CN112552141B - 一种2-氯-1,1,1,4,4,4-六氟-2-丁烯的制备方法 - Google Patents
一种2-氯-1,1,1,4,4,4-六氟-2-丁烯的制备方法 Download PDFInfo
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- JRENXZBKMHPULY-UPHRSURJSA-N (z)-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)\C=C(/Cl)C(F)(F)F JRENXZBKMHPULY-UPHRSURJSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 14
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 13
- 150000005309 metal halides Chemical class 0.000 claims abstract description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 6
- 239000003446 ligand Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 4
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical group [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims 1
- SNNIPOQLGBPXPS-UHFFFAOYSA-M tetraoctylazanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC SNNIPOQLGBPXPS-UHFFFAOYSA-M 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 150000001805 chlorine compounds Chemical group 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 description 18
- RWNKSTSCBHKHTB-UHFFFAOYSA-N Hexachloro-1,3-butadiene Chemical compound ClC(Cl)=C(Cl)C(Cl)=C(Cl)Cl RWNKSTSCBHKHTB-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NLOLSXYRJFEOTA-UPHRSURJSA-N (z)-1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)\C=C/C(F)(F)F NLOLSXYRJFEOTA-UPHRSURJSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XDIDQEGAKCWQQP-OWOJBTEDSA-N (e)-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)C(\Cl)=C(/Cl)C(F)(F)F XDIDQEGAKCWQQP-OWOJBTEDSA-N 0.000 description 1
- SXAFZSJBIOXONF-UPHRSURJSA-N (z)-1,2-dichloro-1,1,4,4,4-pentafluorobut-2-ene Chemical compound FC(F)(F)\C=C(/Cl)C(F)(F)Cl SXAFZSJBIOXONF-UPHRSURJSA-N 0.000 description 1
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910018287 SbF 5 Inorganic materials 0.000 description 1
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical group [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 1
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 1
- ZDINGUUTWDGGFF-UHFFFAOYSA-N antimony(5+) Chemical compound [Sb+5] ZDINGUUTWDGGFF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- MBAKFIZHTUAVJN-UHFFFAOYSA-I hexafluoroantimony(1-);hydron Chemical compound F.F[Sb](F)(F)(F)F MBAKFIZHTUAVJN-UHFFFAOYSA-I 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- -1 ion salt Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/42—Tin
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了一种高选择性地制备2‑氯‑1,1,1,4,4,4‑六氟‑2‑丁烯的方法,化合物CF3CH=CClCFxCl3‑x与无水氟化氢在离子盐催化剂作用下,进行氟化反应生成2‑氯‑1,1,1,4,4,4‑六氟‑2‑丁烯,其中化合物通式中x=0、1或2,离子盐催化剂由金属卤化物和配体组成,金属卤化物为锡或钛的氯化物或氟化物,配体为季铵盐。
Description
技术领域
本发明属于发泡剂技术领域,涉及顺式-1,1,1,4,4,4-六氟-2-丁烯中间体的制备,具体涉及一种2-氯-1,1,1,4,4,4-六氟-2-丁烯的制备方法。
背景技术
顺式-1,1,1,4,4,4-六氟-2-丁烯(Z-HFO-1336mzz)作为新一代绿色环保发泡剂,其臭氧消耗潜值(ODP)为零,温室效应潜值(GWP)为9,对环境影响很小,已成为氢氯氟烃、氢氟烃类发泡剂的理想替代品。2-氯-1,1,1,4,4,4-六氟-2-丁烯(HCFO-1326mxz)作为合成Z-HFO-1336mzz的重要中间体,其高效合成方法是实现Z-HFO-1336mzz工业化关键技术之一。
中国专利CN104072333B和CN105418361A报道了通过六氯丁二烯与无水氟化氢在五氯化锑催化下合成HCFO-1326mxz,然而所用五氯化锑催化剂存在着价态易降低失活等问题;中国专利CN106008147B报道了六氯丁二烯与无水氟化氢在气相氟化催化剂下合成HCFO-1326mxz的方法,但由于需要使用氯气稳定催化剂,使得产物选择性低;中国专利CN106536462A和CN103524297B则通过2,3-二氯-1,1,1,4,4,4-六氟-2-丁烯通过加氢脱氯反应合成HCFO-1326mxz,但由于加氢反应难以控制选择性,使得产物选择性低。中国专利CN110372472A报道了以1,2-二氯-1,1,4,4,4-五氟-2-丁烯为原料与无水氟化氢反应得到HCFO-1326mxz的方法,液相氟化条件下,以五氟化锑为催化剂的收率为90.4%,虽然未提及HCFO-1326mxz的选择性,但是在超强酸体系五氟化锑-氟化氢HCFO-1326mxz会继续反应打开双键,使得产物的选择性降低,同时催化剂也存在着价态易降低失活的问题。
发明内容
本发明要解决的技术问题是针对现有技术的不足,本发明提供了一种2-氯-1,1,1,4,4,4-六氟-2-丁烯的制备方法,解决现有的制备方法存在的催化剂寿命短、产物选择性低的问题。
本发明涉及的制备2-氯-1,1,1,4,4,4-六氟-2-丁烯的方法,在离子盐催化剂作用下,化合物CF3CH=CClCFxCl3-x与无水氟化氢进行氟化反应生成HCFO-1326mxz,其中化合物通式中x=0、1或2,反应方程式如下:
本发明离子盐催化剂由金属卤化物与配体季铵盐,经过氟化氢氟化处理得到,通过调节季铵盐与金属卤化物的比例,以获得与反应相匹配催化活的性离子盐催化剂。所述季铵盐与金属卤化物的比例为0~1:1,优选为0.1~0.5:1。
所述的金属卤化物为四氯化锡、四氟化锡,四氯化钛或四氟化钛,优选四氯化锡或四氟化锡。
本发明可以不加入季铵盐,反应可以进行,但加入所述的季铵盐可以获得与反应相匹配催化活的性离子盐催化剂,反应选择性更优,具体选择的季铵盐为四甲基氯化铵,四乙基氯化铵,四丁基氯化铵或四辛基氯化铵,优选四甲基氯化铵,四乙基氯化铵,更优选四乙基氯化铵。
本发明无水氟化氢与CF3CH=CClCFxCl3-x摩尔比为3~30:1,优选为5~10:1;离子盐催化剂与CF3CH=CClCFxCl3-x的摩尔比为1~10:1,优选为2~5:1;反应温度为80~150℃,优选为100~130℃;反应时间为3~5h。
本发明所述化合物CF3CH=CClCFxCl3-x为CF3CH=CClCF2Cl、CF3CH=CClCFCl2或CF3CH=CClCCl3。
所述化合物CF3CH=CClCFxCl3-x选自CF3CH=CClCF2Cl。
与现有技术相比,本发明具有的有益效果:选用的离子盐催化剂酸性可调控,可高选择性地制备得到HCFO-1326mxz,在较优条件下,选择性可达99.5%。
具体实施方式
下面通过具体实施例对本发明作进一步详细说明,但并非对本发明做任何形式上的限制。
本发明通过CF3CH=CClCFxCl3-x与氟化氢氟氯交换反应生成CF3CH=CClCF3,其中化合物通式中x=0、1或2,需要保证催化体系的酸性在一定范围内,才能维持反应物的双键的稳定,过强的酸性的催化剂如SbCl5或SbF5,会在氟氯交换反应后继续打开双键,使得目标产物的选择性降低,且五价锑不稳定,会降低为三价锑,从而失活。例如在300mL不锈钢带搅拌高压反应釜中加入15g SbCl5、50g HF和CF3CH=CClCF2Cl,室温搅拌后升温至100℃反应3小时,反应结束后取样经水洗除酸后气相色谱分析,CF3CH=CClCF2Cl的转化率为100%,HCFO-1326mxz选择性为85.5%。产物经核磁检测,数据如下:
1H NMR(500MHz,CDCl3)δ6.64(q,1H,J=6.5Hz);
13C NMR(500MHz,CDCl3)δ132.0(qq,J=39.3Hz,J=5.4Hz),121.9(q,J=37.5Hz),120.6(q,J=270Hz),119.1(q,J=272.5Hz);
19F NMR(470MHz,CDCl3)δ-71.3(m,CF3),-61.3(m,CF3).
上述数据证明制得产物就是2-氯-1,1,1,4,4,4-六氟-2-丁烯。
本发明采用离子盐催化剂作为催化剂,由金属卤化物与配体季铵盐,通过改变季铵盐与金属卤化物的比例,实现了催化体系酸性的微调,以获得与反应相匹配催化活的性离子盐催化剂,同时,季铵盐具有相转移作用,增加了有机物与HF溶解,使得反应效率和选择性更优。此外,本发明选择的锡或钛的氯化物或氟化物,价态稳定,不易失活。
实施例1:
向300mL不锈钢带搅拌高压反应釜中,依次加入26.1g四氯化锡、3.3g四乙基氯化铵和40g无水氟化氢,室温搅拌0.5h,20℃/h程序升温至90℃后维持2h。随后一次性加入10.7g CF3CH=CClCF2Cl,升温至120℃反应4小时,反应结束后取样经水洗除酸后气相色谱分析,CF3CH=CClCF2Cl的转化率为100%,HCFO-1326mxz选择性为99.5%。
实施例2~9
实施例2~9按照实施例1中相同的方法制备HCFO-1326mxz,所不同的是,在不改变各反应物配比的前提下,改变离子盐组分、反应温度和反应时间,反应结果如表1所示。
表1
实施例10~15
实施例11~15按照实施例1中相同的方法制备HCFO-1326mxz,所不同的是催化剂组分比例、HF与CF3CH=CClCF2Cl的摩尔比和CF3CH=CClCF2Cl的投料量,反应结果如表2所示。
表2
实施例16~17
实施例16~17按照实施例1中相同的方法制备HCFO-1326mxz,所不同的是原料,反应结果如表3所示。
表3
实施例18
连续液相氟化反应在2L不锈钢高压釜中进行,高压釜的上方装有蒸馏塔和回流冷凝器,底部使用油锅加热,塔顶物料经过水洗碱性除酸后收集于-20℃低温浴槽。向反应釜中依次投入260.5g SnCl4,33.1g四乙基氯化铵,400g HF,通过气相口排除生成的HCl,升温至90℃,恒温4h。通过计量泵连续将CF3CH=CClCF2Cl与HF打入至反应器中,CF3CH=CClCF2Cl的进料速率为86g/h,HF的进料速率为24g/h,反应温度为110℃~120℃,反应压力为1.3~1.5MPa。分析塔顶气相物料的组成,反应结果见表4。由表4可知,连续运行300h内,CF3CH=CClCF2Cl转化率接近100%,HCFO-1326mxz平均选择性为99.1%,反应过程中催化剂保持很好的稳定性。
表4
从上述实施例可以看出,本发明选用的离子盐催化剂酸性可调控,可高选择性地制备得到HCFO-1326mxz,且催化剂性能稳定,使用寿命长。
Claims (4)
1.一种2-氯-1,1,1,4,4,4-六氟-2-丁烯的制备方法,其特征在于:在离子盐催化剂作用下,化合物CF3CH=CClCF2Cl或CF3CH=CClCCl3与无水氟化氢进行氟化反应生成2-氯-1,1,1,4,4,4-六氟-2-丁烯;
所述的离子盐催化剂由金属卤化物与配体季铵盐经过氟化氢氟化处理得到,通过调节季铵盐与金属卤化物的比例,以获得与反应相匹配催化活的性离子盐催化剂;季铵盐与金属卤化物的比例为0.1~0.5:1;
无水氟化氢与CF3CH=CClCF2Cl或CF3CH=CClCCl3摩尔比为3~30:1,离子盐催化剂与CF3CH=CClCF2Cl或CF3CH=CClCCl3的摩尔比为1~10:1,反应温度为80~150℃,反应时间为3~5 h;
所述金属卤化物为四氯化锡、四氟化锡或四氟化钛;
所述季铵盐为四甲基氯化铵,四乙基氯化铵,四丁基氯化铵或四辛基氯化铵。
2.如权利要求1所述的2-氯-1,1,1,4,4,4-六氟-2-丁烯的制备方法,其特征在于所述金属卤化物为四氯化锡或四氟化锡。
3.如权利要求1所述的2-氯-1,1,1,4,4,4-六氟-2-丁烯的制备方法,其特征在于所述季铵盐为四乙基氯化铵。
4.如权利要求2-3任一所述的2-氯-1,1,1,4,4,4-六氟-2-丁烯的制备方法,其特征在于反应条件为:无水氟化氢与CF3CH=CClCF2Cl或CF3CH=CClCCl3摩尔比为5~10:1,离子盐催化剂与CF3CH=CClCF2Cl或CF3CH=CClCCl3的摩尔比为2~5:1,反应温度为100~130℃。
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