CN114031479A - 一种六氟丙烯二聚体d1的制备方法 - Google Patents
一种六氟丙烯二聚体d1的制备方法 Download PDFInfo
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- CN114031479A CN114031479A CN202111360584.XA CN202111360584A CN114031479A CN 114031479 A CN114031479 A CN 114031479A CN 202111360584 A CN202111360584 A CN 202111360584A CN 114031479 A CN114031479 A CN 114031479A
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- hexafluoropropylene
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- PBVZTJDHQVIHFR-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC(F)=C(F)C(F)(F)F.FC(F)=C(F)C(F)(F)F PBVZTJDHQVIHFR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000004817 gas chromatography Methods 0.000 claims abstract description 7
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000007789 sealing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 20
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- QLPMKRZYJPNIRP-UHFFFAOYSA-M methyl(trioctyl)azanium;bromide Chemical compound [Br-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC QLPMKRZYJPNIRP-UHFFFAOYSA-M 0.000 claims description 6
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- TUDUDQJRUPFUMA-UHFFFAOYSA-M ethyl(trioctyl)phosphanium;bromide Chemical compound [Br-].CCCCCCCC[P+](CC)(CCCCCCCC)CCCCCCCC TUDUDQJRUPFUMA-UHFFFAOYSA-M 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- RYVBINGWVJJDPU-UHFFFAOYSA-M tributyl(hexadecyl)phosphanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC RYVBINGWVJJDPU-UHFFFAOYSA-M 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- 239000013638 trimer Substances 0.000 abstract description 10
- 239000002585 base Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
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- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000000539 dimer Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000006384 oligomerization reaction Methods 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- 150000003983 crown ethers Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- -1 fluoroalkyl amine Chemical class 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical group [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- ZVVSSOQAYNYNPP-UHFFFAOYSA-N olaflur Chemical compound F.F.CCCCCCCCCCCCCCCCCCN(CCO)CCCN(CCO)CCO ZVVSSOQAYNYNPP-UHFFFAOYSA-N 0.000 description 1
- 229960001245 olaflur Drugs 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- RZWQDAUIUBVCDD-UHFFFAOYSA-M sodium;benzenethiolate Chemical compound [Na+].[S-]C1=CC=CC=C1 RZWQDAUIUBVCDD-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
- C07C17/281—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons of only one compound
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0217—Mercaptans or thiols
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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
- B01J31/02—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
- B01J31/0237—Amines
- B01J31/0238—Amines with a primary amino group
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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- 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
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
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Abstract
本发明公开了一种六氟丙烯二聚体D1的制备方法，在反应容器中加入催化剂和溶剂后，密封，缓慢搅拌下加热，通入六氟丙烯进行反应，反应结束后，气相色谱分析六氟丙烯二聚体D1产物的收率，催化剂为复合催化剂，由交界碱、软碱和作为助催化剂的相转移催化剂组成，溶剂为复合溶剂，由两种或两种以上的极性较小的非质子溶剂组成。本发明采用“软碱”和“交界碱”复配，以相转移催化剂为助催化剂组成的催化体系，并采用极性较小的非质子复合溶剂，制得六氟丙烯二聚体D1≥99%，D2≤1%，无六氟丙烯三聚体生成。催化剂原料便宜易得，制作工艺简单，操作安全，成本低，是一项有广阔应用前景的可持续发展合成技术，该技术适用于规模化生产。
Description
技术领域
本发明涉及一种六氟丙烯二聚体的制备方法，具体的是涉及一种六氟丙烯二聚体异构体D1的制备方法，属于氟化工技术领域。
背景技术
六氟丙烯二聚体是由六氟丙烯经齐聚制得。反应体系是由溶剂、阴离子和催化剂三部分组成。六氟丙烯二聚体具有一对顺反异构体D1和支链结构的异构体D2三个同分异构体。D1性质稳定且毒性较低，可直接用作溶剂、清洗剂、发泡剂；D2有一定的毒性，但是双键活性较大，可进行多种化学反应。
六氟丙烯二聚体的制备方法概括起来可分为气相法和液相法。气相法工艺为无溶剂的聚合过程。通常将催化剂装于管式反应器中,将六氟丙烯气体通过催化剂层进行连续反应。由于要保证体系中的物料处于气态,反应温度需要在250℃以上。反应的后处理是将反应气冷凝直接进行精馏。气相法聚合工艺所用的催化剂为碱金属的氟化物，主要以吸附于活性碳或氧化镍上的CsF或KF为催化剂，或者直接用活性碳做催化剂,把六氟丙烯的气体在410～420℃温度下通过装有活性碳小粒的管式反应器中制得。液相法工艺是将催化剂及其添加剂溶于非质子极性溶剂中,通入六氟丙烯进行反应。反应过程可以是间歇式反应也可以是连续式反应。反应产物的分离可以利用产物在溶剂中不互溶进行直接分离。液相法所用的催化剂主要以氟化物为主,但选择的范围较宽，可以使用金属氟化物、金属氟氢化物、有机氟化胺、季铵盐、季磷盐、芳烃类铬配合物、氰化物、氰酸盐和硫代氰酸盐等，或者采用价格非常昂贵的冠醚为助催化剂。但是，不管是气相法还是液相法，在六氟丙烯二聚体的制备中，都难以制得单一的纯度高的异构体D1或D2。因此，研究和开发选择性合成六氟丙烯二聚体D1或D2异构体的方法具有广阔的前景。
2005年，武宏科等人利用二甲基乙酰胺作为溶剂进行了六氟丙烯齐聚反应的研究，讨论了催化剂用量、反应时间和温度对生成而具体的影响。并报道了在液相齐聚反应中催化剂的种类，使用的催化剂除金属氟化物外,还可以选择金属氢氟化物、氟化铵、含氟烷基胺、季铵盐、季磷盐、P双(芳烃)铬配合物、三(二取代氨基)硫全氟负碳离子盐、氰化物、氰酸盐、硫代氰酸盐、冠醚和聚乙二醇。2007年徐金和等人报道了二甲基甲酰胺作溶剂，溴离子催化反应，可以得到98%的二聚体异构体D1产物；以环丁砜作溶剂，氟离子催化异构化反应，在130℃温度下，二聚体D1异构化为二聚体D2的转化率达到99%。2009年雷志刚和2013年纪朝聪等人都系统地研究了六氟丙烯齐聚制备二聚体和三聚体的反应。讨论了溶剂、催化剂、温度等条件对反应的影响。结果发现，选择极性较低的乙腈作溶剂利于二聚体的产生，选择极性较高的二甲基甲酰胺利于三聚体的产生；催化剂选择KSCN，或者KF和有机胺混合使用，在乙腈溶剂中也能得到较高收率的二聚体。加入冠醚利于反应速度的提高。另外发现在极性溶剂环丁砜和KF反应体系中，温度100℃，即温度较高时六氟丙烯二聚体异构体D1易转化为异构体D2。
因此，根据上述实验结果我们认为在六氟丙烯二聚体D1异构体的制备过程中，最佳反应条件是选择低极性溶剂和低反应温度，催化剂选择具有较低电荷密度和较大离子半径的共轭碱，有利于六氟丙烯二聚体异构体D1的产生。
在软硬酸碱理论的定义中，较低电荷密度和较大离子半径的共轭碱属于“软碱”的范畴，即离子的极化性较高，但极性较小。根据软硬酸碱理论的基本规则“硬”亲“硬”，“软”亲“软”的结合理论。我们认为六氟丙烯形成六氟丙烯碳负离子和六氟丙烯二聚体碳负离子时，溶剂极性大和反应温度高，催化剂电荷密度大和离子半径小利于生成六氟丙烯二聚体碳负离子，而且六氟丙烯碳负离子也易于发生离子重排，即易于生成六氟丙烯三聚体，也容易使六氟丙烯二聚体D1发生异构化形成六氟丙烯二聚体D2。
发明内容
本发明所要解决的技术问题是提供一种选择性合成六氟丙烯二聚体异构体D1的方法。
为解决以上技术问题，本发明公开了一种六氟丙烯二聚体D1的制备方法，在反应容器中加入催化剂和溶剂后，密封，缓慢搅拌下加热，通入六氟丙烯进行反应，反应结束后，气相色谱分析六氟丙烯二聚体D1产物的收率，
所述催化剂为复合催化剂，由交界碱、软碱和作为助催化剂的相转移催化剂组成，
所述溶剂为复合溶剂，由两种或两种以上的极性较小的非质子溶剂组成。
进一步地，所述软碱为I-、SCN-、CN-、H-、C6H6、C2H5、CO、（C6H5）3P、C6H5SNa中的一种；所述交界碱为Br-、C6H5NH2、C6H5N、N3 -、SO3 2+、N2、NO2 -中的一种；所述相转移催化剂为溴化三正辛基甲基铵、溴化四正丁基铵、溴化三正辛基乙基鏻盐、溴化正十六烷基三正丁基鏻、溴化三乙基苄基铵中的一种。
进一步地，所述复合溶剂由甲苯、苯、氯苯、石油醚、氯仿、二氯乙烷、三氯乙烷、乙酸乙酯、乙酸丁酯和二氯丙烷中的一种或两种以上组成。
进一步地，所述交界碱与软碱的重量用量比为1 ：0.1～1，相转移催化剂重量用量为交界碱和软碱重量之和的1～15%。
进一步地，所述催化剂的重量用量为六氟丙烯重量用量的1～15%。
进一步地，所述催化剂的重量用量为六氟丙烯重量用量的5～10%。
进一步地，所述复合溶剂由两种或两种以上极性较小的非质子溶剂按任意比例混合得到。
进一步地，所述溶剂的重量用量为六氟丙烯重量用量的0.5～1.5倍。
进一步地，所述溶剂的重量用量为六氟丙烯重量用量的0.5～1.0倍。
进一步地，六氟丙烯的进料速度为15～150克/分钟，通入六氟丙烯后反应温度为10～50℃，反应时间为1～10小时。
本发明的反应采用“软碱”和“交界碱”复配，以相转移催化剂为助催化剂组成的催化体系，并采用极性较小的非质子复合溶剂，可以制得六氟丙烯二聚体D1≥99%，D2≤1%，无六氟丙烯三聚体生成。本发明的催化剂原料便宜易得，制作工艺简单，操作安全，成本低，是一项有广阔应用前景的可持续发展合成技术，该技术适用于规模化生产。
具体实施方式
下面结合实施例对本发明做更进一步地解释。下列实施例仅用于说明本发明，但并不用来限定本发明的实施范围。
一、催化剂的配制
实施例1
KBr 100克，KSCN 10克，溴化三正辛基甲基铵 11克混合备用。
实施例2
苯胺（C6H5NH2）100克，苯（C6H6）100克，溴化三正辛基甲基铵 20克混合备用。
实施例3
吡啶（C6H5N）100克，三苯基膦（PPh3）50克，溴化正十六烷基三正丁基鏻 22.5克混合备用。
实施例4
NaNO2 100克，苯硫酚钠（C6H5SNa）30克，溴化三正辛基甲基铵 13克混合备用。
实施例5
亚硫酸钠（Na2SO3）100克，碘化钾（KI） 80克，溴化三正辛基乙基鏻盐 20克混合备用。
二、六氟丙烯二聚体D1的制备
实施例6
在5升的高压反应釜中，加入甲苯200克，苯50克，氯苯50克，采用实施例1配置的催化剂30克，密封，缓慢搅拌下加热到30℃，以每分钟30克的流量通入六氟丙烯600克进入反应釜后，反应5小时，气相色谱分析六氟丙烯二聚体D1≥99.1%，D2≤0.9%，无六氟丙烯三聚体。
实施例7
在5升的高压反应釜中，加入石油醚100克，乙酸乙酯50克，氯苯50克，采用实施例2配置的催化剂30克，密封，缓慢搅拌下加热到10℃，以每分钟15克的流量通入六氟丙烯300克进入反应釜后，反应10小时，气相色谱分析六氟丙烯二聚体D1≥99.5%，D2≤0.5%，无六氟丙烯三聚体。
实施例8
在5升的高压反应釜中，加入三氯乙烷200克，氯仿200克，氯苯50克，采用实施例3配置的催化剂45克，密封，缓慢搅拌下加热到50℃，以每分钟150克的流量通入六氟丙烯900克进入反应釜后，反应1小时，气相色谱分析六氟丙烯二聚体D1≥99.2%，D2≤0.8%，无六氟丙烯三聚体。
实施例9
在5升的高压反应釜中，加入三氯乙烷200克，氯仿200克，氯苯50克，采用实施例4配置的催化剂30克，密封，缓慢搅拌下加热到20℃，以每分钟50克的流量通入六氟丙烯300克进入反应釜后，反应1小时，气相色谱分析六氟丙烯二聚体D1≥99.6%，D2≤0.4%，无六氟丙烯三聚体。
实施例10
在5升的高压反应釜中，加入三氯乙烷200克，氯仿200克，氯苯200克，采用实施例5配置的催化剂45克，密封，缓慢搅拌下加热到20℃，以每分钟30克的流量通入六氟丙烯600克进入反应釜后，反应3小时，气相色谱分析六氟丙烯二聚体D1≥99.8%，D2≤0.2%，无六氟丙烯三聚体。
Claims (10)
1.一种六氟丙烯二聚体D1的制备方法，其特征在于：在反应容器中加入催化剂和溶剂后，密封，缓慢搅拌下加热，通入六氟丙烯进行反应，反应结束后，气相色谱分析六氟丙烯二聚体D1产物的收率，
所述催化剂为复合催化剂，由交界碱、软碱和作为助催化剂的相转移催化剂组成，
所述溶剂为复合溶剂，由两种或两种以上的极性较小的非质子溶剂组成。
2.根据权利要求1所述六氟丙烯二聚体D1的制备方法，其特征在于：所述软碱为I-、SCN-、CN-、H-、C6H6、C2H5、CO、（C6H5）3P、C6H5SNa中的一种；所述交界碱为Br-、C6H5NH2、C6H5N、N3 -、SO3 2+、N2、NO2 -中的一种；所述相转移催化剂为溴化三正辛基甲基铵、溴化四正丁基铵、溴化三正辛基乙基鏻盐、溴化正十六烷基三正丁基鏻、溴化三乙基苄基铵中的一种。
3.根据权利要求1所述六氟丙烯二聚体D1的制备方法，其特征在于：所述复合溶剂由甲苯、苯、氯苯、石油醚、氯仿、二氯乙烷、三氯乙烷、乙酸乙酯、乙酸丁酯和二氯丙烷中的一种或两种以上组成。
4.根据权利要求1或2所述六氟丙烯二聚体D1的制备方法，其特征在于：所述交界碱与软碱的重量用量比为1 ：0.1～1，相转移催化剂重量用量为交界碱和软碱重量之和的1～15%。
5.根据权利要求1或2所述六氟丙烯二聚体D1的制备方法，其特征在于：所述催化剂的重量用量为六氟丙烯重量用量的1～15%。
6.根据权利要求5所述六氟丙烯二聚体D1的制备方法，其特征在于：所述催化剂的重量用量为六氟丙烯重量用量的5～10%。
7.根据权利要求1或3所述六氟丙烯二聚体D1的制备方法，其特征在于：所述复合溶剂由两种或两种以上极性较小的非质子溶剂按任意比例混合得到。
8.根据权利要求1或3所述六氟丙烯二聚体D1的制备方法，其特征在于：所述溶剂的重量用量为六氟丙烯重量用量的0.5～1.5倍。
9.根据权利要求8所述六氟丙烯二聚体D1的制备方法，其特征在于：所述溶剂的重量用量为六氟丙烯重量用量的0.5～1.0倍。
10.根据权利要求1所述六氟丙烯二聚体D1的制备方法，其特征在于：六氟丙烯的进料速度为15～150克/分钟，通入六氟丙烯后反应温度为10～50℃，反应时间为1～10小时。
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