CN107721928A - A kind of iron-based cyano-containing anion imidazole ion liquid and its preparation method and application - Google Patents
A kind of iron-based cyano-containing anion imidazole ion liquid and its preparation method and application Download PDFInfo
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- CN107721928A CN107721928A CN201711063367.8A CN201711063367A CN107721928A CN 107721928 A CN107721928 A CN 107721928A CN 201711063367 A CN201711063367 A CN 201711063367A CN 107721928 A CN107721928 A CN 107721928A
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- Prior art keywords
- iron
- ion liquid
- reaction
- imidazole ion
- alkyl
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 97
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000007788 liquid Substances 0.000 title claims abstract description 70
- -1 anion imidazole ion Chemical class 0.000 title claims abstract description 68
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 45
- 125000004093 cyano group Chemical group *C#N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 16
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 20
- 150000002431 hydrogen Chemical group 0.000 claims description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 17
- 229910000077 silane Inorganic materials 0.000 claims description 17
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 14
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 11
- 150000004702 methyl esters Chemical class 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- NAVJNPDLSKEXSP-UHFFFAOYSA-N Fe(CN)2 Chemical class N#C[Fe]C#N NAVJNPDLSKEXSP-UHFFFAOYSA-N 0.000 claims description 6
- 238000007259 addition reaction Methods 0.000 claims description 6
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 150000002118 epoxides Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- FKLSONDBCYHMOQ-UHFFFAOYSA-N 9E-dodecenoic acid Natural products CCC=CCCCCCCCC(O)=O FKLSONDBCYHMOQ-UHFFFAOYSA-N 0.000 claims description 3
- GRAORJFMGCQWRN-UHFFFAOYSA-N Butyl undecylenate Chemical compound CCCCOC(=O)CCCCCCCCC=C GRAORJFMGCQWRN-UHFFFAOYSA-N 0.000 claims description 3
- 238000005349 anion exchange Methods 0.000 claims description 3
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 claims description 3
- XKZKQTCECFWKBN-UHFFFAOYSA-N dec-4-enoic acid Chemical class CCCCCC=CCCC(O)=O XKZKQTCECFWKBN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- HCOKJWUULRTBRS-UHFFFAOYSA-N propan-2-yloxysilane Chemical compound CC(C)O[SiH3] HCOKJWUULRTBRS-UHFFFAOYSA-N 0.000 claims description 3
- 229960002703 undecylenic acid Drugs 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 210000005252 bulbus oculi Anatomy 0.000 claims description 2
- RWNJOXUVHRXHSD-UHFFFAOYSA-N hept-6-enoic acid Chemical class OC(=O)CCCCC=C RWNJOXUVHRXHSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 abstract description 24
- 150000001875 compounds Chemical class 0.000 abstract description 23
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- 238000012544 monitoring process Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 150000002460 imidazoles Chemical class 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical class CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 2
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical class CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 2
- JMTFLSQHQSFNTE-UHFFFAOYSA-N 1-dodecylimidazole Chemical class CCCCCCCCCCCCN1C=CN=C1 JMTFLSQHQSFNTE-UHFFFAOYSA-N 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- IYVYLVCVXXCYRI-UHFFFAOYSA-N 1-propylimidazole Chemical class CCCN1C=CN=C1 IYVYLVCVXXCYRI-UHFFFAOYSA-N 0.000 description 2
- QBNJPSHRAWSBDW-UHFFFAOYSA-N 2-methylpropane;hydrobromide Chemical class Br.CC(C)C QBNJPSHRAWSBDW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical class CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines 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
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- XZJZNZATFHOMSJ-KTKRTIGZSA-N cis-3-dodecenoic acid Chemical compound CCCCCCCC\C=C/CC(O)=O XZJZNZATFHOMSJ-KTKRTIGZSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000002027 dichloromethane extract Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- IQQDLHGWGKEQDS-UHFFFAOYSA-N methyl hept-2-enoate Chemical class CCCCC=CC(=O)OC IQQDLHGWGKEQDS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- DCXPBOFGQPCWJY-UHFFFAOYSA-N trisodium;iron(3+);hexacyanide Chemical group [Na+].[Na+].[Na+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCXPBOFGQPCWJY-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
-
- 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
-
- 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
- B01J31/0298—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 the ionic liquids being characterised by the counter-anions
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a kind of iron-based cyano-containing anion imidazole ion liquid and its preparation method and application, the ionic liquid has structure shown in formula I, the preparation method of the iron-based cyano-containing anion imidazole ion liquid is simple, synthesis condition is gentle, it is relatively low to prepare cost, easily it is biodegradable, the iron-based cyano-containing anion imidazole ion liquid can be as the catalyst of the hydrosilylation of unsaturated alkyl ester, dosage is few, catalytic activity is high, high conversion rate, reaction condition is gentle, process is simple, it is easy to operate easily controllable, it is selectively good that reaction terminates rear addition compound product, product and catalyst can be automatically subjected to phase splitting, raw material availability is high, and catalyst is repeatable to be utilized, greatly reduce cost.
Description
Technical field
The present invention relates to chemical catalysis field, and in particular to a kind of iron-based cyano-containing anion imidazole ion liquid and its system
Preparation Method and application.
Background technology
Catalyzing addition reaction of silicon with hydrogen occupies an important position in synthetic organic chemistry, is synthesizing organo-silicon coupling agent and work(
Can one of organo-silicon compound and the most important approach of organosilicon macromolecule polymer.Si―H addition reaction typically directly uses chloroplatinic acid
As catalyst.Speier catalyst (isopropyl alcohol solution of chloroplatinic acid) and Karstedt catalyst ([(ViMe2Si)20]PtCl2)
With certain catalytic activity, it is widely applied in organosilicon production.Though these platinum catalysis systems have higher
Activity, but reaction often carried out under high-temperature and high-pressure conditions, and reaction terminate after, difficulty is separated with product, catalyst is difficult to back
The problem of receipts can not recycle, catalyst cost is higher.
Willing method is further improved on the basis of forefathers by Karstedt, uses chloroplatinic acid or chloroplatinic acid
Salt with sodium acid carbonate and vinylsiloxane heating response, forms the vinylsiloxane complex compound of platinum in ethanol, such a to go
Except the catalyst of halogen, compared with the vinylsiloxane complex compound of chloroplatinic acid before, its catalytic efficiency has catalytic efficiency
Further raising, such a catalyst today still it is applied to as catalyst the most frequently used in hydrosilylation organic
The industrial numerous areas of chemistry of silicones, although such a catalyst relatively before catalyst compare, have higher catalytic efficiency,
But simultaneously there is also storage it is unstable, it is more sensitive to the moisture in environment and oxygen, easily with the huge sum of money in storage condition
Belong to ion and other active compounds produce reaction, form the unstable platinum compounds of new high-valence state, ultimately form platinum black
Precipitation, loses catalytic activity.Therefore, developing one kind can keep higher catalytic activity simultaneously again to storage with industrialized production
Active ion species in environment are less sensitive, the hydrosilylation catalyst of storage-stable can just seem particularly under the conditions of more
It is 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.CN101322946A discloses a kind of catalyst, should
Catalyst is the mixture of platinum and the amino-compound of carboxy-containing acid group, but the catalyst can not recycling, increase
The production cost of catalyst article is added.
The research conditions of catalyst are used for current hydrosilylation, prepare new, efficient, recyclable catalysis
Agent, which is used for hydrosilylation, has important application prospect and very major and immediate significance.
The content of the invention
It is an object of the invention to provide a kind of iron-based cyano-containing anion imidazole ion liquid and preparation method thereof and answer
With.
To use following technical scheme up to this purpose, the present invention：
On the one hand, the present invention provides a kind of iron-based cyano-containing anion imidazole ion liquid, and the ionic liquid has such as
Structure shown in following formula I：
Wherein, R is hydrogen, alkyl, alkoxy, hydroxy alkyl or alkylene ,-CnH2n+1For straight chained alkyl or branched alkyl, and
N is 2,4,6 or 8.
In the present invention, the iron-based cyano-containing anion imidazole ion liquid is a kind of novel ion liquid, to water and
Air-stable, toxicity is low, is easily biodegradable.The addition of this kind of ionic liquid-catalyzed unsaturated alkyl ester and a variety of silane containing hydrogens
During reaction, dosage is few, and reaction condition is gentle, and feed stock conversion is high, and addition compound product is selectively good, and course of reaction is simple, is easy to control
System, and can be a kind of excellent catalyst with recycling.
Preferably, the R is hydrogen, C1~C12 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12)
Straight chained alkyl or branched alkyl, ethoxy or vinyl.
Such as the straight chained alkyl or branched alkyl of the C1~C12 can be methyl, ethyl, propyl group, isopropyl, positive fourth
Base, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, undecyl, dodecyl.
In the present invention, the preferred C1-C8 of the alkoxy (such as C1, C2, C3, C4, C5, C6, C7 or C8) alkoxy,
Such as the alkoxy can be methoxyl group, ethyoxyl, propoxyl group or butoxy etc..
In the present invention, the hydroxy alkyl is the alkyl group containing hydroxyl, such as the hydroxy alkyl can be hydroxyl
Ethyl, hydroxypropyl, hydroxybutyl etc..
In the present invention, the alkylene is the group containing carbon-carbon double bond, such as can be vinyl, acrylic etc..
N is 2,4,6 or 8 in the present invention, if n selects other numerical value, such as 1,3,5,7 etc., is then catalyzed unsaturated alkane
Catalytic effect is poor when base ester and the addition reaction of a variety of silane containing hydrogens, and feed stock conversion and addition compound product have selectively dropped
It is low.
Preferably, the iron-based cyano-containing anion imidazole ion liquid is the imidazoles with the structure as shown in following formula A-F
Ionic liquid：
Wherein-CnH2n+1For straight chained alkyl or branched alkyl, and n is 2,4,6 or 8, and wherein C12H25- and C3H7- it is straight
Alkyl group.
On the other hand, the invention provides the preparation method of iron-based cyano-containing anion imidazole ion liquid as described above,
Comprise the following steps：
(1) N- alkyl imidazoles shown in Formula II and halogenated alkane CnH2n+1X reacts, and obtains imidazole ion liquid shown in formula III,
Reaction equation is as follows：
(2) imidazole ion liquid shown in formula III carries out anion exchange reaction with iron cyanide salt, obtains iron shown in Formulas I
Base cyano-containing anion imidazole ion liquid, reaction equation are as follows：
Wherein R is hydrogen, alkyl, alkoxy, hydroxy alkyl or alkylene ,-CnH2n+1For straight chained alkyl or branched alkyl, and n
For 2,4,6 or 8；X is halogen (such as can be chlorine or bromine).
In the present invention, the preparation method prepares ionic liquid, takes N- alkyl imidazoles, adds halogenated alkane and carries out quaternary amine
Change reaction, then addition adds the progress anion exchange of iron cyanide salt and obtains iron-based cyano-containing anion imidazol ion liquid
Body.This method synthesis condition is gentle, and the reaction time is short, and preparing raw material cost is low, is prepared beneficial to extensive.
In preparation method of the present invention, N- alkyl imidazoles shown in step (1) described Formula II and halogenated alkane CnH2n+1X's feeds intake
Mol ratio is (1-1.5):1, such as can be 1:1、1.1:1、1.2:1、1.3:1、1.4:1 or 1.5:1 preferably 1.2:1.
Preferably, step (1) described halogenated alkane is brominated alkanes.
Preferably, the temperature of step (1) described reaction is 110-180 DEG C, for example, can be 110 DEG C, 120 DEG C, 130 DEG C,
140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C or 180 DEG C, preferably 150 DEG C.
Preferably, the time of step (1) described reaction is 3-20 hours, for example, can be 3 hours, 4 hours, 5 hours, 7
Hour, 8 hours, 10 hours, 13 hours, 15 hours, preferably 18 hours or 20 hours, 5-10 hours.
Preferably, step (2) iron cyanide salt is Na3[Fe(CN)6]。
Preferably, the iron cyanide salt and imidazole ion liquid mol ratio are 1:(1-2000), such as can be 1:1、
1:50、1:100、1:300、1:400、1:500、1:1000、1:1200、1:1500 or 1:2000, it is more highly preferred to 1:(1-1200),
Most preferably 1:(300-500).
Preferably, step (2) reaction is carried out in organic solvent, such as can be acetone or acetonitrile, described organic
The preferred second eyeball of solvent.
Preferably, the temperature of step (2) described reaction is room temperature.
Preferably, the time of step (2) described reaction is 5-72 hours, for example, can be 5 hours, 8 hours, 12 hours,
18 hours, 30 hours, 40 hours, 48 hours, 56 hours, 65 hours or 72 hours, preferably 12-48 hours.
On the other hand, the present invention provides iron-based cyano-containing anion imidazole ion liquid as described above as unsaturated alkyl
The application of the catalyst for addition reaction of hydrogen and silicon of ester.
Iron-based cyano-containing anion imidazole ion liquid in the present invention can be used as catalyst to be catalyzed unsaturated alkyl
Ester hydrosilylation, its catalytic activity is high, and reaction-ure conversion-age is high, and reaction terminates rear product and catalyst stratification, can
It is automatically subjected to phase splitting, product is distributed, and course of reaction is simple, easy to operate, easily controllable, the recyclable recycling of catalyst,
Save cost.
Preferably, the unsaturated alkyl ester has been selected from methyl acrylate, 4- amylene-4 acid methyl esters, 4- decenoates, 5-
E pioic acid methyl ester, 6- heptenoic acids methyl esters, 6- heptenoates, butyl 10-hendecenoate, 10 hendecenoic acid ethyl ester or lauroleic acid
Any one in methyl esters or at least two combination.
Preferably, the mol ratio of the iron-based cyano-containing anion imidazole ion liquid and unsaturated alkyl ester is l:500-
5000, such as can be 1:500、1:550、1:600、1:700、1:800、1:1000、1:1300、1:1500、1:1800、1:
2000、1:2400、1:2800、1:3000、1:3500、1:4000、1:4500 or 1:5000 etc., preferably 1:1000-3000, more
Preferably 1:1200-2500.
Preferably, the paraffin hydrocarbons activation used in the hydrosilylation of the unsaturated alkyl ester is selected from three ethoxies
Any one in base hydrogen silane, trimethoxy hydrogen silane, methyl dimethoxy epoxide hydrogen dimethylamino base silane or three isopropoxy silane
Or at least two combination.
Preferably, the mol ratio of the unsaturated alkyl ester and paraffin hydrocarbons activation is 1:1-3, such as can be 1:1、
1:1.5、1:2、1:2.5 or 1:3.
Preferably, the temperature of the hydrosilylation is the synthesis under normal pressure carried out at 60-140 DEG C, such as can be 60
DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, the synthesis under normal pressure that carries out at 130 DEG C or 140 DEG C.
Preferably, the time of the hydrosilylation is 4-24h, for example, can be 4h, 6h, 8h, 9h, 12h, 17h,
20h, 22h or 24h.
Relative to prior art, the invention has the advantages that：
(1) iron-based cyano-containing anion imidazole ion liquid is a kind of novel ion liquid in the present invention, to water and air
Stable, toxicity is low, is easily biodegradable, and catalyst can be used as to be used to be catalyzed unsaturated alkyl ester hydrosilylation, and dosage is few,
Catalytic activity is high, and reaction-ure conversion-age is high, and reaction condition is gentle, and process is simple, easy to operate easily controllable, and reaction adds after terminating
Into good product selectivity, product and catalyst can be automatically subjected to phase splitting, and product is distributed, and raw material availability is high, and catalyst can weigh
It is multiple to utilize, greatly reduce cost.
(2) iron-based cyano-containing anion imidazole ion liquid synthesis condition is gentle in the present invention, the reaction time is short, prepares former
Expect that cost is relatively low, large-scale production can be achieved.
Embodiment
Technical scheme is further illustrated below by embodiment.Those skilled in the art should be bright
, the embodiment be only to aid in understand the present invention, be not construed as to the present invention concrete restriction.
Embodiment 1
Iron-based cyano-containing anion imidazole ion liquid A preparation：
(1) in 100mL round-bottomed flask, 120mmol N- dodecyl imidazoles and 35mL toluene, magnetic agitation are added
After uniformly, 100mmol 1- butyl bromides, 150 DEG C of heating reflux reactions 8 are slowly added dropwise into flask using constant pressure funnel
Hour.TLC monitoring reactions terminate, and lower floor's product is washed with toluene, removes unreacted N- dodecyl imidazoles and 1- bromo fourth
Alkane, rotary evaporation are gone out solvent, are obtained during thick product direct plunges into and react in next step.
(2) by obtained product and Na in above-mentioned steps (1)3[Fe(CN)6] liquid mole ratio be 400：1 ratio is dissolved in
In acetonitrile, add sodium bromide and reaction 20 hours is stirred at room temperature, after reaction terminates, vacuum distillation removes solvent, dichloromethane extraction production
Thing, target compound is obtained after solvent is evaporated off, be yellow oil, yield 76.7%.
Embodiment 2
Iron-based cyano-containing anion imidazole ion liquid B preparation：
(1) in 100mL round-bottomed flask, add 100mmol 1- (2- ethoxys) imidazoles and 35mL toluene, magnetic force stir
After mixing uniformly, 100mmol bromic ethers, 180 DEG C of heating reflux reactions 20 are slowly added dropwise into flask using constant pressure funnel
Hour.TLC monitoring reactions terminate, and lower floor's product is washed with toluene, removes unreacted 1- (2- ethoxys) imidazoles and bromo second
Alkane, rotary evaporation are gone out solvent, are obtained during thick product direct plunges into and react in next step.
(2) by obtained product and Na in above-mentioned steps (1)3[Fe(CN)6] liquid mole ratio be 1：1 ratio is dissolved in second
In nitrile, adding sodium bromide and reaction 72 hours is stirred at room temperature, after reaction terminates, vacuum distillation removes solvent, and dichloromethane extracts product,
Target compound is obtained after solvent is evaporated off, is yellow oil, yield 64.6%.
Embodiment 3
Iron-based cyano-containing anion imidazole ion liquid C preparation：
(1) in 100mL round-bottomed flask, 150mmol imidazoles and 35mL toluene are added, after magnetic agitation is uniform, is utilized
Constant pressure funnel is slowly added dropwise 100mmol bromic ethers into flask, 110 DEG C of heating reflux reactions 3 hours.TLC monitorings are anti-
It should terminate, lower floor's product is washed with toluene, removes unreacted imidazoles and bromic ether, and rotary evaporation is gone out solvent, is glued
Thick shape product is direct plungeed into reaction in next step.
(2) by obtained product and Na in above-mentioned steps (1)3[Fe(CN)6] liquid mole ratio be 2000：1 ratio is dissolved in
In acetone, add sodium bromide and reaction 5 hours is stirred at room temperature, after reaction terminates, vacuum distillation removes solvent, dichloromethane extraction production
Thing, target compound is obtained after solvent is evaporated off, be yellow oil, yield 65.5%.
Embodiment 4
Iron-based cyano-containing anion imidazole ion liquid D preparation：
(1) in 100mL round-bottomed flask, 120mmol N- methylimidazoles is added and 35mL toluene, magnetic agitation are uniform
Afterwards, 100mmol 1- bromooctanes are slowly added dropwise into flask using constant pressure funnel, 140 DEG C of heating reflux reactions 8 hours.
TLC monitoring reactions terminate, and lower floor's product is washed with toluene, removes unreacted N- methylimidazoles and 1- bromooctanes, rotary evaporation
Go out solvent, obtain during thick product direct plunges into and react in next step.
(2) by obtained product and Na in above-mentioned steps (1)3[Fe(CN)6] liquid mole ratio be 400：1 ratio is dissolved in
In acetonitrile, add sodium bromide and reaction 20 hours is stirred at room temperature, after reaction terminates, vacuum distillation removes solvent, dichloromethane extraction production
Thing, target compound is obtained after solvent is evaporated off, be yellow oil, yield 68.4%.
Embodiment 5
Iron-based cyano-containing anion imidazole ion liquid E preparation：
(1) in 100mL round-bottomed flask, 120mmol N- ethyl imidazol(e)s is added and 35mL toluene, magnetic agitation are uniform
Afterwards, 100mmol 1- bromo hexanes are slowly added dropwise into flask using constant pressure funnel, 120 DEG C of heating reflux reactions 8 hours.
TLC monitoring reactions terminate, and lower floor's product is washed with toluene, remove unreacted N- ethyl imidazol(e)s and 1- bromo hexane, and rotation is steamed
Solvent is sent out, thick product is obtained and direct plunges into reaction in next step.
(2) by obtained product and Na in above-mentioned steps (1)3[Fe(CN)6] liquid mole ratio be 400：1 ratio is dissolved in
In acetonitrile, add sodium bromide and reaction 20 hours is stirred at room temperature, after reaction terminates, vacuum distillation removes solvent, dichloromethane extraction production
Thing, target compound is obtained after solvent is evaporated off, be yellow oil, yield 71.5%.
Embodiment 6
Iron-based cyano-containing anion imidazole ion liquid F preparation：
(1) in 100mL round-bottomed flask, 120mmol N- propyl imidazoles is added and 35mL toluene, magnetic agitation are uniform
Afterwards, 100mmol isobutane bromides are slowly added dropwise into flask using constant pressure funnel, 160 DEG C of heating reflux reactions 8 hours.
TLC monitoring reactions terminate, and lower floor's product is washed with toluene, remove unreacted N- propyl imidazoles and isobutane bromide, and rotation is steamed
Solvent is sent out, thick product is obtained and direct plunges into reaction in next step.
(2) by obtained product and Na in above-mentioned steps (1)3[Fe(CN)6] liquid mole ratio be 400：1 ratio is dissolved in
In acetonitrile, add sodium bromide and reaction 20 hours is stirred at room temperature, after reaction terminates, vacuum distillation removes solvent, dichloromethane extraction production
Thing, target compound is obtained after solvent is evaporated off, be yellow oil, yield 74.6%.
Embodiment 7
The iron-based cyano-containing anion imidazole ion liquid (0.2mmo1) that embodiment 1 is prepared, is added to magnetic force
In the three-necked flask of agitating heater and condensing unit, under inert gas shielding, 70 DEG C are to slowly warm up to.Then again to liquid
Methyl acrylate (0.6mol) and trimethoxy hydrogen silane (0.8mo1) is added dropwise in catalyst system successively by dropping funel, protects
90 DEG C of reaction temperature is held, opens condensing reflux, continues stirring reaction 6h, stops reaction, standing is cooled to the following ionic liquid of room temperature
Body solidifies, and separates product and ionic liquid.It is evaporated under reduced pressure and collects corresponding cut, the conversion of methyl acrylate is determined by GC-MS
Rate is that 97.9%, β-addition compound product yield is 95.5%.
Embodiment 8
The iron-based cyano-containing anion imidazole ion liquid (0.2mmo1) that embodiment 2 is prepared, is added to magnetic force
In the three-necked flask of agitating heater and condensing unit, under inert gas shielding, 70 DEG C are to slowly warm up to.Then again to liquid
4- amylene-4 acid methyl esters (0.6mol) and trimethoxy hydrogen silane (0.7mo1) is added dropwise in catalyst system successively by dropping funel,
100 DEG C of reaction temperature is kept, opens condensing reflux, continues stirring reaction 4h, stops reaction, standing is cooled to the following ion of room temperature
Liquid solidifies, and separates product and ionic liquid.It is evaporated under reduced pressure and collects corresponding cut, 4- amylene-4 acid methyl esters is determined by GC-MS
Conversion ratio is that 96.9%, β-addition compound product yield is 94.5%.
Embodiment 9
The iron-based cyano-containing anion imidazole ion liquid (0.1mmo1) that embodiment 3 is prepared, is added to magnetic force
In the three-necked flask of agitating heater and condensing unit, under inert gas shielding, 80 DEG C are to slowly warm up to.Then again to liquid
It is added dropwise successively by dropping funel in catalyst system, 4- decenoates (0.3mol) and triethoxy hydrogen silane
(0.5mo1), 140 DEG C of reaction temperature is kept, open condensing reflux, continue stirring reaction 24h, stop reaction, standing is cooled to room
The following ionic liquid solidification of temperature, separates product and ionic liquid.It is evaporated under reduced pressure and collects corresponding cut, is determined by GC-MS, the 4- last of the ten Heavenly stems
The conversion ratio of e pioic acid methyl ester is that 98.9%, β-addition compound product (hendecyl trimethoxy silane) yield is 95.5%.
Embodiment 10
The iron-based cyano-containing anion imidazole ion liquid (0.01mmo1) that embodiment 4 is prepared, is added to magnetic
In the three-necked flask of power agitating heater and condensing unit, under inert gas shielding, 80 DEG C are to slowly warm up to.Then again to liquid
5- e pioic acid methyl ester (0.6mol) and methyl dimethoxy epoxide hydrogen silane is added dropwise in body catalyst system successively by dropping funel
(0.8mo1), 90 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, 5- alkene is determined by GC-MS
The conversion ratio of sour methyl esters is that 98.9%, β-addition compound product yield is 96.5%.
Embodiment 11
The iron-based cyano-containing anion imidazole ion liquid (0.2mmo1) that embodiment 5 is prepared, is added to magnetic force
In the three-necked flask of agitating heater and condensing unit, under inert gas shielding, it is to slowly warm up to 80 DEG C of catalyst and melts.So
6- heptenoic acids methyl esters (0.7mol) and triethoxy hydrogen silicon is added dropwise successively by dropping funel into Liquid catalyst systems again afterwards
Alkane (0.7mo1), 100 DEG C of reaction temperature is kept, open condensing reflux, continue stirring reaction 8h, 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, 6- is determined by GC-MS
The conversion ratio of heptenoic acid methyl esters is that 98.4%, β-addition compound product yield is 96.5%.
Embodiment 12
The iron-based cyano-containing anion imidazole ion liquid (0.2mmo1) that embodiment 6 is prepared, is added to magnetic force
In the three-necked flask of agitating heater and condensing unit, under inert gas shielding, 70 DEG C are to slowly warm up to.Then again to liquid
Butyl 10-hendecenoate (0.7mol) and methyl dimethoxy epoxide hydrogen silane is added dropwise in catalyst system successively by dropping funel
(1.4mo1), 110 DEG C of reaction temperature is kept, open condensing reflux, continue stirring reaction 12h, stop reaction, standing is cooled to room
The following ionic liquid solidification of temperature, separates product and ionic liquid.It is evaporated under reduced pressure and collects corresponding cut, 10- ten is determined by GC-MS
The conversion ratio of monoenoic acid butyl ester is that 98.9%, β-addition compound product yield is 95.5%.
Embodiment 13
The iron-based cyano-containing anion imidazole ion liquid (0.01mmo1) that embodiment 4 is prepared, is added to magnetic
In the three-necked flask of power agitating heater and condensing unit, under inert gas shielding, 80 DEG C are to slowly warm up to.Then again to liquid
10 hendecenoic acid ethyl ester (0.6mol) and three isopropoxy silane is added dropwise in body catalyst system successively by dropping funel
(1.8mo1), 90 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, 10- 11 is determined by GC-MS
The conversion ratio of olefin(e) acid ethyl ester is that 96.9%, β-addition compound product yield is 93.5%.
Embodiment 14
The iron-based cyano-containing anion imidazole ion liquid (0.02mmo1) that embodiment 3 is prepared, is added to magnetic
In the three-necked flask of power agitating heater and condensing unit, under inert gas shielding, 70 DEG C are to slowly warm up to.Then again to liquid
Lauroleic acid methyl esters (0.6mol) and methyl dimethoxy epoxide hydrogen silane is added dropwise in body catalyst system successively by dropping funel
(0.8mo1), 100 DEG C of reaction temperature is kept, open condensing reflux, continue stirring reaction 5h, stop reaction, standing is cooled to room
The following ionic liquid solidification of temperature, separates product and ionic liquid.It is evaporated under reduced pressure and collects corresponding cut, 12 is determined by GC-MS
The conversion ratio of e pioic acid methyl ester is that 94.9%, β-addition compound product yield is 90.5%.
Embodiment 15
In the present embodiment, to repeating to be catalyzed unsaturated alkyl using iron-based cyano-containing anion imidazole ion liquid
The effect of ester hydrosilylation is verified that method is as follows：
After example 7 to be performed stops reacted reaction liquid layer, catalyst system, inertia are left after upper solution is poured out
Under gas shield, methyl acrylate (0.6mol) and three are then added dropwise successively by dropping funel into Liquid catalyst systems again
Methoxyl group hydrogen silane (0.8mo1), 90 DEG C of reaction temperature is kept, open condensing reflux, continue stirring reaction 6h, stop reaction, it is quiet
Put and be 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, passes through GC-
The conversion ratio of MS measure methyl acrylates is that 98.9%, β-addition compound product yield is 97.5%, by the ionic liquid of embodiment 7 again
Reuse 5 times, reaction condition is constant, and experimental result is shown in Table 1.
Table 1
As can be seen from Table 1, reuse 5 times, the catalytic effect of ionic-liquid catalyst slightly floats, but unsaturated alkane
The selectivity of base ester conversion ratio and silane all maintains higher level, therefore, utilizes iron-based cyano-containing anion imidazol ion
The method that liquid catalyst prepares silane has feasibility.
As above identical is carried out after stopping reacted reaction liquid layer to embodiment 8-14 also with same method
Processing, it is anti-that the iron-based cyano-containing anion imidazole ion liquid after being reclaimed with checking repeats catalysis unsaturated alkyl ester Si―H addition reaction
The effect answered, reuse 5 times, every time using unsaturated alkyl ester conversion rate more than 94%, β-addition compound product yield is equal
More than 91%, result when ionic liquid the 5th that table 2 lists embodiment 8-14 separation is catalyzed.
Table 2
From the result of Tables 1 and 2, the iron-based cyano-containing anion imidazole ion liquid that the present invention is prepared is used for
When being catalyzed unsaturated alkyl ester hydrosilylation, catalytic activity is high, and reaction-ure conversion-age is high, good product selectivity, and should
Iron-based cyano-containing anion imidazole ion liquid can reuse, recycling can also reach for 5 times higher catalytic activity and
Higher selectivity of product, greatly reduce catalyst and utilize cost.
Applicant states that the present invention illustrates the iron-based cyano-containing anion imidazol ion of the present invention by above-described embodiment
Liquid and its preparation method and application, but the invention is not limited in above-mentioned method detailed, that is, do not mean that the present invention must be according to
Above-mentioned method detailed is relied to implement.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to this
The equivalence replacement of each raw material of invention product and the addition of auxiliary element, the selection of concrete mode etc., all fall within the protection of the present invention
Within the scope of scope and disclosure.
Claims (10)
1. a kind of iron-based cyano-containing anion imidazole ion liquid, it is characterised in that it has the structure as shown in following formula I：
Wherein, R is hydrogen, alkyl, alkoxy, hydroxy alkyl or alkylene ,-CnH2n+1For straight chained alkyl or branched alkyl, and n is
2nd, 4,6 or 8.
2. iron-based cyano-containing anion imidazole ion liquid according to claim 1, it is characterised in that R be hydrogen, C1~
C12 straight chained alkyl or branched alkyl, ethoxy or vinyl；
Preferably, the iron-based cyano-containing anion imidazole ion liquid is the imidazol ion with the structure as shown in following formula A-F
Liquid：
Wherein-CnH2n+1For straight chained alkyl or branched alkyl, and n is 2,4,6 or 8.
3. the preparation method of iron-based cyano-containing anion imidazole ion liquid according to claim 1 or 2, its feature exist
In the described method comprises the following steps：
(1) N- alkyl imidazoles shown in Formula II and halogenated alkane CnH2n+1X reacts, and obtains imidazole ion liquid shown in formula III, reacts
Formula is as follows：
(2) imidazole ion liquid shown in formula III carries out anion exchange reaction with iron cyanide salt, obtains iron-based shown in Formulas I and contains
Cyano group anion imidazole ion liquid, reaction equation are as follows：
Wherein R is hydrogen, alkyl, alkoxy, hydroxy alkyl or alkylene ,-CnH2n+1For straight chained alkyl or branched alkyl, and n be 2,
4th, 6 or 8, X be halogen.
4. preparation method according to claim 3, it is characterised in that N- alkyl imidazoles shown in step (1) described Formula II with
Halogenated alkane CnH2n+1X molar ratio is (1-1.5):1, preferably 1.2:1；
Preferably, step (1) described halogenated alkane is brominated alkanes；
Preferably, the temperature of step (1) described reaction is 110-180 DEG C, preferably 150 DEG C；
Preferably, the time of step (1) described reaction is 3-20 hours, preferably 5-10 hours.
5. the preparation method according to claim 3 or 4, it is characterised in that step (2) iron cyanide salt is Na3[Fe
(CN)6]；
Preferably, the iron cyanogen compound and imidazole ion liquid mol ratio are 1:(1-2000), is more highly preferred to 1:(1-1200),
Most preferably 1:(300-500).
6. according to the preparation method any one of claim 3-5, it is characterised in that step (2) reaction is organic
Carried out in solvent, the preferred second eyeball of organic solvent；
Preferably, the temperature of step (2) described reaction is room temperature；
Preferably, the time of step (2) described reaction is 5-72 hours, preferably 12-48 hours.
7. silicon of the iron-based cyano-containing anion imidazole ion liquid according to claim 1 or 2 as unsaturated alkyl ester
The application of catalyst for addition reaction of hydrogen.
8. application according to claim 7, it is characterised in that the unsaturated alkyl ester is selected from methyl acrylate, 4- penta
E pioic acid methyl ester, 4- decenoates, 5- e pioic acid methyl ester, 6- heptenoic acids methyl esters, 6- heptenoates, butyl 10-hendecenoate,
Any one in 10 hendecenoic acid ethyl ester or lauroleic acid methyl esters or at least two combination.
9. the application according to claim 7 or 8, it is characterised in that the iron-based cyano-containing anion imidazole ion liquid
Mol ratio with unsaturated alkyl ester is l:500-5000, preferably 1:1000-3000, more preferably 1:1200-2500；
Preferably, the paraffin hydrocarbons activation used in the hydrosilylation of the unsaturated alkyl ester is selected from triethoxy hydrogen
Any one in silane, trimethoxy hydrogen silane, methyl dimethoxy epoxide hydrogen silane or three isopropoxy silane or at least two
Combination；
Preferably, the mol ratio of the unsaturated alkyl ester and paraffin hydrocarbons activation is 1:1-3.
10. according to the application any one of claim 7-9, it is characterised in that the temperature of the hydrosilylation is
The synthesis under normal pressure carried out at 60-140 DEG C；
Preferably, the time of the hydrosilylation is 4-24h.
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| CN109456270A (en) * | 2018-11-13 | 2019-03-12 | 徐州工程学院 | A kind of ion liquid preparation device |
| CN111265809A (en) * | 2020-03-29 | 2020-06-12 | 浙江红狮环保股份有限公司 | Preparation and application of high-chlorine fly ash washing agent |
| CN114591375A (en) * | 2022-03-23 | 2022-06-07 | 国科广化精细化工孵化器(南雄)有限公司 | Imidazoline modified iron metal complex and preparation method and application thereof |
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| CN111265809A (en) * | 2020-03-29 | 2020-06-12 | 浙江红狮环保股份有限公司 | Preparation and application of high-chlorine fly ash washing agent |
| CN114591375A (en) * | 2022-03-23 | 2022-06-07 | 国科广化精细化工孵化器(南雄)有限公司 | Imidazoline modified iron metal complex and preparation method and application thereof |
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