A, R1R2R3PHA), react with dialkyl carbonate the most again
Obtain quaternary salt.Especially when carrying protogenic reactant and being aqueous solution, preferably it is conducted batch-wise, to avoid water to second step
The impact of reaction.When being carried out continuously, after first step reaction terminates, any process can not be made, add dialkyl carbonate with
And suitable solvent continues second step reaction in right amount.
The invention provides a kind of method preparing quaternary salt, all can only be with tertiary phosphine for initial reactant system according to conventional method
Standby quaternary salt, is with hydrogen phosphide (PH in one embodiment of the present invention3) or organic phosphoric compound (include primary phosphine R1PH2、
Secondary phosphine R1R2PH, tertiary phosphine R1R2R3P) synthesizing quaternary salt with initial reactant, the selection degree of freedom of reaction mass is bigger.Example
As, prepare tetramethyl tetrafluoroborate, according to the inventive method, hydrogen phosphide (PH3), methylphosphine, dimethylphosphine, front three
Phosphine can be employed as initial reactant.Furthermore, it is possible to by using different Bronsted acids, " freely " selects the moon of quaternary salt
Ionic species.By hydrogen phosphide (PH3) or organic phosphoric compound react with Bronsted acid, by this way introduce required for the moon
Ion is in final products quaternary salt, it is possible to obtain the various quaternary salts of various structures, and product purity is high, does not exist many
Plant anion the problem depositing (former anion residual).Additionally, the inventive method low cost.By hydrogen phosphide or phosphine and acid
Neutralize reaction introduce quaternary salt anion, and under normal circumstances acid price be intended to well below corresponding slaine chemical combination
Thing, therefore greatly reduces Material Cost.
Additionally, low melting point quaternary salt prepared according to the methods of the invention, belong to the category of ionic liquid.Due in preparation process
In can not introduce halide ion, be particularly well-suited to the electro-chemical systems sensitive to halide ion, such as lithium ion
Secondary cell, electric chemical super capacitor etc..
Present invention also offers a kind of electrolyte for secondary cell, including the quaternary salt prepared according to above-mentioned preparation method.
The present invention still further provides a kind of secondary cell, including electrolyte as above.
Detailed description of the invention
The present invention is described in detail by following specific embodiment, but the present invention is not restricted to following example.
Embodiment 1
Hydrochloric acid (260.0g, 36%, 2.60mol) is placed in (N in reaction vessel2Protection), it is cooled with an ice bath to 10 DEG C,
It is slowly added into triethyl phosphine (300.0g, 2.54mol) while stirring, adds when reactant mixture viscosity is difficult to more greatly stirring
Enter appropriate methanol, react about 0.5 hour；Being heated to 60 DEG C, decompression is distilled off overwhelming majority water and methanol, obtains chlorine
Change triethyl group salt；Chlorination triethyl group salt is transferred in pressure reacting container, with vacuum pump, container inner pressure is down to 1
Below kPa, is warming up to 140 DEG C, then controls the addition speed of methanol and dimethyl carbonate with effusion meter, maintains reaction vessel
Interior pressure is 1.3～1.5MPa, and when hypertonia, (air valve front end assembling condensing tube is to prevent solvent and reaction to open air valve
Thing is discharged) release gas (CO2)；A total of about addition 100g methanol and 500g dimethyl carbonate, the complete continuation that feeds exists
Reacting 2 hours under the conditions of 150 DEG C and 1.6～1.8MPa, the response time amounts to 8 hours；After reaction terminates, subtract at 80 DEG C
Pressure is distilled off major part low boilers, obtains crude product methyl chloride triethyl group quaternary salt, then at 45 DEG C and 0.1kPa
Decompression is lower to be dried 8 hours, obtains methyl chloride triethyl group salt (419.0g, 2.49mol), productivity about 98%.
Embodiment 2
Use N2Displacement tainer air, is placed in tributylphosphine (300.0g, 1.49mol) together with 1000mL methanol
In reaction vessel, be cooled with an ice bath to 10 DEG C, be slowly added into while stirring double (trimethyl fluoride sulfonyl) imines (427.6g,
1.49mol), it is subsequently adding dimethyl carbonate (202.0g, 2.24mol), is warming up to 180 DEG C, 1.6～1.7MPa
React 6 hours under pressure；Reaction is reduced pressure at 80 DEG C after terminating and is distilled decompression removing low boilers, then at 60 DEG C and 0.1
KPa decompression is lower to be dried 4 hours, obtain double (trimethyl fluoride sulfonyl) formimino group tributyl quaternary salt of product (705.7g,
1.42mol), productivity about 95%.
Embodiment 3
Use N2Displacement tainer air, is placed in triphenylphosphine (300.0g, 1.14mol) instead together with 500mL methanol
Answer in container, be cooled with an ice bath to 10 DEG C, be slowly added into while stirring double (trimethyl fluoride sulfonyl) imines (321.8g, 1.14
Mol), it is subsequently adding dimethyl carbonate (202.0g, 2.24mol), is warming up to 160 DEG C, at 1.4～1.5MPa pressure
Lower reaction 4 hours；Reaction is reduced pressure at 80 DEG C after terminating and is distilled decompression removing low boilers, then at 60 DEG C and 0.1kPa
Decompression is lower to be dried 4 hours, obtains double (trimethyl fluoride sulfonyl) formimino group triphenyl quaternary salt (584.8g, 1.05mol) of product,
Productivity about 92%.
Embodiment 4
Use N2Displacement tainer air, is placed in reaction by triphenylphosphine (300.0g, 1.14mol) together with 500mL methanol
In container, under room temperature, it is slowly added into fluoborate solution (250.8g, 40%, 1.14mol) while stirring, reacts 1 hour.
It is warming up to 50 DEG C, removes major part first alcohol and water under reduced pressure, be subsequently adding dimethyl carbonate (202.0g, 2.24mol), rise
Temperature, to 160 DEG C, is reacted 6 hours under 1.4～1.5MPa pressure；Reaction is reduced pressure at 80 DEG C after terminating and is distilled decompression removing
Low boilers, is dried 4 hours under then reducing pressure at 60 DEG C and 0.1kPa, obtains product fluoboric acid methyl triphenyl quaternary salt
(375.0g, 1.03mol), productivity about 90%.
Embodiment 5
Use N2Displacement tainer air, is placed in diphenylphosphine (400.0g, 2.15mol) instead together with 400mL methanol
Answer in container, be cooled with an ice bath to 10 DEG C, be slowly added into while stirring double (trimethyl fluoride sulfonyl) imines (604.3g, 2.15
Mol), reacting 1 hour, be then heated to 60 DEG C, decompression is distilled off overwhelming majority methanol, obtains double (trifluoromethyl
Sulphonyl) inferior amine salt；Double (trimethyl fluoride sulfonyl) inferior amine salts are transferred in pressure reacting container, will hold with vacuum pump
In device, pressure is down to below 1kPa, is warming up to 140 DEG C, then controls the addition speed of methanol and dimethyl carbonate with effusion meter,
Maintain in reaction vessel that pressure is 1.2～1.4MPa, when hypertonia, open air valve (air valve front end assembling condensing tube in case
Only solvent is discharged with reactant) release gas (CO2)；A total of about addition 300g methanol and 500g dimethyl carbonate, add
4 hours material time, the complete continuation that feeds reacts 4 hours under the conditions of 150 DEG C and about 1.6MPa, and the response time amounts to 8
Hour；After reaction terminates, at 80 DEG C, decompression is distilled off major part low boilers, obtains double (the trifluoromethyl sulphur of crude product
Acyl) imines dimethyl diphenyl quaternary salt, it is dried 4 hours under then reducing pressure at 60 DEG C and 0.1kPa, obtains product double (three
Methyl fluoride sulphonyl) imines dimethyl diphenyl quaternary salt (1009.8g, 2.04mol), productivity about 95%.
Embodiment 6
Use N2Displacement tainer air, is placed in diethyl Phenylphosphine (200g, 1.2mol) instead together with 400mL methanol
Answer in container, be cooled with an ice bath to 15 DEG C, be slowly added into while stirring double (trimethyl fluoride sulfonyl) imines (338.6g, 1.2
Mol), react 10 hours, be subsequently adding dimethyl carbonate (202g, 2.24mol), be warming up to 180 DEG C, 1.4～1.7
React 6 hours under MPa pressure；Reaction is reduced pressure at 80 DEG C after terminating and is distilled decompression removing low boilers, then at 60 DEG C
Lower with 0.1kPa decompression dry 4 hours, obtain double (trimethyl fluoride sulfonyl) formimino group diethyl phenyl quaternary salt of product
(533.1g, 1.12mol), productivity about 93%.
Embodiment 7
Use N2Displacement tainer air, is placed in reaction by diphenylphosphine (200g, 1.08mol) together with 400mL methanol
In container, it is cooled with an ice bath to 10 DEG C, is slowly added into acetic acid (71.34g, 1.19mol) while stirring, react 5 hours,
It is subsequently adding dimethyl carbonate (202g, 2.24mol), is warming up to 170 DEG C, under 1.4～1.7MPa pressure, react 6 little
Time；Reaction is reduced pressure at 80 DEG C after terminating and is distilled decompression removing low boilers, then dry under 60 DEG C and 0.1kPa decompressions
4 hours, obtain acetic acid product dimethyl diphenyl quaternary salt (279.8g, 1.02mol), productivity about 94%.
Embodiment 8
Use N2Displacement tainer air, is placed in triphenylphosphine (300.0g, 1.14mol) instead together with 500mL methanol
Answer in container, be cooled with an ice bath to 10 DEG C, be slowly added into while stirring double (trimethyl fluoride sulfonyl) imines (320.3g, 1.14
Mol), it is subsequently adding diethyl carbonate (264.3g, 2.24mol), is warming up to 180 DEG C, at 1.4～1.5MPa pressure
Lower reaction 4 hours；Reaction is reduced pressure at 80 DEG C after terminating and is distilled decompression removing low boilers, then at 60 DEG C and 0.1kPa
Decompression is lower to be dried 4 hours, obtains double (trimethyl fluoride sulfonyl) iminoethyl triphenyl quaternary salt (599.5g, 1.05mol) of product,
Productivity about 92%.
Embodiment 9
In draughty ventilating kitchen, hydrochloric acid (520g, 36%, 5.20mol) is placed in (N in reaction vessel2Protection),
It is cooled with an ice bath to 0 DEG C, the most slowly hydrogen phosphide is slowly introducing in hydrochloric acid, before the intake of hydrogen phosphide is according to gas tank
After of poor quality be calculated (180.2g, 5.30mol), react about 4 hours；Being heated to 45 DEG C, decompression is distilled off
Major part water, obtains chlorate；Chlorate is transferred in pressure reacting container, with vacuum pump, container inner pressure is dropped
To below 1kPa, add 500g methanol, be warming up to 180 DEG C, then control the addition speed of dimethyl carbonate with effusion meter
Degree, in maintaining reaction vessel, pressure is 1.6～1.7MPa, when hypertonia, opens air valve (air valve front end assembling condensing tube
To prevent solvent from discharging with reactant) release gas (CO2), amount to and add dimethyl carbonate (2052g, 22.8mol),
The complete continuation that feeds is reacted 2 hours under the conditions of 160 DEG C and 1.6～1.7MPa, and the response time amounts to 12 hours；Reaction knot
Shu Hou, at 80 DEG C, decompression is distilled off major part low boilers, obtains crude product tetramethyl phosphonium chloride quaternary salt, then at 45 DEG C
Lower with 0.1kPa decompression dry 6 hours, obtain tetramethyl phosphonium chloride quaternary salt (619.8g, 4.9mol), productivity about 94%.
Embodiment 10
Use N2Displacement tainer air, is placed in triphenylphosphine (300.0g, 1.14mol) instead together with 500mL methanol
Answer in container, be heated to 60 DEG C, be slowly added into double (trimethyl fluoride sulfonyl) imines (321.8g, 1.14mol) while stirring,
It is subsequently adding ethylene carbonate (176.0g, 2.0mol), is warming up to 160 DEG C, under 1.4～1.5MPa pressure, react 4
Hour；Reaction is reduced pressure at 80 DEG C after terminating and is distilled decompression removing low boilers, then does under 60 DEG C and 0.1kPa decompressions
Dry 4 hours, obtain double (trimethyl fluoride sulfonyl) imines 2-hydroxyethyl triphenyl quaternary salt (616.3g, 1.05mol) of product,
Productivity about 92%.
Claims (27)
1. a preparation method for quaternary salt, including: the first step is reacted, by phosphorus-containing compound R1R2R3P reacts with Bronsted acid
Generate corresponding salt；Second step reacts, the salt and the dialkyl carbonate that generate during the first step is reacted, ethylene carbonate,
At least one reaction in Allyl carbonate, phenyl-carbonic acid methyl ester, diphenyl carbonate and dimethyl benzyl prepares quaternary salt；
Wherein, R1、R2、R3Separately selected from H, alkyl, thiazolinyl, alkynyl, aryl or above-mentioned organic group
In containing boron, silicon, nitrogen, phosphorus, oxygen, sulfur, fluorine, chlorine, bromine, the group of iodine at least one of which element；R1、R2、
R3Can be independent substituted radical, it is also possible to be that adjacent group combines cyclization；
Described Bronsted acid is selected from mineral acid, or organic acid, or non-acids proton compound, and described non-acids proton compound is permissible
Discharge active proton, and and phosphorus-containing compound reaction generation salt；
Described mineral acid is selected from carborane acid (H [CHB11Cl11]), hydrosulphuric acid (H2S), fluoboric acid (HBF4), fluorine silicon
Acid (H2SiF6), hexafluorophosphoric acid (HPF6), Fluohydric acid. (HF), hydrochloric acid (HCl), hydrobromic acid (HBr),
Hydroiodic acid (HI), arsenic acid (H3AsO4), arsenious acid (H3AsO3), pyroarsenic acid (H4As2O7), boric acid (H3BO3)、
12 tungsten boric acid (H5BW12O40), phosphoric acid (H3PO4), phosphorous acid (H3PO3), hypophosphorous acid (H3PO2)、
Hypophosphoric acid (H4P2O6), pyrophosphoric acid (H4P2O7), sulphuric acid (H2SO4), sulfurous acid (H2SO3), chlorine sulphur
Acid (HSO3Cl), fluosulfonic acid (HSO3F), metasilicic acid (H2SiO3Or SiO2·H2And orthosilicic acid (H O)4SiO4)、
In at least one；
Described organic acid selected from oxalic acid, formic acid, acetic acid, propanoic acid, succinic acid, trifluoracetic acid, trifluoromethanesulfonic acid, methanesulfonic acid,
Mandelic acid, methylsulfuric acid, ethyl sulfuric acid, oleic acid, stearic acid, acrylic acid, maleic acid, citric acid, double (adjacent benzene two
Phenol) boric acid, double oxalic acid boric acid, dimalonic acid boric acid, three (pentafluoroethyl group) three fluorophosphoric acid, triethyl group three fluorophosphoric acid,
Four cyano boric acid, tartaric acid, malic acid, citric acid, ascorbic acid, benzoic acid, benzenesulfonic acid, p-methyl benzenesulfonic acid, water
At least one in poplar acid and caffeic acid.
The preparation method of quaternary salt the most according to claim 1, it is characterised in that described phosphorus-containing compound R1R2R3P selects
At least one in hydrogen phosphide and organic phosphoric compound.
The preparation method of quaternary salt the most according to claim 2, it is characterised in that described organic phosphoric compound selected from primary phosphine,
At least one in secondary phosphine and tertiary phosphine.
The preparation method of quaternary salt the most according to claim 3, it is characterised in that described R1、R2、R3Separately
Selected from the alkyl that H, aryl, carbon number are 1～20.
The preparation method of quaternary salt the most according to claim 2, it is characterised in that described organic phosphoric compound selected from methylphosphine,
Dimethylphosphine, three methylphosphines, ethyl phosphine, diethyl phosphine, triethyl phosphine, tripropyl phosphine, di-t-butyl phosphine, tri-butyl phosphine,
Tributylphosphine, three n-pentyl phosphines, cyclohexyl phosphine, dicyclohexylphosphontetrafluoroborate, tricyclohexyl phosphine, three hexyl phosphines, tri octyl phosphine,
Phenylphosphine, diphenylphosphine, triphenylphosphine, dimethylphenylphosphine, diethyl Phenylphosphine, diphenyl butylphosphine, tribenzyl
At least one in phosphine, tris hydroxymethyl phosphine, 2-chloroethyl diethyl phosphine and three (pentafluoroethyl group) phosphine.
The preparation method of quaternary salt the most according to claim 1, it is characterised in that described non-acids proton compound is selected from
There is the imide analog compounds of structure as shown in formula 1 or formula 2:
Formula 1:HN (CmF2m+1SO2)(CnF2n+1SO2)；
Formula 2:HNCxF2x(SO2)2；
Wherein m is the integer of 0～5, and n is the integer of 0～5, and X is the integer of 1～10.
The preparation method of quaternary salt the most according to claim 6, it is characterised in that described imide analog compounds is selected from In at least one.
The preparation method of quaternary salt the most according to claim 1, it is characterised in that described non-acids proton compound is selected from
In three (trimethyl fluoride sulfonyl) methane, phenol, p-methyl phenol, betanaphthol, 2,4 dichloro phenol and para-aminophenol
At least one.
The preparation method of quaternary salt the most according to claim 1, it is characterised in that described dialkyl carbonate is selected from carbonic acid two
At least one in methyl ester, Ethyl methyl carbonate and diethyl carbonate.
The preparation method of quaternary salt the most according to claim 1, it is characterised in that the reaction of the described first step is in a solvent
Carry out.
The preparation method of 11. quaternary salts according to claim 10, it is characterised in that described solvent selected from water, alkane,
At least one in cycloalkane, alkyl halide, aromatic hydrocarbons, alcohol, ether, ketone, ester, nitrile and amide.
The preparation method of 12. quaternary salts according to claim 1, it is characterised in that the reaction temperature of first step reaction is
-20 DEG C～80 DEG C.
The preparation method of 13. quaternary salts according to claim 12, it is characterised in that the reaction temperature of first step reaction is
0 DEG C～60 DEG C.
The preparation method of 14. quaternary salts according to claim 1, it is characterised in that the reaction pressure of first step reaction is
0.05～2MPa.
The preparation method of 15. quaternary salts according to claim 14, it is characterised in that the reaction pressure of first step reaction is
0.09～0.5MPa.
The preparation method of 16. quaternary salts according to claim 1, it is characterised in that the first step reaction response time be
0.1～12 hour.
The preparation method of 17. quaternary salts according to claim 16, it is characterised in that the first step reaction response time be
0.5～8 hour.
The preparation method of 18. quaternary salts according to claim 1, it is characterised in that after the first step has been reacted, by washing
The mode washed and distill removes unreacted reactant and solvent.
The preparation method of 19. quaternary salts according to claim 1, it is characterised in that the reaction temperature of second step reaction is
60～280 DEG C.
The preparation method of 20. quaternary salts according to claim 19, it is characterised in that the reaction temperature of second step reaction is
100～200 DEG C.
The preparation method of 21. quaternary salts according to claim 1, it is characterised in that the reaction pressure of second step reaction is
0.1～3MPa.
The preparation method of 22. quaternary salts according to claim 21, it is characterised in that the reaction pressure of second step reaction is
0.8～2MPa.
The preparation method of 23. quaternary salts according to claim 1, it is characterised in that second step reaction response time be
0.5～24 hour.
The preparation method of 24. quaternary salts according to claim 23, it is characterised in that second step reaction response time be
2～15 hours.
The preparation method of 25. quaternary salts according to claim 1, it is characterised in that before second step reaction starts, reaction is held
Device noble gas is replaced or is evacuated.
The preparation method of 26. quaternary salts according to claim 1, it is characterised in that after second step has reacted, by steaming
The mode evaporated removes remaining reactant and solvent.
The preparation method of 27. quaternary salts according to claim 1, it is characterised in that after second step has reacted, by weight
Crystallization or the Methods For Purification product of extraction.
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| CN201310684970.3A CN104710475B (en) | 2013-12-13 | A kind of preparation method of quaternary salt | |
| US14/565,250 US9365596B2 (en) | 2013-12-13 | 2014-12-09 | Method for preparing quaternary phosphonium salts |
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| CN201310684970.3A CN104710475B (en) | 2013-12-13 | A kind of preparation method of quaternary salt |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4725926A (en) * | 1986-01-17 | 1988-02-16 | Asahi Glass Company Ltd. | Electric double layer capacitor having high capacity |
| US4892944A (en) * | 1987-05-13 | 1990-01-09 | Mitsubishi Petrochemical Co., Ltd. | Process for producing quaternary salts |
| CN1503778A (en) * | 2001-03-26 | 2004-06-09 | �����֯��ʽ���� | Ionic liquid electrolyte salt for storage device electrolytic solution for storage device electric double layer capacitor and secondary battery |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4725926A (en) * | 1986-01-17 | 1988-02-16 | Asahi Glass Company Ltd. | Electric double layer capacitor having high capacity |
| US4892944A (en) * | 1987-05-13 | 1990-01-09 | Mitsubishi Petrochemical Co., Ltd. | Process for producing quaternary salts |
| CN1503778A (en) * | 2001-03-26 | 2004-06-09 | �����֯��ʽ���� | Ionic liquid electrolyte salt for storage device electrolytic solution for storage device electric double layer capacitor and secondary battery |
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