CN107670690A - A kind of iron-based cyano-containing anion imidazole ion liquid catalyst and its preparation method and application - Google Patents
A kind of iron-based cyano-containing anion imidazole ion liquid catalyst and its preparation method and application Download PDFInfo
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- CN107670690A CN107670690A CN201710804085.2A CN201710804085A CN107670690A CN 107670690 A CN107670690 A CN 107670690A CN 201710804085 A CN201710804085 A CN 201710804085A CN 107670690 A CN107670690 A CN 107670690A
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- catalyst
- iron
- ion liquid
- imidazole ion
- containing anion
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 82
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000007788 liquid Substances 0.000 title claims abstract description 55
- -1 anion imidazole ion Chemical class 0.000 title claims abstract description 51
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 35
- 125000004093 cyano group Chemical group *C#N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 150000001336 alkenes Chemical class 0.000 claims abstract description 28
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 20
- 229910000077 silane Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- PANJMBIFGCKWBY-UHFFFAOYSA-N iron tricyanide Chemical compound N#C[Fe](C#N)C#N PANJMBIFGCKWBY-UHFFFAOYSA-N 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 8
- 239000012188 paraffin wax Substances 0.000 claims description 8
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- DCXPBOFGQPCWJY-UHFFFAOYSA-N trisodium;iron(3+);hexacyanide Chemical compound [Na+].[Na+].[Na+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCXPBOFGQPCWJY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229940095068 tetradecene Drugs 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims 2
- ZOAMZFNAPHWBEN-UHFFFAOYSA-N 2-$l^{1}-oxidanylpropane Chemical compound CC(C)[O] ZOAMZFNAPHWBEN-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 150000003851 azoles Chemical class 0.000 claims 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 26
- 239000002608 ionic liquid Substances 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 15
- 150000002431 hydrogen Chemical class 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 9
- 238000007711 solidification Methods 0.000 description 9
- 230000008023 solidification Effects 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000007259 addition reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000165940 Houjia Species 0.000 description 1
- 229910019032 PtCl2 Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- AYIAVKOUTBEANG-UHFFFAOYSA-N ethoxy-dimethoxy-(2-phenylethyl)silane Chemical compound CCO[Si](OC)(OC)CCC1=CC=CC=C1 AYIAVKOUTBEANG-UHFFFAOYSA-N 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VRINOTYEGADLMW-UHFFFAOYSA-N heptyl(trimethoxy)silane Chemical compound CCCCCCC[Si](OC)(OC)OC VRINOTYEGADLMW-UHFFFAOYSA-N 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- HCOKJWUULRTBRS-UHFFFAOYSA-N propan-2-yloxysilane Chemical compound CC(C)O[SiH3] HCOKJWUULRTBRS-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- SVKDNKCAGJVMMY-UHFFFAOYSA-N triethoxy(tetradecyl)silane Chemical compound CCCCCCCCCCCCCC[Si](OCC)(OCC)OCC SVKDNKCAGJVMMY-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to catalytic field, it can not be recycled to solve the problems, such as that catalyst is costly in current hydrosilylation, deposits unstable and catalyst, the invention provides a kind of preparation method of iron-based cyano-containing anion imidazole ion liquid catalyst and the catalyst to be used for the method that catalyzed alkene and hydrogeneous alkoxy silane carry out hydrosilylation, the catalysis process reaction condition is gentle, feed stock conversion is high, catalyst amount is few, catalytic activity is high, reaction, which terminates rear product and catalyst, to be automatically subjected to phase splitting, and realize the recoverable of catalyst.
Description
Technical field
The invention belongs to catalytic field, and in particular to a kind of system of iron-based cyano-containing anion imidazole ion liquid catalyst
Preparation Method and its method for catalyzed alkene and alkoxy silane hydrosilylation.
Background technology
Catalyzed alkene hydrosilylation occupies an important position in synthetic organic chemistry, is synthesizing organo-silicon coupling agent
With one of function organo-silicon compound and the most important approach of organosilicon macromolecule polymer.Alkene Si―H addition reaction typically directly makes
Catalyst is used as by the use of chloroplatinic acid.Speier catalyst (isopropyl alcohol solution of chloroplatinic acid) and Karstedt catalyst ([(ViMe2Si)20]PtCl2) there is certain catalytic activity, it is widely used in organosilicon production.Though platinum catalysis system has
There is a greater activity, but after reaction generally requires to carry out under high-temperature and high-pressure conditions, and reaction terminates, separate difficulty with product, urge
Agent, which is difficult to recovery, to be recycled, and catalyst cost is higher.
Willing method is further improved on the basis of forefathers by Karstedt, uses chloroplatinic acid or chlorine platinum
Hydrochlorate with sodium acid carbonate and vinylsiloxane heating response, forms the vinylsiloxane complex compound of platinum in ethanol, such a
The catalyst of halogen is eliminated, catalytic efficiency is compared with the vinylsiloxane complex compound of chloroplatinic acid before, its catalytic efficiency
There is further raising, be still applied to as catalyst the most frequently used in hydrosilylation such a catalyst today
The industrial numerous areas of machine chemistry of silicones, although such a catalyst relatively before catalyst compare, have higher catalysis effect
Rate, but simultaneously there is also storage it is unstable, it is more sensitive to the moisture in environment and oxygen, easily with the weight in storage condition
Metal ion and other active compounds produce reaction, form the unstable platinum compounds of new high-valence state, ultimately form platinum
Gloomy shallow lake, loses catalytic activity.Therefore, higher catalytic activity can be kept simultaneously with industrialized production by developing one kind, and to storage
Active ion species in dis environment are less sensitive, can just seem outstanding by the hydrosilylation catalyst of storage-stable under the conditions of more
To be important.
In addition, there are some high-molecular compounds also to obtain preferable catalysis as carrier loaded complexing platinum catalyst
Effect, but these catalyst preparation process are complex, are not easy to repeat.Publication No. CN101322946A Chinese invention is special
Profit provides a kind of catalyst, and the catalyst is the mixture of platinum and the amino-compound of carboxy-containing acid group, but the catalyst
Can not recycling, considerably increase the production cost of catalyst article.
The research conditions of catalyst are used for current hydrosilylation of olefins, are prepared new, efficient, recyclable
Catalyst, which is used for hydrosilylation of olefins, has important application prospect and very major and immediate significance.
The content of the invention
To solve, catalyst cost in current hydrosilylation of olefins is high, deposits unstable and catalyst can not reclaim profit
With the problem of, the invention provides a kind of iron-based cyano-containing anion imidazole ion liquid catalyst and preparation method thereof, and make
It is used for catalyzed alkene hydrosilylation with the catalyst, using its mild condition of catalyst progress addition reaction, raw material turns
Rate is high, and the selectivity of addition compound product is good.
The present invention is that solve the problems, such as that prior art is present by following technical proposals：It is cloudy to provide a kind of iron-based cyano-containing
Ion imidazole ion liquid catalyst, the catalyst structure formula are：
Wherein, n=2,4,6,8；R is H, C1~C12Alkyl, C1~C12Hydroxyalkyl or C1~C12Alkenyl.
The preparation method of the iron-based cyano-containing anion imidazole ion liquid catalyst is specially：First will be anti-with inert gas
Answer the air in container to exclude, N- alkyl imidazoles and halogenated alkane are carried out under the conditions of 150 DEG C to 8 hours quaternized anti-
Should, then add organic solvent remove impurity, filter, dry, obtain thick imidazole ion liquid, add the iron cyanide and
Organic solvent, the anion exchange of 48 hours is carried out at room temperature, vacuum distillation removes solvent, then adds dichloromethane extraction production
Thing, that is, iron-based cyano-containing anion imidazole ion liquid catalyst is made.
Wherein, inert gas is nitrogen, and the mol ratio that N- alkyl imidazoles and halogenated alkane feed intake is 1:0.5~0.9.
The iron cyanide is 1 with imidazole ion liquid mol ratio：1~2000, it is more highly preferred to 1：1200, most preferably 1：300
~600.
Described organic solvent is acetonitrile.
The structural formula of obtained imidazole ion liquid is as follows：
Wherein, n=2,4,6,8；R is H, C1~C12Alkyl, C1~C12Hydroxyalkyl or C1~C12Alkylene, X-For
Cl-Or Br-, the imidazole ion liquid can improve the catalytic activity and selectivity of iron catalyst in hydrosilylation.
The described iron cyanide is iron cyanide Na3[Fe(CN)6]。
Present invention also offers a kind of iron-based cyano-containing anion imidazole ion liquid catalyzed alkene hydrosilylation
Method, it is using iron-based cyano-containing anion imidazole ion liquid as catalyst, is added in alkene and paraffin hydrocarbons activation and urges
Change alkene and carry out hydrosilylation.The imidazole ion liquid of different functional groups and iron compound composition catalyst system, should
For alkene and paraffin hydrocarbons activation addition reaction, the activity of catalyst and the selectivity of addition compound product, reaction can be improved
Conveniently, safely, fast.
The present invention silicon-hydrogen additive reaction method be specially：In iron-based cyano-containing anion imidazole ion liquid catalyst
In, addition alkene and paraffin hydrocarbons activation, 60~140 DEG C of reaction temperature of holding, condensing reflux, continuation stirring reaction 4~
24h, stop reaction, be cooled to room temperature, be evaporated under reduced pressure and collect corresponding cut, obtain the product of hydrosilylation.
Described alkene is selected from butylene, amylene, hexene, heptene, octene, decene, hendecene, laurylene, tetradecene, 16
One kind in alkene, octadecylene, styrene, p-methylstyrene, p-chlorostyrene.
Described iron-based cyano-containing anion imidazole ion liquid catalyst and the mol ratio of alkene are l：300~5000,
Preferably 1：1000~3000, more preferably 1：1200~2500.
Described paraffin hydrocarbons activation is selected from triethoxy hydrogen silane, trimethoxy hydrogen silane, methyl dimethoxy epoxide silicon
The mol ratio of one kind in alkane, three isopropoxy silane, alkene and paraffin hydrocarbons activation is 1：1~3.
Described hydrosilylation system, after reaction terminates, by stratification, you can realize catalyst and product
Separation, what is left after the upper solution of reaction product is poured out is catalyst system, can be reused, and saves cost.
Iron-based cyano-containing anion imidazole ion liquid is hydrogeneous with alkoxy to alkene as hydrosilylation catalyst system
The addition reaction of silane has good catalytic effect, and activity is high, good product selectivity, can be with catalyzed alkene and a variety of Silicon Containing Hydrogens
The addition reaction of alkane, catalyst is repeatable to be recycled.
It is an advantage of the invention that：
1, introduce cyano group and can solve the problem that the problem of ionic liquid generally existing is more sticky, while be also used as being catalyzed
The part of agent.
2nd, the synthesis condition for preparing ionic-liquid catalyst is gentle, the reaction time is short, and preparing raw material cost is relatively low, can advise greatly
Prepared by mould, obtained ionic-liquid catalyst is stable to water and air, has stronger acidity, toxicity is low, green.
3rd, catalyst amount is few, and catalytic activity is high, and high conversion rate, product is distributed after reaction, and raw material availability is high；Reaction
Product and catalyst can be automatically subjected to phase splitting after end, the recyclable recycling of post catalyst reaction.
4th, catalyzed alkene hydrosilylation mild condition, 60-140 DEG C of temperature, synthesis under normal pressure；Course of reaction is simple, peace
Entirely, it is easy to operate, easy to control.
Embodiment
The present invention is described in more detail below by reference to embodiment, but protection scope of the present invention is not limited
In these embodiments.
First the air in reaction vessel is excluded with nitrogen, by N- alkyl imidazoles and halogenated alkane under the conditions of 150 DEG C
The quaterisation of 8 hours is carried out, acetonitrile is then added and removes impurity, filter, dry, obtain thick imidazole ion liquid,
Add Na3[Fe(CN)6] and acetonitrile, the anion exchange of 48 hours is carried out at room temperature, and vacuum distillation removes acetonitrile, Ran Houjia
Enter dichloromethane extraction product, that is, iron-based cyano-containing anion imidazole ion liquid catalyst is made.
Catalyst represents such as following formula：
Embodiment 1：
Iron-based cyano-containing anion imidazole ion liquid catalyst A (0.2mmo1), it is added to and heats dress with magnetic agitation
Put in the three-necked flask with condensing unit, under nitrogen protection, 1- hexenes (0.6mol) are added dropwise successively by dropping funel, slowly rise
Temperature is to 65 DEG C of reaction temperature.Then trimethoxy hydrogen silane (0.8mo1) is added dropwise into Liquid catalyst systems again, opens condensation
Backflow, 65 DEG C of reaction temperature being kept, continue stirring reaction 6h, stop reaction, standing is cooled to the following ionic liquid solidification of room temperature,
Separate product and ionic liquid.It is evaporated under reduced pressure and collects corresponding cut, the conversion ratio that 1- hexenes are determined by GC-MS is 98.9%,
β-addition compound product (hexyl trimethoxy silane) yield is 97.5%.
Embodiment 2：
Iron-based cyano-containing anion imidazole ion liquid B (0.2mmo1), it is added to magnetic agitation heater and cold
In the three-necked flask of solidifying device, under nitrogen protection, 1- heptene (0.6mol) is added dropwise successively by dropping funel, is to slowly warm up to 85
℃.Then trimethoxy hydrogen silane (0.7mo1) is added dropwise into Liquid catalyst systems again, keeps 85 DEG C of reaction temperature, opens cold
Solidifying backflow, continues stirring reaction 6h, stops reaction, and standing is cooled to the following ionic liquid solidification of room temperature, separates product and ion
Liquid.It is evaporated under reduced pressure and collects corresponding cut, the conversion ratio that 1- heptene is determined by GC-MS is 96.9%, β-addition compound product (heptyl
Trimethoxy silane) yield be 94.5%.
Embodiment 3：
Iron-based cyano-containing anion imidazole ion liquid C (0.1mmo1), it is added to magnetic agitation heater and cold
In the three-necked flask of solidifying device, under nitrogen protection, 1- hendecenes (0.3mol) are added dropwise successively by dropping funel, are to slowly warm up to
85 DEG C of reaction temperature.Then trimethoxy hydrogen silane (0.5mo1) is added dropwise into Liquid catalyst systems again, keeps reaction temperature
85 DEG C, condensing reflux is opened, continues stirring reaction 6h, stops reaction, standing is cooled to the following ionic liquid solidification of room temperature, separation
Product and ionic liquid.Be evaporated under reduced pressure and collect corresponding cut, by GC-MS determine the conversion ratios of 1- hendecenes for 88.9%, β-
Addition compound product (hendecyl trimethoxy silane) yield is 85.5%.
Embodiment 4：
Iron-based cyano-containing anion imidazole ion liquid D (0.01mmo1), be added to magnetic agitation heater and
In the three-necked flask of condensing unit, under nitrogen protection, 1-tetradecylene (0.6mol) is to slowly warm up to 135 DEG C of reaction temperature.Then
Triethoxy hydrogen silane (0.8mo1) is added dropwise into Liquid catalyst systems again, keeps 135 DEG C of reaction temperature, opening condenses back
Stream, continue stirring reaction 6h, stop reaction, standing is cooled to the following ionic liquid solidification of room temperature, separates product and ionic liquid.
It is evaporated under reduced pressure and collects corresponding cut, the conversion ratio that 1-tetradecylene is determined by GC-MS is 98.9%, β-addition compound product (tetradecyl
Triethoxysilane) yield be 97.5%.
Embodiment 5：
Iron-based cyano-containing anion imidazole ion liquid E (0.2mmo1), it is added to magnetic agitation heater and cold
In the three-necked flask of solidifying device, under nitrogen protection, 1- hexadecylenes (0.7mol) are added dropwise by dropping funel, are to slowly warm up to 90
℃.Then trimethoxy hydrogen silane (0.7mo1) is added dropwise into Liquid catalyst systems again, keeps 90 DEG C of reaction temperature, opens cold
Solidifying backflow, continues stirring reaction 6h, stops reaction, and standing is cooled to the following ionic liquid solidification of room temperature, separates product and ion
Liquid.It is evaporated under reduced pressure and collects corresponding cut, the conversion ratio that 1- hexadecylenes are determined by GC-MS is 98.4%, β-addition compound product (ten
Six base trimethoxy silanes) yield be 97.5%.
Embodiment 6：
Iron-based cyano-containing anion imidazole ion liquid F (0.2mmo1), it is added to magnetic agitation heater and cold
In the three-necked flask of solidifying device, under nitrogen protection, 1- octadecylenes (0.7mol) are added dropwise by dropping funel, are to slowly warm up to 90
℃.Then trimethoxy hydrogen silane (0.8mo1) is added dropwise into Liquid catalyst systems again, keeps 90 DEG C of reaction temperature, opens cold
Solidifying backflow, continues stirring reaction 6h, stops reaction, and standing is cooled to the following ionic liquid solidification of room temperature, separates product and ion
Liquid.It is evaporated under reduced pressure and collects corresponding cut, the conversion ratio that 1- octadecylenes are determined by GC-MS is 88.9%, β-addition compound product (ten
Eight base trimethoxy silanes) yield be 87.5%.
Embodiment 7：
Iron-based cyano-containing anion imidazole ion liquid D (0.01mmo1), be added to magnetic agitation heater and
In the three-necked flask of condensing unit, under nitrogen protection, styrene (0.6mol) is added dropwise successively by dropping funel, is to slowly warm up to
90℃.Then trimethoxy hydrogen silane (0.8mo1) is added dropwise into Liquid catalyst systems again, keeps 90 DEG C of reaction temperature, opens
Condensing reflux, continue stirring reaction 6h, stop reaction, standing is cooled to the solidification of room temperature following ionic liquid, separation product with from
Sub- liquid.It is evaporated under reduced pressure and collects corresponding cut, the conversion ratio that styrene is determined by GC-MS is 96.9%, β-addition compound product (benzene
Ethyl trimethoxy silane) yield be 93.5%.
Embodiment 8：
Iron-based cyano-containing anion imidazole ion liquid C (0.02mmo1), be added to magnetic agitation heater and
In the three-necked flask of condensing unit, under nitrogen protection, p-methylstyrene (0.6mol) is added dropwise successively by dropping funel, slowly
It is warming up to 90 DEG C.Then trimethoxy hydrogen silane (0.8mo1) is added dropwise into Liquid catalyst systems again, keeps reaction temperature 90
DEG C, condensing reflux is opened, continues stirring reaction 6h, stops reaction, standing is cooled to the following ionic liquid solidification of room temperature, separation production
Product and ionic liquid.It is evaporated under reduced pressure and collects corresponding cut, the conversion ratio that p-methylstyrene is determined by GC-MS is 90.9%,
β-addition compound product (to methylphenethyl trimethoxy silane) yield is 87.5%.
Embodiment 9：
In example 1 to be performed after reaction liquid layer, catalyst system, inert gas shielding are left after upper solution is poured out
Under, then 1- hexenes (0.6mol) and trimethoxy hydrogen silane is added dropwise successively by dropping funel into Liquid catalyst systems
(0.8mo1), 65 DEG C of reaction temperature is kept, open condensing reflux, continue stirring reaction 6h, stop reaction, standing is cooled to room temperature
Following ionic liquid solidification, separates product and ionic liquid.It is evaporated under reduced pressure and collects corresponding cut, 1- hexenes is determined by GC-MS
Conversion ratio be that 98.9%, β-addition compound product (hexyl trimethoxy silane) yield is 97.5%, by the ionic liquid of embodiment 1
Re-use 5 times, reaction condition is constant, and result of the test is shown in Table 1.
The ionic-liquid catalyst of table 1 reuses experimental result
As can be seen from Table 1, reuse 5 times, the catalytic effect of ionic-liquid catalyst slightly floats, but alkene converts
Rate and the selectivity of silane all maintain higher level, therefore, utilize iron-based pyrrolidonium ionic liquids catalyst preparation silicon
The method of alkane has feasibility.
Claims (9)
- A kind of 1. iron-based cyano-containing anion imidazole ion liquid catalyst, it is characterised in that：The catalyst structure formula is：Wherein, n=2,4,6,8；R is H, C1~C12Alkyl, C1~C12Hydroxyalkyl or C1~C12Alkenyl.
- 2. a kind of preparation method of iron-based cyano-containing anion imidazole ion liquid catalyst as claimed in claim 1, it is special Sign is：The preparation method of the catalyst is：First the air in reaction vessel is excluded with inert gas, by N- alkyl miaows Azoles and halogenated alkane carry out the quaterisation of 8 hours under the conditions of 150 DEG C, then add organic solvent and remove impurity, filter, Dry, obtain thick imidazole ion liquid, add the iron cyanide and organic solvent, carry out at room temperature 48 hours it is cloudy from Son exchanges, and vacuum distillation removes solvent, then adds dichloromethane extraction product, iron-based cyano-containing anion imidazol ion liquid is made Body catalyst.
- 3. the preparation method of iron-based cyano-containing anion imidazole ion liquid catalyst as claimed in claim 2, its feature exist In：The inert gas is nitrogen, and the iron cyanide is iron cyanide Na3[Fe(CN)6], organic solvent is acetonitrile.
- 4. the preparation method of iron-based cyano-containing anion imidazole ion liquid catalyst as claimed in claim 2, its feature exist In：The mol ratio of the N- alkyl imidazoles and halogenated alkane is 1：0.5~0.9, mole of the iron cyanide and imidazole ion liquid Than for 1：1~2000.
- 5. the preparation method of iron-based cyano-containing anion imidazole ion liquid catalyst as claimed in claim 4, its feature exist In：The mol ratio of the iron cyanide and imidazole ion liquid is 1：300~600.
- 6. a kind of application of iron-based cyano-containing anion imidazole ion liquid catalyst as claimed in claim 1, its feature exist In：The catalyst is used for catalyzed alkene hydrosilylation, and specific hydrosilylation of olefins method is：Contain cyanogen in iron-based In base anion imidazole ion liquid catalyst, alkene and paraffin hydrocarbons activation are added, keeps 60~140 DEG C of reaction temperature, 0.5~5h of condensing reflux, continue 4~24h of stirring reaction, stop reaction, be cooled to room temperature, be evaporated under reduced pressure and collect corresponding cut, Obtain the product of hydrosilylation.
- 7. the application of iron-based cyano-containing anion imidazole ion liquid catalyst as claimed in claim 6, it is characterised in that：Institute State alkene and be selected from butylene, amylene, hexene, heptene, octene, decene, hendecene, laurylene, tetradecene, hexadecylene, octadecylene, benzene One kind in ethene, p-methylstyrene, p-chlorostyrene；The mol ratio of the catalyst and alkene is l：300-5000.
- 8. the application of iron-based cyano-containing anion imidazole ion liquid catalyst as claimed in claim 7, it is characterised in that：Institute The mol ratio for stating catalyst and alkene is 1:1200~2500.
- 9. the application of iron-based cyano-containing anion imidazole ion liquid catalyst as claimed in claim 6, it is characterised in that：Institute The paraffin hydrocarbons activation stated is selected from triethoxy hydrogen silane, trimethoxy hydrogen silane, methyl dimethoxysilane, three isopropyl oxygen The mol ratio of one kind in base silane, alkene and paraffin hydrocarbons activation is 1：1~3.
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