CN103483381A - Preparation method of first-class phosphorus functionalized ionic liquid and application of ionic liquid in hydroformylation - Google Patents
Preparation method of first-class phosphorus functionalized ionic liquid and application of ionic liquid in hydroformylation Download PDFInfo
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- CN103483381A CN103483381A CN201310370138.6A CN201310370138A CN103483381A CN 103483381 A CN103483381 A CN 103483381A CN 201310370138 A CN201310370138 A CN 201310370138A CN 103483381 A CN103483381 A CN 103483381A
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- ionic liquid
- phosphine
- alkene
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- functionalization
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 66
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title abstract 4
- 229910052698 phosphorus Inorganic materials 0.000 title abstract 4
- 239000011574 phosphorus Substances 0.000 title abstract 4
- 238000002360 preparation method Methods 0.000 title description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 15
- 150000003624 transition metals Chemical class 0.000 claims abstract description 15
- -1 alkyl guanidinium Chemical compound 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 6
- 238000005342 ion exchange Methods 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 150
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 105
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 54
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 42
- 238000007306 functionalization reaction Methods 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 230000006837 decompression Effects 0.000 claims description 28
- 150000002500 ions Chemical class 0.000 claims description 28
- 150000001336 alkenes Chemical class 0.000 claims description 27
- 229910052786 argon Inorganic materials 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 230000003197 catalytic effect Effects 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- 230000035484 reaction time Effects 0.000 claims description 14
- 239000010948 rhodium Substances 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 12
- 239000010935 stainless steel Substances 0.000 claims description 12
- 230000009466 transformation Effects 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 150000003003 phosphines Chemical class 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- LYXHWHHENVLYCN-QMDOQEJBSA-N (1z,5z)-cycloocta-1,5-diene;rhodium;tetrafluoroborate Chemical compound [Rh].F[B-](F)(F)F.C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 LYXHWHHENVLYCN-QMDOQEJBSA-N 0.000 claims description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 2
- VTMSSJKVUVVWNJ-UHFFFAOYSA-N 1-ethenyl-4-(2-methylpropyl)benzene Chemical compound CC(C)CC1=CC=C(C=C)C=C1 VTMSSJKVUVVWNJ-UHFFFAOYSA-N 0.000 claims description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 claims description 2
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 claims description 2
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006053 organic reaction Methods 0.000 abstract description 2
- 239000004721 Polyphenylene oxide Substances 0.000 abstract 3
- 229920000570 polyether Polymers 0.000 abstract 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 55
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 25
- 239000012071 phase Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- 239000000706 filtrate Substances 0.000 description 15
- 239000011541 reaction mixture Substances 0.000 description 15
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 11
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 11
- 238000004587 chromatography analysis Methods 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical group CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 230000002051 biphasic effect Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 229950000081 metilsulfate Drugs 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Abstract
The invention relates to synthesis of first-class phosphorus functionalized polyether alkyl guanidinium ionic liquid, and an application of the first-class phosphorus functionalized polyether alkyl guanidinium ionic liquid in a homogeneous catalytic reaction. The functionalized ionic liquid of such class can be easily prepared by an ion exchange reaction between the polyether alkyl guanidinium ionic liquid and sulfonic acid type water soluble phosphine ligand. The designed phosphorus functionalized ionic liquid can be applied to organic reactions, including hydroformylation, hydroesterification, hydrocarboxylation and catalytic hydrogenation under the catalyzing of a transition metal; the dosage of the ionic liquid used in the catalytic reaction can be decreased; the activity of the catalytic reaction can be improved; a catalyst can be separated and cycled simply and conveniently.
Description
Technical field
The present invention relates to technical field of chemistry and chemical engineering, relate to particularly the preparation of a class phosphine functionalized ion liquid and the application in hydroformylation reaction thereof.
Background technology
The homogeneous phase noble metal catalyst has advantages of that catalytic activity is high, selectivity good, reaction conditions is gentle, receives in recent decades increasing concern.How from the homogeneous catalytic reaction product, high efficiency separation and circulation noble metal catalyst are challenging research topics always.Water/organic two-phase system is successfully applied in the production of the separation of homogeneous catalyst and hydroformylation of propene producing butyladehyde, but a lot of solubleness of organic reaction substrate in water is lower, causes the reaction mass transfer problem, and its range of application is restricted.In recent years, concept based on " homogeneous catalysis heterogenize ", various new methods are constantly developed to address this problem, as: organic fluorine two-phase, ionic liquid at room temperature, supercutical fluid two-phase system etc., wherein the development of non-aqueous ionic liquid system is very rapid, has become one of biphasic catalysis system of tool application prospect.
Although noble metal catalyst is carried in ionic liquid and realizes that the biphasic catalysis reaction is proved by a large amount of successful research and reports, some crucial problems still have to be solved.One of problem is: supported precious metal catalyst needs a large amount of ionic liquids, and the preparation cost of ionic liquid is higher, and economy is not good; The 2nd: under most non-aqueous ionic liquid systems, the restriction that is subject to solubleness in ionic liquid due to reactant molecule must overcome mass transfer and diffusional resistance could arrive active sites, causes catalytic activity to reduce.
Recently; we are at Chem.Commun.2012; reported in 48,9017-9019 and patent CN201210064537.5 that a class has polyoxyalkylene alkyl guanidine metilsulfate ionic liquid and the application in higher olefins two-phase hydroformylation reaction thereof of the liquid-solid phase-change characteristic of room temperature.The novel functional ion liquid of this class can effective immobilized Rh-TPPTS catalyzer, and has the ability of stablizing the rhodium catalytic activity species significantly.But due to the restriction that is subject to biphasic catalysis system resistance to mass transfer, to C
10above its activity of straight chain 1-alkene has reduction by a relatively large margin.
Summary of the invention
For the deficiencies in the prior art, the present invention gets up the advantages of polyoxyalkylene alkyl guanidinium ionic liquid and Water-soluble Sulphonated phosphines, and the polyoxyalkylene alkyl guanidinium ionic liquid (PPGIL) of a class phosphine functionalization has been synthesized in design.
The polyoxyalkylene alkyl guanidinium ionic liquid of this class Novel phosphine functionalization has advantages of following uniqueness: (1) is synthetic very simple, by polyoxyalkylene alkyl guanidine metilsulfate ionic liquid, with the ion exchange reaction between sodium sulfonate type water-soluble phosphine ligand, can prepare; (2) the cationic introducing of polyoxyalkylene alkyl guanidinesalt can be transformed into ionic liquid by dystectic sodium sulfonate type water-soluble phosphine ligand, according to the needs of application, the physics and chemistry character of PPGIL (polarity, solvability, viscosity, zero pour, specific conductivity, hydrophilic-lipophilic balance and thermostability etc.) can regulate and control easily by EO value, N-alkyl and the O-alkyl changed on polyoxyalkylene alkyl guanidinesalt positively charged ion.As, sodium sulfonate type water-soluble phosphine ligand generally be insoluble to low-pole organic solvent (as, benzene, toluene, methylene dichloride etc.) and some polar solvents (as, methyl alcohol, acetonitrile, tetrahydrofuran (THF) etc.), and PPGIL is soluble in above-mentioned solvent, this has expanded the range of application of Water-soluble Sulphonated phosphines to a great extent; (3) as the Water-soluble Sulphonated phosphines synthetic method maturation of PPGIL negatively charged ion, source is abundant, and range of choice is wide, can regulate and control easily activity, chemo-selective, regioselectivity and the stereoselectivity of catalyzer by the structure that changes negatively charged ion; (4) in catalystic converter system, PPGIL has played the part of the role of support of the catalyst and part simultaneously as ionic liquid, and need not be more additional other ionic liquid, as carrier, therefore greatly reduces the consumption of ionic liquid; (5) be soluble in the intensive polar solvents such as the weak polar solvents such as benzene, toluene, methylene dichloride and methyl alcohol, acetonitrile, tetrahydrofuran (THF) due to PPGIL, be insoluble in alkane solvent, therefore catalyzed reaction can be carried out in benzene, toluene, methylene dichloride, methyl alcohol, acetonitrile, tetrahydrofuran (THF) equal solvent, realize homogeneous reaction, after reaction finishes, lower boiling solvent is removed in decompression, for containing carbon number, being less than 8 alkene, directly underpressure distillation obtains product aldehyde, and the residual ion liquid phase can continue next catalytic cycle; For containing carbon number, being more than or equal to 8 alkene, use C
6-C
8alkane or petroleum ether extraction product aldehyde, the residual ionic liquid next catalytic cycle of rear continuation that is separated, because reaction is to carry out under homogeneous phase condition, there do not is mass transfer problem, improving catalytic activity and optionally the while has also been realized high efficiency separation and the circulation of catalyzer.
The present invention designs the ionic liquid that has synthesized a class phosphine functionalization, it is characterized in that: the positively charged ion of this class phosphine functionalized ion liquid is polyoxyalkylene alkyl guanidinesalt positively charged ion, and negatively charged ion is the Water-soluble Sulphonated phosphines negatively charged ion, and its structural formula is:
In formula: m=1-100; R
1for C
1-C
16normal chain alkyl; R
2for H, C
1-C
16normal chain alkyl or benzyl; R
3for C
1-C
16normal chain alkyl or phenyl; R
4for the negatively charged ion of the Water-soluble Sulphonated phosphines shown in following, n is the number of sulfonic group negatively charged ion on the phosphine part, n=1-8;
In formula: R
5for C
6h
5or C
6h
4-3-SO
3 -; R
6, R
7, R
8, R
9, R
10, R
11, R
12and R
13be respectively the parent fraction of different Water-soluble Sulphonated phosphines.
The synthetic method of the ionic liquid 1 of phosphine functionalization is as follows:
In formula: R
14for CH
3or p-CH
3-C
6h
4.
The ionic liquid 1 of phosphine functionalization is by polyoxyalkylene alkyl guanidinium ionic liquid 2 and sodium sulfonate type water-soluble phosphine ligand [Na
+]
n[R
4]
n-at CH
3carry out prepared by ion exchange reaction in CN, temperature of reaction is 0-80 ℃, reaction times 8-72h.
The ionic liquid 1 of phosphine functionalization can be applicable to hydroformylation; hydroesterification; hydrocarboxylation and catalytic hydrogenation, have for the metal with the described phosphine functionalized ion liquid formation of claim 1 transition metal complex catalysts: rhodium (Rh), ruthenium (Ru), iridium (Ir), palladium (Pd), platinum (Pt), osmium (Os), gold (Au) or cobalt (Co).
The ionic liquid 1 of phosphine functionalization can be applicable to the hydroformylation reaction of alkene, and the alkene of use is C
3-C
16linear alpha-olefin, tetrahydrobenzene, vinylbenzene, p-methylstyrene, o-methyl styrene, p-tert-butylstyrene, p-isobutylstyrene, to methoxy styrene, to chloro-styrene, chloro styrene or 2-vinyl naphthalene, the transition metal complex catalysts precursor of employing is RhCl
33H
2o, Rh (acac) are (CO)
2(rhodium dicarbonyl acetylacetonate), [Rh (COD)
2] BF
4(COD:1,5-cyclooctadiene) or [Rh (COD) Cl]
2, transition metal complex catalysts is generated in-situ under the hydroformylation reaction condition by phosphine functionalized ion liquid 1 and transition metal complex catalysts precursor.
The ionic liquid 1 of phosphine functionalization is for the hydroformylation reaction of alkene; it is characterized in that: phosphine functionalized ion liquid 1, transition metal complex catalysts precursor, alkene and organic solvent are added in the stainless steel autoclave; make 1 with the transition metal complex catalysts precursor in the mol ratio of rhodium be 1:1-50:1; in alkene and transition metal complex catalysts precursor, the mol ratio of rhodium is 100:1-10000:1; the volume ratio of organic solvent and alkene is 1:1-10:1; with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1:1) be forced into 1.0-7.0MPa, start stirring, temperature of reaction 70-130 ℃, reaction times 0.5-24 hour, then be cooled to room temperature, the emptying synthetic gas, organic solvent is removed in decompression, obtain product aldehyde for the direct underpressure distillation of alkene that is less than 8 containing carbon number, residual catalyst phase (comprising ionic liquid 1 and catalyzer) continues next catalytic cycle after adding new organic solvent and alkene; For containing carbon number, being more than or equal to 8 alkene, use C
6-C
8normal paraffin or petroleum ether extraction product aldehyde, obtain the upper strata product phase that contains product aldehyde through simply being separated, lower floor's catalyzer phase (comprising ionic liquid 1 and catalyzer) continues next catalytic cycle after adding new organic solvent and alkene; The single transformation efficiency of alkene is 90-99%, and the selectivity of aldehyde is 90-99%, and the mol ratio of n-alkanal and isomery aldehyde is 0.05:1-50:1.
The ionic liquid 1 of phosphine functionalization, for the hydroformylation reaction of alkene, is characterized in that: applied organic solvent is benzene, toluene, methyl alcohol, ethanol, acetonitrile, methylene dichloride or tetrahydrofuran (THF).
Embodiment
Embodiment 1
The ionic liquid 1:[R of phosphine functionalization
3(EO)
mn
+r
2=C (NR
1 2)
2]
n[R
4] synthetic (R
1=CH
3; R
2=H; R
3=CH
3; R
4=(SO
3 -)
n-R
6; M=16, n=3)
Under argon shield, add (the SO of 1.56mmol in the 50mLSchlenk bottle
3na)
3-R
6, [the CH of 4.73mmol
3(EO)
16n
+h=C (N (CH
3)
2)
2] [CH
3sO
3 -] and the 10mL acetonitrile, reaction mixture at room temperature stirs 72 hours, filters, and filtrate decompression is removed acetonitrile and is obtained orange-yellow thick liquid, yield 95%.
Embodiment 2
The ionic liquid 1:[R of phosphine functionalization
3(EO)
mn
+r
2=C (NR
1 2)
2]
n[R
4] synthetic (R
1=CH
3; R
2=H; R
3=C
6h
5; R
4=(SO
3 -)
n-R
6; M=16, n=3)
Under argon shield, add (the SO of 1.56mmol in the 50mLSchlenk bottle
3na)
3 -r
6, [the C of 4.73mmol
6h
5(EO)
16n
+h=C (N (CH
3)
2)
2] [CH
3sO
3 -] and the 10mL acetonitrile, reaction mixture at room temperature stirs 72 hours, filters, and filtrate decompression is removed acetonitrile and is obtained orange-yellow thick liquid, yield 90%.
Embodiment 3
The ionic liquid 1:[R of phosphine functionalization
3(EO)
mn
+r
2=C (NR
1 2)
2]
n[R
4] synthetic (R
1=CH
3; R
2=H; R
3=n-C
16h
33; R
4=(SO
3 -)
n-R
6; M=16, n=3)
Under argon shield, add (the SO of 1.56mmol in the 50mLSchlenk bottle
3na)
3-R
6, [the n-C of 4.73mmol
16h
33(EO)
16n
+h=C (N (CH
3)
2)
2] [CH
3sO
3 -] and the 20mL acetonitrile, reaction mixture at room temperature stirs 72 hours, filters, and filtrate decompression is removed acetonitrile and is obtained orange-yellow thick liquid, yield 94%.
Embodiment 4
The ionic liquid 1:[R of phosphine functionalization
3(EO)
mn
+r
2=C (NR
1 2)
2]
n[R
4] synthetic (R
1=CH
3; R
2=n-C
6h
13; R
3=CH
3; R
4=(SO
3 -)
n-R
6; M=16, n=3)
Under argon shield, add (the SO of 1.56mmol in the 50mLSchlenk bottle
3na)
3-R
6, [the CH of 4.73mmol
3(EO)
16n
+(n-C
6h
13)=C (N (CH
3)
2)
2] [CH
3sO
3 -] and the 10mL acetonitrile, reaction mixture at room temperature stirs 72 hours, filters, and filtrate decompression is removed acetonitrile and is obtained orange-yellow thick liquid, yield 95%.
Embodiment 5
The ionic liquid 1:[R of phosphine functionalization
3(EO)
mn
+r
2=C (NR
1 2)
2]
n[R
4] synthetic (R
1=CH
3; R
2=C
6h
5cH
2; R
3=CH
3; R
4=(SO
3 -)
n-R
6; M=16, n=3)
Under argon shield, add (the SO of 1.56mmol in the 50mLSchlenk bottle
3na)
3-R
6, [the CH of 4.73mmol
3(EO)
16n
+(C
6h
5cH
2)=C (N (CH
3)
2)
2] [CH
3sO
3 -] and the 10mL acetonitrile, reaction mixture at room temperature stirs 72 hours, filters, and filtrate decompression is removed acetonitrile and is obtained orange-yellow thick liquid, yield 92%.
Embodiment 6
The ionic liquid 1:[R of phosphine functionalization
3(EO)
mn
+r
2=C (NR
1 2)
2]
n[R
4] synthetic (R
1=n-C
16h
33; R
2=H; R
3=CH
3; R
4=(SO
3 -)
n-R
6; M=16, n=3)
Under argon shield, add (the SO of 1.56mmol in the 50mLSchlenk bottle
3na)
3-R
6, [the CH of 4.73mmol
3(EO)
16n
+h=C (N (n-C
16h
33)
2)
2] [CH
3sO
3 -] and the 20mL acetonitrile, reaction mixture at room temperature stirs 72 hours, filters, and filtrate decompression is removed acetonitrile and is obtained orange-yellow thick liquid, yield 96%.
Embodiment 7
The ionic liquid 1:[R of phosphine functionalization
3(EO)
mn
+r
2=C (NR
1 2)
2]
n[R
4] synthetic (R
1=CH
3; R
2=H; R
3=CH
3; R
4=(SO
3 -)
n-R
6; M=4, n=3)
Under argon shield, add (the SO of 1.56mmol in the 50mLSchlenk bottle
3na)
3-R
6, [the CH of 4.73mmol
3(EO)
4n
+h=C (N (CH
3)
2)
2] [CH
3sO
3 -] and the 10mL acetonitrile, reaction mixture at room temperature stirs 72 hours, filters, and filtrate decompression is removed acetonitrile and is obtained orange-yellow thick liquid, yield 91%.
Embodiment 8
The ionic liquid 1:[R of phosphine functionalization
3(EO)
mn
+r
2=C (NR
1 2)
2]
n[R
4] synthetic (R
1=CH
3; R
2=H; R
3=CH
3; R
4=(SO
3 -)
n-R
6; M=42, n=3)
Under argon shield, add (the SO of 1.56mmol in the 50mLSchlenk bottle
3na)
3-R
6, [the CH of 4.73mmol
3(EO)
42n
+h=C (N (CH
3)
2)
2] [CH
3sO
3 -] and the 25mL acetonitrile, reaction mixture at room temperature stirs 72 hours, filters, and filtrate decompression is removed acetonitrile and is obtained orange-yellow thick liquid, yield 96%.
Embodiment 9
The ionic liquid 1:[R of phosphine functionalization
3(EO)
mn
+r
2=C (NR
1 2)
2]
n[R
4] synthetic (R
1=CH
3; R
2=H; R
3=CH
3; R
4=(SO
3 -)
n-R
7; M=16, n=4)
Under argon shield, add (the SO of 1.56mmol in the 50mLSchlenk bottle
3na)
4-R
7, [the CH of 6.30mmol
3(EO)
16n
+h=C (N (CH
3)
2)
2] [CH
3sO
3 -] and the 15mL acetonitrile, reaction mixture at room temperature stirs 72 hours, filters, and filtrate decompression is removed acetonitrile and is obtained orange-yellow thick liquid, yield 94%.
Embodiment 10
The ionic liquid 1:[R of phosphine functionalization
3(EO)
mn
+r
2=C (NR
1 2)
2]
n[R
4] synthetic (R
1=CH
3; R
2=H; R
3=CH
3; R
4=(SO
3 -)
n-R
8; M=16, n=4)
Under argon shield, add (the SO of 1.56mmol in the 50mLSchlenk bottle
3na)
4-R
8, [the CH of 6.30mmol
3(EO)
16n
+h=C (N (CH
3)
2)
2] [CH
3sO
3 -] and the 15mL acetonitrile, reaction mixture at room temperature stirs 72 hours, filters, and filtrate decompression is removed acetonitrile and is obtained orange-yellow thick liquid, yield 92%.
Embodiment 11
The ionic liquid 1:[R of phosphine functionalization
3(EO)
mn
+r
2=C (NR
1 2)
2]
n[R
4] synthetic (R
1=CH
3; R
2=H; R
3=CH
3; R
4=(SO
3 -)
n-R
9; M=16, n=4)
Under argon shield, add (the SO of 1.56mmol in the 50mLSchlenk bottle
3na)
4-R
9, [the CH of 6.30mmol
3(EO)
16n
+h=C (N (CH
3)
2)
2] [CH
3sO
3 -] and the 15mL acetonitrile, reaction mixture at room temperature stirs 72 hours, filters, and filtrate decompression is removed acetonitrile and is obtained orange-yellow thick liquid, yield 93%.
Embodiment 12
The ionic liquid 1:[R of phosphine functionalization
3(EO)
mn
+r
2=C (NR
1 2)
2]
n[R
4] synthetic (R
1=CH
3; R
2=H; R
3=CH
3; R
4=(SO
3 -)
n-R
10; M=16, n=4)
Under argon shield, add (the SO of 1.56mmol in the 50mLSchlenk bottle
3na)
4-R
10, [the CH of 6.30mmol
3(EO)
16n
+h=C (N (CH
3)
2)
2] [CH
3sO
3 -] and the 15mL acetonitrile, reaction mixture at room temperature stirs 72 hours, filters, and filtrate decompression is removed acetonitrile and is obtained orange-yellow thick liquid, yield 90%.
Embodiment 13
The ionic liquid 1:[R of phosphine functionalization
3(EO)
mn
+r
2=C (NR
1 2)
2]
n[R
4] synthetic (R
1=CH
3; R
2=H; R
3=CH
3; R
4=(SO
3 -)
n-R
11; M=16, n=2)
Under argon shield, add (the SO of 1.56mmol in the 50mLSchlenk bottle
3na)
2-R
11, [the CH of 3.20mmol
3(EO)
16n
+h=C (N (CH
3)
2)
2] [CH
3sO
3 -] and the 15mL acetonitrile, reaction mixture at room temperature stirs 72 hours, filters, and filtrate decompression is removed acetonitrile and is obtained orange-yellow thick liquid, yield 89%.
Embodiment 14
The ionic liquid 1:[R of phosphine functionalization
3(EO)
mn
+r
2=C (NR
1 2)
2]
n[R
4] synthetic (R
1=CH
3; R
2=H; R
3=CH
3; R
4=(SO
3 -)
n-R
12; M=16, n=4)
Under argon shield, add (the SO of 1.56mmol in the 50mLSchlenk bottle
3na)
4-R
12, [the CH of 6.30mmol
3(EO)
16n
+h=C (N (CH
3)
2)
2] [CH
3sO
3 -] and the 20mL acetonitrile, reaction mixture at room temperature stirs 72 hours, filters, and filtrate decompression is removed acetonitrile and is obtained orange-yellow thick liquid, yield 93%.
Embodiment 15
The ionic liquid 1:[R of phosphine functionalization
3(EO)
mn
+r
2=C (NR
1 2)
2]
n[R
4] synthetic (R
1=CH
3; R
2=H; R
3=CH
3; R
4=(SO
3 -)
n-R
13; M=16, n=2)
Under argon shield, add (the SO of 1.56mmol in the 50mLSchlenk bottle
3na)
2-R
13, [the CH of 3.20mmol
3(EO)
16n
+h=C (N (CH
3)
2)
2] [CH
3sO
3 -] and the 20mL acetonitrile, reaction mixture at room temperature stirs 72 hours, filters, and filtrate decompression is removed acetonitrile and is obtained orange-yellow thick liquid, yield 90%.
Embodiment 16
RhCl
33H
2o/[CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
61-hexene hydroformylation reaction under]/toluene system
Add RhCl in the stainless steel autoclave
33H
2o, [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
6], toluene and 1-hexene, its ratio is: [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
6]/RhCl
33H
2o=10:1 (mol ratio), 1-hexene/RhCl
33H
2o=1000:1 (mol ratio), toluene/1-hexene=3:1-5:1 (volume ratio), with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1:1) be forced into 5.0MPa, 85 ℃ of temperature of reaction, 2 hours reaction times, then be cooled to room temperature, after emptying, toluene, then underpressure distillation product aldehyde are removed in decompression.Gas chromatographic analysis, the transformation efficiency of 1-hexene is 96%, the selectivity 96% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 2.8:1, residual ionic liquid continues next catalytic cycle after adding new toluene and 1-hexene.
Embodiment 17
RhCl
33H
2o/[CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
61-octene hydroformylation reaction under]/toluene system
Add RhCl in the stainless steel autoclave
33H
2o, [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
6], toluene and 1-octene, its ratio is: [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
6]/RhCl
33H
2o=10:1 (mol ratio), 1-octene/RhCl
33H
2o=1000:1 (mol ratio), toluene/1-octene=3:1-5:1 (volume ratio), with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1:1) be forced into 5.0MPa, 85 ℃ of temperature of reaction, in 2 hours reaction times, then be cooled to room temperature, after emptying, toluene is removed in decompression, add the normal heptane extraction, separate upper strata product aldehyde phase, through gas chromatographic analysis, the transformation efficiency of 1-octene is 90%, the selectivity 95% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 2.7:1, lower floor's catalyzer continues next catalytic cycle after adding new toluene and 1-octene.
Embodiment 18
RhCl
33H
2o/[CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -) 3-R
61-decene hydroformylation reaction under]/toluene system
Add RhCl in the stainless steel autoclave
33H
2o, [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
6], toluene and 1-decene, its ratio is: [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
6]/RhCl
33H
2o=10:1 (mol ratio), 1-decene/RhCl
33H
2o=1000:1 (mol ratio), toluene/1-decene=3:1-5:1 (volume ratio), with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1:1) be forced into 5.0MPa, 85 ℃ of temperature of reaction, in 2 hours reaction times, then be cooled to room temperature, after emptying, toluene is removed in decompression, add the normal heptane extraction, separate upper strata product aldehyde phase, through gas chromatographic analysis, the transformation efficiency of 1-decene is 95%, the selectivity 96% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 2.6:1, lower floor's catalyzer continues next catalytic cycle after adding new toluene and 1-decene.
Embodiment 19
RhCl
33H
2o/[CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
61-laurylene hydroformylation reaction under]/toluene system
Add RhCl in the stainless steel autoclave
33H
2o, [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
6], toluene and 1-laurylene, its ratio is: [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
6]/RhCl
33H
2o=10:1 (mol ratio), 1-laurylene/RhCl
33H
2o=1000:1 (mol ratio), toluene/1-laurylene=3:1-5:1 (volume ratio), with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1:1) be forced into 5.0MPa, 85 ℃ of temperature of reaction, in 2 hours reaction times, then be cooled to room temperature, after emptying, toluene is removed in decompression, add the normal heptane extraction, separate upper strata product aldehyde phase, through gas chromatographic analysis, the transformation efficiency of 1-laurylene is 93%, the selectivity 94% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 2.6:1, lower floor's catalyzer continues next catalytic cycle after adding new toluene and 1-laurylene.
Embodiment 20
RhCl
33H
2o/[CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
61-tetradecylene hydroformylation reaction under]/toluene system
Add RhCl in the stainless steel autoclave
33H
2o, [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
6], toluene and 1-tetradecylene, its ratio is: [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
6]/RhCl
33H
2o=10:1 (mol ratio), 1-tetradecylene/RhCl
33H
2o=1000:1 (mol ratio), toluene/1-tetradecylene=3:1-5:1 (volume ratio), with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1:1) be forced into 5.0MPa, 85 ℃ of temperature of reaction, in 2 hours reaction times, then be cooled to room temperature, after emptying, toluene is removed in decompression, add the normal heptane extraction, separate upper strata product aldehyde phase, through gas chromatographic analysis, the transformation efficiency of 1-tetradecylene is 92%, the selectivity 93% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 2.5:1, lower floor's catalyzer continues next catalytic cycle after adding new toluene and 1-tetradecylene.
Embodiment 21
RhCl
33H
2o/[CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
6vinylbenzene hydroformylation reaction under]/toluene system
Add RhCl in the stainless steel autoclave
33H
2o, [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
6], toluene and vinylbenzene, its ratio is: [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
6]/RhCl
33H
2o=10:1 (mol ratio), vinylbenzene/RhCl
33H
2o=1000:1 (mol ratio), toluene/vinylbenzene=3:1-5:1 (volume ratio), with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1:1) be forced into 5.0MPa, 85 ℃ of temperature of reaction, in 2 hours reaction times, then be cooled to room temperature, after emptying, toluene is removed in decompression, add the normal heptane extraction, separate upper strata product aldehyde phase, through gas chromatographic analysis, cinnamic transformation efficiency is 98%, the selectivity 97% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 1:11, lower floor's catalyzer continues next catalytic cycle after adding new toluene and vinylbenzene.
Embodiment 22
Rh (acac) (CO)
2/ [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
61-octene hydroformylation reaction under]/methanol system
Add Rh (acac) (CO) in the stainless steel autoclave
2, [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
6], methyl alcohol and 1-octene, its ratio is: [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
3[(SO
3 -)
3-R
6]/Rh (acac) (CO)
2=10:1 (mol ratio), 1-octene/Rh (acac) (CO)
2=1000:1 (mol ratio), methyl alcohol/1-octene=3:1-5:1 (volume ratio), with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1:1) be forced into 5.0MPa, 85 ℃ of temperature of reaction, in 2 hours reaction times, then be cooled to room temperature, after emptying, methyl alcohol is removed in decompression, add the normal heptane extraction, separate upper strata product aldehyde phase, through gas chromatographic analysis, the transformation efficiency of 1-octene is 97%, the selectivity 97% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 2.8:1, lower floor's catalyzer continues next catalytic cycle after adding new methyl alcohol and 1-octene.
Embodiment 23
RhCl
33H
2o/[CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
2[(SO
3 -)
2-R
111-octene hydroformylation reaction under]/toluene system
Add RhCl in the stainless steel autoclave
33H
2o, [CH
3(EO)
16n+H=C (N (CH
3)
2)
2]
2[(SO
3 -)
2-R
11], toluene and 1-octene, its ratio is: [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
2[(SO
3 -)
2-R
11]/RhCl
33H
2o=10:1 (mol ratio), 1-octene/RhCl
33H
2o=1000:1 (mol ratio), toluene/1-octene=3:1-5:1 (volume ratio), with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1:1) be forced into 5.0MPa, 110 ℃ of temperature of reaction, in 2 hours reaction times, then be cooled to room temperature, after emptying, toluene is removed in decompression, add the normal heptane extraction, separate upper strata product aldehyde phase, through gas chromatographic analysis, the transformation efficiency of 1-octene is 96%, the selectivity 95% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 19:1, lower floor's catalyzer continues next catalytic cycle after adding new toluene and 1-octene.
Embodiment 24
RhCl
33H
2o/[CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
4[(SO
3 -)
4-R
121-octene hydroformylation reaction under]/toluene system
Add RhCl in the stainless steel autoclave
33H
2o, [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
4[(SO
3 -)
4-R
12], toluene and 1-octene, its ratio is: [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
4[(SO
3 -)
4-R
12]/RhCl
33H
2o=10:1 (mol ratio), 1-octene/RhCl
33H
2o=1000:1 (mol ratio), toluene/1-octene=3:1-5:1 (volume ratio), with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1:1) be forced into 5.0MPa, 110 ℃ of temperature of reaction, in 2 hours reaction times, then be cooled to room temperature, after emptying, toluene is removed in decompression, add the normal heptane extraction, separate upper strata product aldehyde phase, through gas chromatographic analysis, the transformation efficiency of 1-octene is 97%, the selectivity 96% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 21:1, lower floor's catalyzer continues next catalytic cycle after adding new toluene and 1-octene.
Embodiment 25
RhCl
33H
2o/[CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
2[(SO
3 -)
2-R
131-octene hydroformylation reaction under]/toluene system
Add RhCl in the stainless steel autoclave
33H
2o, [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
2[(SO
3 -)
2-R
13], toluene and 1-octene, its ratio is: [CH
3(EO)
16n
+h=C (N (CH
3)
2)
2]
2[(SO
3 -)
2-R
13]/RhCl
33H
2o=10:1 (mol ratio), 1-octene/RhCl
33H
2o=1000:1 (mol ratio), toluene/1-octene=3:1-5:1 (volume ratio), with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1:1) be forced into 5.0MPa, 110 ℃ of temperature of reaction, in 2 hours reaction times, then be cooled to room temperature, after emptying, toluene is removed in decompression, add the normal heptane extraction, separate upper strata product aldehyde phase, through gas chromatographic analysis, the transformation efficiency of 1-octene is 97%, the selectivity 95% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 25:1, lower floor's catalyzer continues next catalytic cycle after adding new toluene and 1-octene.
Claims (8)
1. the ionic liquid of a class phosphine functionalization, it is characterized in that: the positively charged ion of this class phosphine functionalized ion liquid is polyoxyalkylene alkyl guanidinesalt positively charged ion, and negatively charged ion is the Water-soluble Sulphonated phosphines negatively charged ion, and its structural formula is:
In formula: m=1-100; R
1for C
1-C
16normal chain alkyl; R
2for H, C
1-C
16normal chain alkyl or benzyl; R
3for C
1-C
16normal chain alkyl or phenyl; R
4mean the negatively charged ion of Water-soluble Sulphonated phosphines, n is the number of sulfonic group negatively charged ion on the phosphine part, n=1-8.
2. according to the ionic liquid of the phosphine functionalization of claim 1, it is characterized in that R
4be:
In formula: R
5for C
6h
5or C
6h
4-3-SO
3 -; R
6, R
7, R
8, R
9, R
10, R
11, R
12and R
13be respectively the parent fraction of different Water-soluble Sulphonated phosphines, n is the number of sulfonic group negatively charged ion on the phosphine part, n=1-8.
3. according to the ionic liquid of the phosphine functionalization of claim 1, it is characterized in that the synthetic method of ionic liquid 1 of described phosphine functionalization is as follows:
In formula: R
14for CH
3or p-CH
3-C
6h
4.
4. according to the synthetic method of the ionic liquid of the described phosphine functionalization of claim 3, it is characterized in that: the ionic liquid 1 of phosphine functionalization is by polyoxyalkylene alkyl guanidinium ionic liquid 2 and sodium sulfonate type water-soluble phosphine ligand [Na
+]
n[R
4]
n-at CH
3carry out prepared by ion exchange reaction in CN, temperature of reaction is 0-80 ℃, reaction times 8-72h.
5. according to the ionic liquid of the phosphine functionalization of claim 1; the ionic liquid 1 that it is characterized in that the phosphine functionalization can be applicable to hydroformylation; hydroesterification; hydrocarboxylation and catalytic hydrogenation, have for the metal with the described phosphine functionalized ion liquid formation of claim 1 transition metal complex catalysts: rhodium (Rh), ruthenium (Ru), iridium (Ir), palladium (Pd), platinum (Pt), osmium (Os), gold (Au) or cobalt (Co).
6. according to the ionic liquid of the phosphine functionalization of claim 1, it is characterized in that the ionic liquid 1 of phosphine functionalization can be applicable to the hydroformylation reaction of alkene, the alkene of use is C
3-C
16linear alpha-olefin, tetrahydrobenzene, vinylbenzene, p-methylstyrene, o-methyl styrene, p-tert-butylstyrene, p-isobutylstyrene, to methoxy styrene, to chloro-styrene, chloro styrene or 2-vinyl naphthalene, the transition metal complex catalysts precursor of employing is RhCl
33H
2o, Rh (acac) are (CO)
2(rhodium dicarbonyl acetylacetonate), [Rh (COD)
2] BF
4(COD:1,5-cyclooctadiene) or [Rh (COD) Cl]
2, transition metal complex catalysts is generated in-situ under the hydroformylation reaction condition by phosphine functionalized ion liquid 1 and transition metal complex catalysts precursor.
7. the hydroformylation reaction for alkene according to the ionic liquid of the phosphine functionalization of claim 6; it is characterized in that: phosphine functionalized ion liquid 1, transition metal complex catalysts precursor, alkene and organic solvent are added in the stainless steel autoclave; make 1 with the transition metal complex catalysts precursor in the mol ratio of rhodium be 1:1-50:1; in alkene and transition metal complex catalysts precursor, the mol ratio of rhodium is 100:1-10000:1; the volume ratio of organic solvent and alkene is 1:1-10:1; with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1:1) be forced into 1.0-7.0MPa, start stirring, temperature of reaction 70-130 ℃, reaction times 0.5-24 hour, then be cooled to room temperature, the emptying synthetic gas, organic solvent is removed in decompression, obtain product aldehyde for the direct underpressure distillation of alkene that is less than 8 containing carbon number, residual catalyst phase (comprising ionic liquid 1 and catalyzer) continues next catalytic cycle after adding new organic solvent and alkene; For containing carbon number, being more than or equal to 8 alkene, use C
6-C
8normal paraffin or petroleum ether extraction product aldehyde, obtain the upper strata product phase that contains product aldehyde through simply being separated, lower floor's catalyzer phase (comprising ionic liquid 1 and catalyzer) continues next catalytic cycle after adding new organic solvent and alkene; The single transformation efficiency of alkene is 90-99%, and the selectivity of aldehyde is 90-99%, and the mol ratio of n-alkanal and isomery aldehyde is 0.05:1-50:1.
8. the hydroformylation reaction for alkene according to the ionic liquid of the phosphine functionalization of claim 7, it is characterized in that: applied organic solvent is benzene, toluene, methyl alcohol, ethanol, acetonitrile, methylene dichloride or tetrahydrofuran (THF).
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