CN111393403B - 一种碳酸亚乙烯酯的制备方法 - Google Patents
一种碳酸亚乙烯酯的制备方法 Download PDFInfo
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- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- UWTUEMKLYAGTNQ-OWOJBTEDSA-N (e)-1,2-dibromoethene Chemical group Br\C=C\Br UWTUEMKLYAGTNQ-OWOJBTEDSA-N 0.000 claims abstract description 18
- -1 alkali metal halide salt Chemical class 0.000 claims abstract description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910001508 alkali metal halide Inorganic materials 0.000 claims abstract description 12
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 27
- 230000008901 benefit Effects 0.000 abstract description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007033 dehydrochlorination reaction Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical class ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
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- 230000008018 melting Effects 0.000 description 1
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- 239000012264 purified product Substances 0.000 description 1
- 238000007347 radical substitution reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C07D317/34—Oxygen atoms
- C07D317/40—Vinylene carbonate; Substituted vinylene carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/068—Polyalkylene glycols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种碳酸亚乙烯酯的制备方法,该制备方法包括:使1,2‑二溴乙烯与碱式碳酸盐在水中、在碱金属卤盐与相转移催化剂存在下反应,生成碳酸亚乙烯酯;本发明方法不仅收率高、纯度好,且反应过程可控、成本低、操作工艺简单,适于工业化应用。
Description
技术领域
本发明属于锂离子电池电解液的有机成膜添加剂和/或过充电保护添加剂领域,具体涉及一种碳酸亚乙烯酯的制备方法。
背景技术
碳酸亚乙烯酯(VC,Vinylene Carbonate),室温下为无色透明液体,熔点为21℃,沸点为165℃/760mmHg,密度(20℃)为1.360g/cm3,1953年Newman等人首次报道了碳酸亚乙烯酯的合成方法(J.Am.Chem.Soc.,1953,75(5),pp1263–1264),利用氯气与碳酸亚乙酯发生自由基取代合成氯代碳酸乙烯酯,而后用三乙胺在醚溶剂下发生消除反应得到碳酸亚乙烯酯。其主要是作为锂离子电池新型有机成膜添加剂与过充电保护添加剂等等,具有良好的高低温性能与防气胀功能,可以提高电池的容量和循环寿命,还可作为制备聚碳酸乙烯酯的单体。
目前合成碳酸亚乙烯酯的方法基本遵循Newman等人的合成方案并加以改进,但是该方法会产生大量的氯化氢废气,大量三乙胺盐酸盐固废以及结焦釜残,对环境以及操作方面产生较大影响。例如中国发明专利CN106831699A公开了一种碳酸亚乙烯酯的合成方法,包括以下步骤:a)将有机溶剂进行干燥脱水;所述有机溶剂为甲基叔丁基醚、四氢呋喃、氯仿、二氯甲烷中的一种或几种;b)氮气保护下,在30℃~100℃向有机溶剂中添加有机溶剂总质量0.2wt%~3wt%阻聚剂和抗氧剂复配物,氯代碳酸乙烯酯在有机溶剂中与含氮类脱氯化氢剂发生脱氯化氢反应,反应2~10小时;其中氯代碳酸乙烯酯与有机溶剂的摩尔比为1:0.5~2,氯代碳酸乙烯酯与含氮类脱氯化氢剂的摩尔比例为1:1.0~1.2;c)所得产物经过滤除盐、负压两次精馏即可得到碳酸亚乙烯酯;虽然此专利在反应的温和度、降低副反应发生等方面做出了改进,但是仍然不可避免的产生了大量的氯化氢废气,对环境造成破坏,对设备造成腐蚀等影响,会间接的增加生产成本。
同时现有技术中还公开了一种由碳酸亚乙酯直接制备碳酸亚乙烯酯的方法,例如中国发明专利CN1789259公开了一种合成碳酸亚乙烯酯的方法,在采用固定床反应器,加入催化剂,在氮气、氩气或氢气作为稀释气体和体积气,反应温度为200℃~600℃,进料空速为1~100g/h·mlcat,反应压力为0.1~10MPa条件下,碳酸乙烯酯催化脱氢得到碳酸亚乙烯酯。此专利虽然避免了通常使用氯代后再进行消除反应过程中产生的氯化氢以及盐类固废以及结焦釜残,但其仍然会产生氢气、且反应温度很高(200℃~600℃),会对实际生产过程中的设备要求以及安全防护措施产生极大负面影响。
又如中国发明CN1290840C以一氯代碳酸乙烯与三乙胺发生脱氯反应合成碳酸亚乙烯酯,然而此类型反应存在副产物多、收率不理想、溶剂使用量大等缺陷,造成后续工艺操作分离难度高等问题。
发明内容
本发明的目的是克服现有技术的不足,提供一种新的制备碳酸亚乙烯酯的方法,该方法不仅收率高、纯度好,且反应过程可控、成本低、操作工艺简单,适于工业化应用。
为达到上述目的,本发明采用的技术方案是:一种碳酸亚乙烯酯的制备方法,所述制备方法包括:使1,2-二溴乙烯与碱式碳酸盐在水中、在碱金属卤盐与相转移催化剂存在下反应,生成所述碳酸亚乙烯酯。
根据本发明的一些优选方面,所述碱金属卤盐与所述相转移催化剂的投料质量比为1∶1.5-5。更优选地,所述碱金属卤盐与所述相转移催化剂的投料质量比为1∶1.5-3.5。进一步优选地,所述碱金属卤盐与所述相转移催化剂的投料质量比为1∶1.5-3。
根据本发明的一些优选方面,以质量百分含量计,所述碱金属卤盐与所述相转移催化剂的总投料量占所述1,2-二溴乙烯的投料量的0.1-1%。更优选地,以质量百分含量计,所述碱金属卤盐与所述相转移催化剂的总投料量占所述1,2-二溴乙烯的投料量的0.1-0.6%。
根据本发明的一些优选方面,使所述反应在温度50-100℃下进行。更优选地,使所述反应在温度60-100℃下进行。进一步优选地,使所述反应在温度70-100℃下进行。更进一步优选地,使所述反应在温度80-95℃下进行。
根据本发明的一些优选方面,所述1,2-二溴乙烯与所述碱式碳酸盐的投料摩尔比为1∶1-10。更优选地,所述1,2-二溴乙烯与所述碱式碳酸盐的投料摩尔比为1∶1-5。进一步优选地,所述1,2-二溴乙烯与所述碱式碳酸盐的投料摩尔比为1∶1.05-3。
根据本发明的一些优选且具体的方面,使所述反应在保护气体存在下反应,所述保护气体包括但不限于氮气、氩气。
根据本发明的一些优选且具体的方面,所述碱式碳酸盐为选自碳酸钠、碳酸钾和碳酸锂中的一种或多种的组合。
根据本发明的一些优选且具体的方面,所述碱金属卤盐为选自碘化钾、溴化钾、碘化钠和溴化钠中的一种或多种的组合。
根据本发明的一些优选且具体的方面,所述相转移催化剂为选自苄基三乙基氯化铵、四丁基溴化铵、四丁基氯化铵和聚乙二醇中的一种或多种的组合。
根据本发明的一些优选且具体的方面,所述制备方法还包括如下步骤:在所述反应完成之后,采用萃取剂萃取,干燥,分离。
根据本发明的一些具体方面,所述反应可以采用保温反应的方式,反应时间为10-24h。
根据本发明的一些具体方面,所述萃取剂为选自乙酸乙酯、碳酸二甲酯、氯仿、二氯甲烷、甲基叔丁基醚和甲苯中的一种或多种组合。
根据本发明的一些具体方面,所述干燥采用分子筛干燥脱水。
根据本发明的一些具体方面,所述分离可以采用将干燥后的混合物减压脱除所述萃取剂,制成碳酸亚乙烯酯的初步提纯产品。
根据本发明的一些具体方面,上述处理后的碳酸亚乙烯酯可经过精馏和重结晶得到电池级碳酸亚乙烯酯。
根据本发明,所述1,2-二溴乙烯可以商购获得,也可以通过如下方法制备而得:12-18℃下将乙炔和含溴4-6%的四氯化碳溶液通过微通道管式反应器,控制二者加入量1:1的摩尔比反应,反应结束闪蒸脱溶,得到1,2-二溴乙烯,含量98%以上。
由于上述技术方案运用,本发明与现有技术相比具有下列优点:
本发明创新地采用1,2-二溴乙烯与碱式碳酸盐作为反应原料,并且采用特定的催化剂组合,使两者的反应不仅可控且收率以及纯度均较为优异,同时整个过程基本能够实现环保,安全性好,萃取剂可回收,且反应后获得的卤盐可以再次使用或者销售,经济效益高。
具体实施方式
以下结合具体实施例对上述方案做进一步说明;应理解,这些实施例是用于说明本发明的基本原理、主要特征和优点,而本发明不受以下实施例的范围限制;实施例中采用的实施条件可以根据具体要求做进一步调整,未注明的实施条件通常为常规实验中的条件。
下述实施例中未作特殊说明,所有原料均来自于商购或通过本领域的常规方法制备而得。
以下制备碳酸亚乙烯酯的反应过程如下:
其中,M2CO3为碱式碳酸盐。
实施例1碳酸亚乙烯酯的制备
氮气保护下,向1000ml四口烧瓶(带冷凝管)中加入碳酸钠130克,去离子水600毫升,搅拌升温至40℃完全溶解后加入1,2-二溴乙烯200克,碘化钾0.2克,聚乙二醇600 0.4克,继续升温至90℃,保温反应10小时,降温至室温。反应液中加入100ml乙酸乙酯萃取2次,合并有机相经分子筛干燥,过滤,减压蒸馏脱除溶剂得到86.4克碳酸亚乙烯酯粗品,纯度91.3%,纯品收率85%。
实施例2碳酸亚乙烯酯的制备
氮气保护下,向1000ml四口烧瓶(带冷凝管)中加入碳酸钠130克,去离子水600毫升,搅拌升温至40℃完全溶解后加入1,2-二溴乙烯200克,碘化钾0.2克,四丁基溴化铵0.4克,继续升温至90℃,保温反应10小时,降温至室温。反应液中加入100ml氯仿萃取2次,合并有机经分子筛干燥,过滤,减压蒸馏脱除溶剂得到90克碳酸亚乙烯酯粗品,纯度90.3%,收率88%。
实施例3碳酸亚乙烯酯的制备
氮气保护下,向1000ml四口烧瓶(带冷凝管)中加入碳酸钾150克,去离子水600毫升,搅拌升温至40℃完全溶解后加入1,2-二溴乙烯200克,溴化钾0.2克,苄基三乙基氯化铵0.5克,继续升温至92℃,保温反应12小时,降温至室温。反应液中加入100ml氯仿萃取2次,合并有机相经分子筛干燥,过滤,减压蒸馏脱除溶剂得到88克碳酸亚乙烯酯粗品,纯度90.5%,收率86%。
实施例4碳酸亚乙烯酯的制备
氮气保护下,向5000ml四口烧瓶(带冷凝管)中加入碳酸钠700克,去离子水3000毫升,搅拌升温至40℃完全溶解后加入1,2-二溴乙烯1000克,碘化钾0.8克,聚乙二醇600 2克,继续升温至92℃,保温反应12小时,降温至室温。反应液中加入500ml氯仿萃取2次,合并有机相经分子筛干燥,过滤,减压蒸馏脱除溶剂得到444克碳酸亚乙烯酯粗品,纯度92.4%,收率88.6%。
进一步,经高真空减压精馏(3mmHg)和结晶(12~22℃)得到320克高纯碳酸亚乙烯酯,纯度99.998%。
对比例1
基本同实施例1,其区别仅在于:不加碘化钾,相应调整聚乙二醇600的用量为0.6克,得到75.2克碳酸亚乙烯酯粗品,纯度92%,收率74.81%。
对比例2
基本同实施例1,其区别仅在于:不加聚乙二醇600,相应调整碘化钾的用量为0.6克,得到54克碳酸亚乙烯酯粗品,纯度89.54%,收率55.28%。
对比例3
基本同实施例1,其区别仅在于:将原料1,2-二溴乙烯替换为同等摩尔量的1,2-二氯乙烯,色谱跟踪分析,未见明显反应。
上述实施例只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (4)
1.一种碳酸亚乙烯酯的制备方法,其特征在于,所述制备方法包括:使1,2-二溴乙烯与碱式碳酸盐在水中、在碱金属卤盐与相转移催化剂存在下、在温度50-100℃下、在保护气体存在下反应,生成所述碳酸亚乙烯酯;其中,所述碱金属卤盐与所述相转移催化剂的投料质量比为1∶1.5-5,所述1,2-二溴乙烯与所述碱式碳酸盐的投料摩尔比为1∶1-10,所述碱金属卤盐为选自碘化钾、溴化钾、碘化钠和溴化钠中的一种或多种的组合,所述相转移催化剂为选自苄基三乙基氯化铵、四丁基溴化铵、四丁基氯化铵和聚乙二醇中的一种或多种的组合,以质量百分含量计,所述碱金属卤盐与所述相转移催化剂的总投料量占所述1,2-二溴乙烯的投料量的0.1-1%,所述碱式碳酸盐为选自碳酸钠、碳酸钾和碳酸锂中的一种或多种的组合。
2.根据权利要求1所述的碳酸亚乙烯酯的制备方法,其特征在于,使所述反应在温度80-95℃下进行。
3.根据权利要求1所述的碳酸亚乙烯酯的制备方法,其特征在于,所述保护气体为氮气或氩气。
4.根据权利要求1所述的碳酸亚乙烯酯的制备方法,其特征在于,所述制备方法还包括如下步骤:在所述反应完成之后,采用萃取剂萃取,干燥,分离。
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