CN116925031A - 氯代碳酸乙烯酯的纯化制备及其应用 - Google Patents
氯代碳酸乙烯酯的纯化制备及其应用 Download PDFInfo
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- CN116925031A CN116925031A CN202210372424.5A CN202210372424A CN116925031A CN 116925031 A CN116925031 A CN 116925031A CN 202210372424 A CN202210372424 A CN 202210372424A CN 116925031 A CN116925031 A CN 116925031A
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- Prior art keywords
- cec
- reaction
- salt
- ammonium
- mixture
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- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000746 purification Methods 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 239000000203 mixture Substances 0.000 claims description 33
- -1 quaternary ammonium cations Chemical class 0.000 claims description 31
- 150000003839 salts Chemical class 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 18
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical group N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 17
- 239000005695 Ammonium acetate Substances 0.000 claims description 17
- 235000019257 ammonium acetate Nutrition 0.000 claims description 17
- 229940043376 ammonium acetate Drugs 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical group [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- YBCVMFKXIKNREZ-UHFFFAOYSA-N acoh acetic acid Chemical compound CC(O)=O.CC(O)=O YBCVMFKXIKNREZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000007517 lewis acids Chemical group 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 150000002825 nitriles Chemical class 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
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 229950000688 phenothiazine Drugs 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims 2
- 239000001099 ammonium carbonate Substances 0.000 claims 2
- 239000007858 starting material Substances 0.000 claims 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 claims 2
- 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 2
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 claims 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims 1
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 claims 1
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- 235000012501 ammonium carbonate Nutrition 0.000 claims 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims 1
- 235000011130 ammonium sulphate Nutrition 0.000 claims 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims 1
- 229910001863 barium hydroxide Inorganic materials 0.000 claims 1
- JMXMXKRNIYCNRV-UHFFFAOYSA-N bis(hydroxymethyl)phosphanylmethanol Chemical compound OCP(CO)CO JMXMXKRNIYCNRV-UHFFFAOYSA-N 0.000 claims 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims 1
- 239000000920 calcium hydroxide Substances 0.000 claims 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims 1
- 239000000347 magnesium hydroxide Substances 0.000 claims 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims 1
- OKDQKPLMQBXTNH-UHFFFAOYSA-N n,n-dimethyl-2h-pyridin-1-amine Chemical compound CN(C)N1CC=CC=C1 OKDQKPLMQBXTNH-UHFFFAOYSA-N 0.000 claims 1
- 150000003003 phosphines Chemical group 0.000 claims 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 claims 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- HIGQQEOWQNDHJD-UHFFFAOYSA-N 4,4-dichloro-1,3-dioxolan-2-one Chemical compound ClC1(Cl)COC(=O)O1 HIGQQEOWQNDHJD-UHFFFAOYSA-N 0.000 description 37
- 239000000047 product Substances 0.000 description 25
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 21
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 14
- 238000004817 gas chromatography Methods 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000010813 internal standard method Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
本发明涉及新材料精细化学品领域,特别涉及氯代碳酸乙烯酯类化合物的新型高效纯化制备工艺方法,以及由此技术突破得到的纯品在制备衍生型碳酸酯化合物中的用途。该类化合物是重要的新能源电池电解液系统功能化学品以及含烯不饱和型可辐射聚合单体。
Description
【技术领域】
本发明涉及新材料精细化学品领域,特别涉及氯代碳酸乙烯酯类化合物的新型高效纯化制备工艺方法,以及由此技术突破得到的纯品在制备衍生型碳酸酯化合物中的用途。该类化合物是重要的新能源电池电解液系统功能化学品以及含烯不饱和型可辐射聚合单体。
【背景技术】
若干碳酸酯类化合物是重要的新能源电池电解液系统功能添加剂材料,同时也是用途广泛的含烯不饱和型可辐射聚合单体材料。市售代表性产品例如碳酸乙烯酯(EC),氯代碳酸乙烯酯(CEC),氟代碳酸乙烯酯(FEC),二氯代碳酸乙烯酯(Di-CEC),和碳酸亚乙烯酯(VC)。工业生产实践中,为本领域从业技术人员所熟知的,通常采用EC的气相或液相氯化法来制备CEC,CEC再经过氟化反应生产FEC,或经过氯化氢消除反应制造VC。
同时为行业从业技术人员所公知的,EC氯化工艺在产生CEC的同时,不可避免地副产二氯化物Di-CEC,且伴随不完全氯化造成的EC残留。因此,典型市售产品则是EC,CEC,和Di-CEC的混合物,难以得到纯净的CEC产品。三者的有效分离是行业内长期未能得到解决的重大技术瓶颈难题(参考文献CN113912581,CN114163413,CN113402494)。传统的精馏工艺流程复杂冗长,高温真空条件苛刻,投资成本高昂,且由于混合物组分的热敏性造成产品分解或聚合副反应废渣,抑或是由于混合物组分的共沸特性造成难以将产品纯化到所需要的纯度。
本项申请的要旨在于,出其不意地发明了一种新奇的化学转化工艺方法,使用简单易得的试剂,在温和反应条件下,选择性地实现了二氯化物Di-CEC的有效去除,从而首次实现了单氯代碳酸乙烯酯(CEC)的低成本和环境友好型纯化制备。由此制备的CEC纯品本身有广泛应用,且可以直接作为前驱体原料生产FEC和VC,简化了后者的生产工艺并显著提升了产品收率与纯度。
【发明内容】
本项申请现已意外地发现,分别如反应式(I)和(II)所示,含有CEC和Di-CEC混合物与盐Salt在反应条件conditions下作用,Di-CEC组分被选择性地去除从而得到单一CEC纯品;或,含有EC,CEC,和Di-CEC混合物与盐Salt在反应条件conditions下作用,Di-CEC被选择性地去除从而得到单一CEC在EC中的纯品。由此得到的纯品CEC在需要时可通过简单蒸馏或精馏进一步提纯到更高等级标准的纯度。这些原料混合物可以方便地通过氯化自制或从市售渠道直接获得,因此该种纯化制备CEC的工艺具备广谱的适用性和卓越的经济成本竞争力价值。
其中盐Salt是(非)金属阳离子的羧酸盐,氢卤酸盐,(亚)硫酸(氢)盐,磺酸盐,磷酸(氢)盐,硝酸盐,碳酸(氢)盐,硼酸盐,氨水,或氢氧化物中的至少一种;金属阳离子是指元素周期表中所涵盖金属元素的阳离子形式,(非)金属阳离子是指季铵阳离子,季磷阳离子,硫鎓阳离子,碘鎓阳离子。氢卤酸是HCl,HBr,HF,HI。
以原料摩尔量为基准,盐Salt的添加量在0.001-100当量区间;优选在0.1-50当量区间;更优选在0.1-30当量区间;进一步更优选在1-10当量区间。
优选的Salt是季铵阳离子的羧酸盐,季铵阳离子是氨,叔胺,或含氮杂环衍生的季铵阳离子;羧酸阴离子是脂肪性或芳香性羧酸阴离子。
更优选的Salt是如下分子结构式描述的季铵阳离子的羧酸盐,其中R1-R5彼此独立的是氢,或一价或二价的含有1-24个碳原子(以下标记为C1-C24)的直链或支链的烷基基团,该基团可以为1-6个非连续的氧原子,氮原子,硫原子,氟原子,硅原子,羰基,羟基,胺基,羧基,双键,三键,硅氧基,或C6-C24芳环取代;或者,R1-R5彼此独立的是或一价或二价的C4-C24(杂)芳基,该芳基可以含有0-4个C1-C24烷基,OC1-C24烷氧基,SC1-C24烷硫基,NHC1-C24烷胺基,N(C1-C24)2烷胺基,或卤素取代基;R2-R5任意二者之间也可以形成一个C3-C12环结构,该环结构可以为1-4个非连续的氧原子,氮原子,硫原子,双键,或羰基间断。
更优选的Salt是氨阳离子的羧酸盐,即R2 = R3 = R4 = R5 = H;
进一步更优选的Salt是氨阳离子的甲酸盐或乙酸盐(醋酸盐),即R1 = H或CH3; R2= R3 = R4 = R5 = H。
是指催化剂,促进剂,阻聚剂,光,热,微波,超声波,真空或压力,溶剂等条件中的至少一种;或优选的,是上述任意两种或两种以上因素的联合使用。
催化剂或促进剂是路易斯酸或路易斯碱化合物;
催化剂或促进剂的添加量是反应原料的0.1-50%;优选的是1-50%,更优选的是1-30%,进一步更优选的是1-20%。
阻聚剂是苯酚,苯酚类衍生物(包括但不限于对苯二酚,邻苯二酚,间苯二酚,对甲基苯酚,对甲氧基苯酚,2,6-二叔丁基-4-甲基苯酚,焦性没食子酸等),三(N-亚硝基-N-苯基羟胺)铝盐,或CuCl,吩噻嗪,亚磷酸酯,亚磷酸三哌啶氮氧自由基酯,N,N-二烷基二硫代氨基甲酸铜,或上述阻聚剂的混合体系;阻聚剂的用量按照原料的摩尔百分比计为0.01-5%,优选的是0.01-3%;
光是指反应体系在光辐照条件下进行,光的波长范围的200-780纳米;
热是指反应体系在加热条件下进行,反应温度是-25-450摄氏度,优选的是-20-400摄氏度;更优选的是0-350摄氏度;进一步更优选的是0-250摄氏度;
微波或超声波是指使用微波或超声波发生器辐射反应体系;
压力是指反应体系在加压或一定真空度条件下进行,反应工艺的压力可以是0.001-200个大气压,优选的是0.01-100个大气压,更优选的是1-80个大气压,进一步更优选的是1-50个大气压。
溶剂可以是芳香性或脂肪性烃,卤代芳香性或脂肪性烃,或各类酯,醇,醚,腈,酮,酰胺,砜,碳酸酯,或水,或新兴的“离子液(Ionic Liquids)型”或超临界二氧化碳(Supercritical CO2)等所谓绿色溶剂;或上述任意二者或二者以上的混合溶剂体系。溶剂的使用是优选但非必需的,在某些条件下,可以不使用溶剂,即使用反应原料的溶解体,熔融体,或反应原料直接混合后在加热,研磨,或气相条件下进行反应。
遵循反应式(I-II)技术原理的一个优选的制备CEC纯品的实施工艺流程方式是,如反应式(III)所示,含有EC,CEC,和Di-CEC的混合物,先与Salt在反应条件conditions下作用,选择性地去除其中的Di-CEC组分,从而得到只含有CEC和EC的中间体混合物;该中间体再作为原料进行氯化反应,EC得到完全消耗从而获得CEC和Di-CEC的混合物,该混合物再与Salt在反应条件conditions下作用,进一步选择性地去除其中的Di-CEC组分,从而得到CEC纯品。优选的Salt是醋酸铵或甲酸铵。
由此制备的CEC纯品本身有广泛应用,且可以直接作为前驱体原料在经历氟化反应后生产FEC,或在经历氯化氢消除反应后生产VC,简化了后者的生产工艺并显著提升了产品收率与纯度。
一个实施的方式是下列反应式(IV)所示的流程,由此得到的EC和CEC混合物和形式为QR6R7R8的胺化物或膦化物作用,得到EC和季胺盐或季膦盐CEC-Q,然后CEC-Q分解为产品VC,蒸馏或精馏由此得到的EC和VC的混合物,即可得到VC纯品;或,先行将EC和CEC-Q经过萃取和(或)结晶分离得到CEC-Q纯品,由此CEC-Q再分解生成VC纯品。其中Q = N或P,R6,R7,或R8的定义彼此独立的与R1相同,基团R6,R7,或R8同时可以相互组成一个环状结构,即此时QR6R7R8是一个杂环;conditions定义与前相同;优选的,QR6R7R8是叔胺,叔膦,氮杂环,膦杂环。
在实施例中我们将进一步说明。
【具体实施方式】
下面结合具体实施例进一步说明本发明要旨:
实施例一:
在常温下,将40.3克CEC和Di-CEC混合物(百分质量比例80:20),15.4克乙酸铵,500毫升碳酸二甲酯加入反应瓶中,常温下搅拌反应3小时,反应完后加入300毫升水,依次用300毫升×3次乙酸乙酯分液萃取,合并有机相,硫酸钠干燥,过滤,浓缩旋干后使用气相色谱GC进行检测,Di-CEC剩余含量为0即完全消失,CEC剩余含量为99.0%(二者比例99:0)。
将投料量放大10倍后,重复上述试验,使用0.1当量联苯为内标,每隔一小时监测CEC和Di-CEC的剩余量,结果如下:1小时二者数值分别为97.3%和47.7%;2小时二者数值分别为96.7%和31.4%;3小时二者数值分别为95.0%和24.8%;4小时二者数值分别为94.3%和8.2%;5小时二者数值分别为92.8%和0.0%;上述结果清晰地表明醋酸铵能选择性地消耗和去除Di-CEC。
重复上述试验,不添加醋酸铵,所得CEC和Di-CEC比例为80:20;
重复上述试验,将醋酸铵换成甲酸铵,所得CEC和Di-CEC比例为98:0;
重复上述试验,将醋酸铵换成醋酸银,所得CEC和Di-CEC比例为94:2;
重复上述试验,将醋酸铵换成醋酸钠,所得CEC和Di-CEC比例为90:8;
重复上述试验,将醋酸铵换成醋酸镁,所得CEC和Di-CEC比例为93:6;
重复上述试验,将醋酸铵换成氯化铵,所得CEC和Di-CEC比例为82:9;
重复上述试验,将醋酸铵换成碳酸氢钠,所得CEC和Di-CEC比例为86:11;
重复上述试验,将醋酸铵换成碳酸钠,所得CEC和Di-CEC比例为89:8;
重复上述试验,将醋酸铵换成氨水,所得CEC和Di-CEC比例为81:10;
重复上述试验,将醋酸铵换成氢氧化钠,所得CEC和Di-CEC比例为78:13;
上述结果清晰地表明多种所批露的Salt具备选择性去除Di-CEC的能力,并以醋酸铵和甲酸铵尤为高效。
重复上述试验,将溶剂DMC换成四氢呋喃THF,所得CEC和Di-CEC比例为98:0;
重复上述试验,不使用任何溶剂,所得CEC和Di-CEC比例为95:0;
重复上述试验,将溶剂DMC换成二氯甲烷或二氯乙烷,所得CEC和Di-CEC比例为80:15和80:12;
上述结果清晰地表明极性溶剂或无溶剂体系有利于Di-CEC的选择性去除。
实施例二:
在常温下,将40.5克CEC,EC,和Di-CEC三元混合物(百分质量比例80:8:12),15.4克乙酸铵,500毫升碳酸二甲酯加入反应瓶中,常温下搅拌反应3小时,反应完后加入300毫升水,依次用300毫升×3次乙酸乙酯分液萃取,合并有机相,硫酸钠干燥,过滤,浓缩旋干后使用气相色谱GC进行检测,Di-CEC剩余含量为0,EC剩余含量为90.0%,CEC剩余含量为97.2%。
实施例三:
在常温下,将500克CEC,EC,和Di-CEC三元混合物(百分质量比例80:8:12),180克乙酸铵加入反应瓶中,常温下搅拌反应3小时,反应完后过滤,滤液加入300毫升水,依次用300毫升×3次乙酸乙酯分液萃取,合并有机相,硫酸钠干燥,过滤,浓缩旋干后得到液体390克,使用气相色谱GC进行检测,所得产物中,Di-CEC含量为0,CEC与EC比例为90:10。
将上述所得产物在紫外灯照射下通入氯气,常温搅拌5小时,利用气相色谱GC检测,其中EC含量降低为0.6%,CEC含量为95.4%,Di-CEC含量为4%。将此混合物重复上述步骤,得到350克纯CEC,其中CEC含量为99.2%,EC含量为0.4%。
实施例四:
在氮气氛围保护下,将 33.8克纯化后的CEC与500 毫升碳酸二甲酯加入反应瓶中,控制温度在55-57 ℃于一小时内缓慢滴入33.3 克三乙胺,之后60-65 ℃下保温反应3小时,反应结束后气相色谱GC检测(联苯内标法测定), 所得VC收率为93.5 %
该结果清晰地表明使用了纯的CEC作为原料,可以显著提升的高收率制备得到VC产品。
实施例五:
在氮气气氛下,将300毫升碳酸二甲酯,300克纯化后的CEC(99.3%)和500克氟化钾加入反应瓶中。控制加热温度95 ℃回流10小时,反应结束后气相色谱检测(联苯内标法测定),CEC全部反应完全,FEC收率83.2%,纯度98.5%。
该结果清晰地表明使用了纯的CEC作为原料,可以显著提升的高收率和高纯度制备得到FEC产品。
实施例六:
直接精馏法:在氮气氛围保护和冷却下,将 23.6克EC和CEC混合物(其中二者质量百分比分别为8.1%和91.9%)用60毫升干燥三乙胺稀释,温度逐渐由零度缓慢升温至50 ℃左右,保温3小时后,继续升温至65-85 ℃,反应进程用气相色谱GC检测(联苯内标法测定),约2小时后反应完全,减压精馏得到VC纯品12.1克。
分离两步法:重复上述实验过程,但在保温3小时后,将反应混合物在600毫升正己烷-半饱和食盐水液相中(体积比1/5)分相分配,有机相用等体积半饱和食盐水洗涤三次,合并水相后用半体积乙酸丁酯萃取六次,合并有机相,无水硫酸钠干燥,滤过,浓缩至80毫升,逐步升温至65-85 ℃,反应进程用气相色谱GC检测(联苯内标法测定), 2小时后反应完全,减压蒸馏得到VC纯品10.5克。
重复上述两步法实验过程,但将60毫升干燥三乙胺替换成45毫升无水吡啶,过程结束后减压蒸馏得到VC纯品8.9克。
需要强调的是,上述实施例仅仅为示例性而非限定性说明,基于本项申请披露,任何从业技术人员所通常可能采用的反应条件或参数等调整或变动均不会偏离本发明的要旨,本专利的保护范围应以相关的权利书记载条目为准。
Claims (10)
1.反应式(I)和(II)所示的氯代碳酸乙烯酯纯化工艺方法:含有CEC和Di-CEC混合物与盐Salt在反应条件conditions下作用,Di-CEC组分被选择性地去除从而得到单一CEC纯品;或,含有EC,CEC,和Di-CEC混合物与盐Salt在反应条件conditions下作用,Di-CEC被选择性地去除从而得到单一CEC在EC中的纯品;
其中盐Salt是(非)金属阳离子的羧酸盐,氢卤酸盐,(亚)硫酸(氢)盐,磺酸盐,磷酸(氢)盐,硝酸盐,碳酸(氢)盐,硼酸盐,氨水,或氢氧化物中的至少一种;金属阳离子是指元素周期表中所涵盖金属元素的阳离子形式,(非)金属阳离子是指季铵阳离子,季磷阳离子,硫鎓阳离子,碘鎓阳离子;氢卤酸是HCl,HBr,HF,HI;以原料摩尔量为基准,Salt的添加量在0.001-100当量区间;
conditions是指催化剂,促进剂,阻聚剂,光,热,微波,超声波,真空或压力,溶剂等条件中的至少一种。
2.根据权利要求(1),催化剂或促进剂是路易斯酸或路易斯碱化合物;阻聚剂是苯酚,苯酚类衍生物(包括但不限于对苯二酚,邻苯二酚,间苯二酚,对甲基苯酚,对甲氧基苯酚,2,6-二叔丁基-4-甲基苯酚,焦性没食子酸等),三(N-亚硝基-N-苯基羟胺)铝盐,或CuCl,吩噻嗪,亚磷酸酯,亚磷酸三哌啶氮氧自由基酯,N,N-二烷基二硫代氨基甲酸铜,或上述阻聚剂的混合体系;光是指反应体系在光辐照条件下进行,光的波长范围的200-780纳米;热是指反应体系在加热条件下进行,反应温度是-25-450摄氏度;微波或超声波是指使用微波或超声波发生器辐射反应体系;压力是指反应体系在加压或一定真空度条件下进行,反应工艺的压力是0.001-200个大气压;溶剂是芳香性或脂肪性烃,卤代芳香性或脂肪性烃,或各类酯,醇,醚,腈,酮,酰胺,砜,碳酸酯,或水,或 “离子液型”或超临界二氧化碳等绿色溶剂;或上述任意二者或二者以上的混合溶剂体系;溶剂的使用是优选但非必需的,在某些条件下,可以不使用溶剂,即使用反应原料的溶解体,熔融体,或反应原料直接混合后在加热,研磨,或气相条件下进行反应。
3.根据权利要求(1),优选的Salt是季铵阳离子的羧酸盐,季铵阳离子是氨,叔胺,或含氮杂环衍生的季铵阳离子;羧酸阴离子是脂肪性或芳香性羧酸阴离子。
4.根据权利要求(1)和(3),更优选的Salt是如下分子结构式描述的季铵阳离子的羧酸盐,其中R1-R5彼此独立的是氢,或一价或二价的含有1-24个碳原子(以下标记为C1-C24)的直链或支链的烷基基团,该基团可以为1-6个非连续的氧原子,氮原子,硫原子,氟原子,硅原子,羰基,羟基,胺基,羧基,双键,三键,硅氧基,或C6-C24芳环取代;或者,R1-R5彼此独立的是或一价或二价的C4-C24(杂)芳基,该芳基可以含有0-4个C1-C24烷基,OC1-C24烷氧基,SC1-C24烷硫基,NHC1-C24烷胺基,N(C1-C24)2烷胺基,或卤素取代基;R2-R5任意二者之间也可以形成一个C3-C12环结构,该环结构可以为1-4个非连续的氧原子,氮原子,硫原子,双键,或羰基间断;
更优选的Salt是氨阳离子的羧酸盐,即R2 = R3 = R4 = R5 = H;
进一步更优选的Salt是氨阳离子的甲酸盐或乙酸盐(醋酸盐),即R1 = H或CH3; R2 = R3= R4 = R5 = H。
5.根据权利要求(1)和(2),以原料摩尔量为基准,盐Salt的添加量优选在0.1-50当量区间;更优选在0.1-30当量区间;进一步更优选在1-10当量区间;conditions优选的是催化剂,促进剂,阻聚剂,光,热,微波,超声波,真空或压力,溶剂等条件中任意两种或两种以上因素的联合使用;催化剂或促进剂的添加量是反应原料的0.1-50%;优选的是1-50%,更优选的是1-30%,进一步更优选的是1-20%;阻聚剂的用量按照原料的摩尔百分比计为0.01-5%,优选的是0.01-3%;优选的反应温度是-20-400摄氏度;更优选的是0-350摄氏度;进一步更优选的是0-250摄氏度;优选的反应压力是0.01-100个大气压,更优选的是1-80个大气压,进一步更优选的是1-50个大气压。
6.根据权利要求(1),优选的一个制备CEC纯品的实施工艺流程方式如反应式(III)所示,即含有EC,CEC,和Di-CEC的混合物,先与盐Salt在反应条件conditions下作用,选择性地去除其中的Di-CEC组分,从而得到只含有CEC和EC的中间体混合物;该中间体再作为原料进行氯化反应,EC得到完全消耗从而获得CEC和Di-CEC的混合物,该混合物再与盐Salt在反应条件conditions下作用,进一步选择性地去除其中的Di-CEC组分,从而得到CEC纯品:
。
7.根据权利要求(1)和(6),优选的Salt是醋酸铵,甲酸铵,醋酸银,草酸铵,氨水,氯化铵,溴化铵,硫酸铵,碳酸铵,碳酸氢铵,硫酸氢氨,硫酸氢钠,氢氧化钠,氢氧化钙,氢氧化钾,氢氧化镁,氢氧化铝,氢氧化钡。
8.根据权利要求(1),由此制备得到的纯CEC作为原材料在生产FEC和VC中的用途。
9.根据权利要求(1)和(8),如反应式(IV)所示的VC制备流程:由EC和CEC的混合物和形式为QR6R7R8的胺化物或膦化物作用,得到EC和季胺盐或季膦盐CEC-Q中间体混合物,然后CEC-Q分解为产品VC,蒸馏或精馏由此产生的EC和VC混合物得到VC纯品;或,先行将EC和CEC-Q经过萃取和(或)结晶分离得到CEC-Q纯品,CEC-Q再分解生成VC纯品;其中Q = N或P,R6,R7,或R8的定义彼此独立的与R1相同,基团R6,R7,或R8同时可以相互组成一个环状结构,即此时QR6R7R8是一个杂环;conditions定义与前相同;
。
10.根据权利要求(9),优选的QR6R7R8是叔胺,叔膦,氮杂环,膦杂环;更优选的QR6R7R8是三甲胺,三乙胺,三丁胺,二异丙基乙胺,DBU,DBN,N-甲基-环己胺,四甲基乙二胺,N, N-二甲基苯胺,吡啶,咪唑,4-N, N-二甲胺基吡啶(DMAP),三苯基膦,三苄基膦,三甲基膦,三乙基膦,三丁基膦,三羟甲基膦。
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