CN103304386B - Method for preparing acetal through alkene hydroformylation-acetalation one-pot method - Google Patents
Method for preparing acetal through alkene hydroformylation-acetalation one-pot method Download PDFInfo
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- CN103304386B CN103304386B CN201310243828.5A CN201310243828A CN103304386B CN 103304386 B CN103304386 B CN 103304386B CN 201310243828 A CN201310243828 A CN 201310243828A CN 103304386 B CN103304386 B CN 103304386B
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- rhodium
- acetal
- acetalation
- phenylglycine
- diphenyl phosphine
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 title claims abstract description 83
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000005580 one pot reaction Methods 0.000 title abstract 2
- 239000010948 rhodium Substances 0.000 claims abstract description 75
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 72
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000002608 ionic liquid Substances 0.000 claims abstract description 27
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 23
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 142
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 102
- 239000007789 gas Substances 0.000 claims description 70
- 229910052786 argon Inorganic materials 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 34
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 19
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical group [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 17
- 238000000605 extraction Methods 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 229910001220 stainless steel Inorganic materials 0.000 claims description 17
- 239000010935 stainless steel Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 230000009466 transformation Effects 0.000 claims description 15
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000006837 decompression Effects 0.000 claims description 12
- 230000001476 alcoholic effect Effects 0.000 claims description 8
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 6
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 4
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- RMLHVYNAGVXKKC-UHFFFAOYSA-N [SH2]=N.C(F)(F)F Chemical compound [SH2]=N.C(F)(F)F RMLHVYNAGVXKKC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture 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
- -1 1-methyl-3-butyl imidazole hexafluorophosphate Chemical compound 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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- 238000002360 preparation method Methods 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 230000001588 bifunctional effect Effects 0.000 abstract 3
- QLEODAVWZCDXJZ-UHFFFAOYSA-N 2-amino-2-(4-diphenylphosphanylphenyl)acetic acid Chemical compound C1=CC(C(C(O)=O)N)=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QLEODAVWZCDXJZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000012071 phase Substances 0.000 abstract 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 65
- 239000000243 solution Substances 0.000 description 28
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 27
- 150000001299 aldehydes Chemical class 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 11
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical class CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 7
- 230000003245 working effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 0 *C(*)c(cc1)ccc1P(c1ccccc1)c1ccccc1 Chemical compound *C(*)c(cc1)ccc1P(c1ccccc1)c1ccccc1 0.000 description 1
- 101100001670 Emericella variicolor andE gene Proteins 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000005451 methyl sulfates Chemical class 0.000 description 1
- 229950000081 metilsulfate Drugs 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing acetal through an alkene hydroformylation-acetalation one-pot method. A catalytic reaction system comprises a Bronsted acid-rhodium bifunctional catalyst, ionic liquid, alcohol and alkene, wherein the Bronsted acid-rhodium bifunctional catalyst is formed from an ammonium salt of 4-diphenylphosphino phenylglycine and a rhodium catalyst precursor. The catalysis system has high activity, high acetal selectivity and longer service life; an ionic liquid phase which contains the acid-rhodium bifunctional catalyst can be recycled for 10-20 times, and the catalytic activity and the acetal selectivity cannot be obviously reduced; and the rhodium lost in each circulation accounts for 0.01%-0.1% of the total amount of added rhodium.
Description
Technical field
The present invention relates to technical field of chemistry and chemical engineering, relate to the method that a kind of olefin hydroformylation-acetalation one kettle way prepares acetal particularly.
Background technology
The hydroformylation reaction of rhodium catalysis is the important method that industrial alkene functionalization produces aldehyde.Due to the activity of aldehyde radical, aldehyde can be further converted to other more valuable product.Based on the principle of the Atom economy in Green Chemistry and less energy-consumption; the hydroformylation reaction of alkene can realize cascade reaction with a lot of other organic reaction combination; such as; series connection hydroformylation-reduction reaction, hydroformylation-nucleophilic addition and hydroformylation-Aldol condensation reaction etc.; wherein, an important application is series connection hydroformylation-acetalation.The formation of acetal may be used for protecting responsive aldehyde radical or synthesizing various fine chemicals further, as spices, and medicine and agrochemicals etc.The series connection of multiple catalyzed reaction due to this One-step Synthesis process implementation, thus decrease the generation of by product, and avoid the abstraction and purification step of intermediate product.
Much to be in the news (O.Diebolt, C.Cruzeuil, C.M ü llerand D.Vogt, Adv.Synth.Catal., 2012,354,670 about the research of the series connection hydroformylation-acetalation of rhodium catalysis although have; C.G.Vieira, J.G.da Silva, C.A.A.Penna, E.N.dos Santos andE.V.Gusevskaya, Appl.Catal.A, 2010,380,125; B.El Ali, J.Tijani, M.Fettouhi, J.Mol.Catal.A, 2005,230,9; B.El Ali, J.Tijani and M.Fettouhi, Appl.Catal.A, 2006,303,213; E.Fern á ndez and S.Castill ó n, TetrahedronLett., 1994,35,2361; K.Soulantica, S.Sirol, S.
g.Pneumatikakis and Ph.Kalck; J.Organomet.Chem.; 1995; 498; C10), but the relevant work of major part is all conceived to the series connection catalyzer of hydroformylation-acetalation and the research of reaction kinetics, and for the noble metal catalyst received much concern in homogeneous catalysis separation and circulatory problems is rare relates to.Up to the present; the catalyst system reported all cannot realize the long-term circulation of rhodium catalyst; also neither one high reactivity, high acetal selectivity and having concurrently are in the news compared with the hydroformylation-acetalation catalyst system of long life, and its major cause is that the high efficiency separation of expensive rhodium catalyst and recycling problem are difficult to solve.
For the deficiencies in the prior art, prepared by ammonium salt and the rhodium catalyst precursor original position of the present invention's application 4-diphenyl phosphine phenylglycine
acid-rhodium dual-function catalyst, invented on this basis a class by
the catalyst system of acid-rhodium dual-function catalyst, ionic liquid, alcohol and alkene composition; the object of the invention is, in order to invent a class, there is high reactivity and high acetal selectivity, having the method preparing acetal compared with the olefin hydroformylation-acetalation one kettle way of long life simultaneously concurrently.
Summary of the invention
The invention provides the method that a kind of olefin hydroformylation-acetalation one kettle way prepares acetal, catalystic converter system is formed by the ammonium salt of 4-diphenyl phosphine phenylglycine (1) and rhodium catalyst precursor
acid-rhodium dual-function catalyst, ionic liquid, alcohol and alkene composition.
Wherein, the chemical structural formula of the ammonium salt of 4-diphenyl phosphine phenylglycine is:
In formula: X
-for BF
4 -, PF
6 -, Tf
2n
-, CH
3sO
3 -, CF
3sO
3 -or tosic acid root negatively charged ion.
Wherein, 0 rhodium catalyst precursor is Rh (acac) (CO)
2(rhodium dicarbonyl acetylacetonate), RhCl
33H
2o, [Rh (COD)
2] BF
4(COD:1,5-cyclooctadiene) or [Rh (COD) Cl]
2.
acid-rhodium dual-function catalyst is formed with rhodium catalyst precursor original position under hydroformylation-acetalation condition by the ammonium salt ([1H] X) of 4-diphenyl phosphine phenylglycine.
The ionic liquid used is 1-methyl-3-butyl imidazole a tetrafluoro borate ([bmim] BF
4), 1-methyl-3-butyl imidazole hexafluorophosphate ([bmim] PF
6) or two fluoroform sulfimide salt ([bmim] Tf of 1-methyl-3-butyl imidazole
2n).
The alcohol used is methyl alcohol, ethanol, n-propyl alcohol, Virahol, ethylene glycol, 1,2-PD or 1,3-PD.
The alkene used is C
6-C
14linear alpha-olefin, vinylbenzene, p-methylstyrene, o-methyl styrene, p-tert-butylstyrene, to methoxy styrene, to chloro-styrene, chloro styrene or 2-vinyl naphthalene.
The method that olefin hydroformylation-acetalation one kettle way prepares acetal is: under argon gas or nitrogen atmosphere, 4-diphenyl phosphine phenylglycine is dissolved in methyl alcohol, ethanol, n-propyl alcohol or Virahol, then adds HBF
4, HPF
6, Tf
2nH, CH
3sO
3h, CF
3sO
3h or tosic acid, the mol ratio of alcohol and 4-diphenyl phosphine phenylglycine is 1000: 1-10000: 1, acid is 1: 1-2: 1 with the mol ratio of 4-diphenyl phosphine phenylglycine, 0.5-3 hour is stirred at 20-60 DEG C, the alcoholic solution of the 4-diphenyl phosphine phenylglycine ammonium salt ([1H] X) obtained can be directly used in olefin hydroformylation-acetalation, specific as follows: under argon gas or nitrogen atmosphere, by the alcoholic solution of above-mentioned [1H] X, ionic liquid, alkene and rhodium catalyst precursor add in stainless steel autoclave, the mol ratio making rhodium in 1 and rhodium catalyst precursor is 3: 1-100: 1, the mass ratio of ionic liquid and rhodium catalyst precursor is 100: 1-2000: 1, in alkene and rhodium catalyst precursor, the mol ratio of rhodium is 100: 1-10000: 1, with nitrogen or argon replaces air 4-6 time, then synthetic gas (H is used
2/ CO=1: 1) be forced into 1.0-7.0MPa, at 70-130 DEG C of reaction 1-10 hour, be then quickly cooled to room temperature, after emptying synthetic gas, decompression removing alcohol, uses C
6-C
8alkane extraction product, the water that acetalation generates under reduced pressure removes, and contains
the ionic liquid of acid-rhodium dual-function catalyst continues next catalytic cycle after adding new alcohol and alkene, the single transformation rate of alkene is 60-100%, and overall selectivity (aldehyde adds acetal) is 80-99%, and the selectivity of acetal is 90-99%, and the mol ratio of positive structure acetal and isomery acetal is 5: 95-85: 15, contain
the ionic liquid of acid-rhodium dual-function catalyst can be recycled 10-20 time mutually, and the rhodium that each circulation is run off is the 0.01-0.1% of the total rhodium amount dropped into.
The method that olefin hydroformylation-acetalation one kettle way prepares acetal is: under argon gas or nitrogen atmosphere, 4-diphenyl phosphine phenylglycine is dissolved in ethylene glycol, 1,2-PD or 1,3-PD, then adds HBF
4, HPF
6, Tf
2nH, CH
3sO
3h, CF
3sO
3h or tosic acid, the mol ratio of alcohol and 4-diphenyl phosphine phenylglycine is 100: 1-1000: 1, acid is 1: 1-2: 1 with the mol ratio of 4-diphenyl phosphine phenylglycine, 0.5-3 hour is stirred at 20-60 DEG C, the alcoholic solution of the 4-diphenyl phosphine phenylglycine ammonium salt ([1H] X) obtained can be directly used in olefin hydroformylation-acetalation, specific as follows: under argon gas or nitrogen atmosphere, by the alcoholic solution of above-mentioned [1H] X, ionic liquid, alkene and rhodium catalyst precursor add in stainless steel autoclave, the mol ratio making rhodium in 1 and rhodium catalyst precursor is 3: 1-100: 1, the mass ratio of ionic liquid and rhodium catalyst precursor is 100: 1-2000: 1, in alkene and rhodium catalyst precursor, the mol ratio of rhodium is 100: 1-10000: 1, with nitrogen or argon replaces air 4-6 time, then synthetic gas (H is used
2/ CO=1: 1) be forced into 1.0-7.0MPa, at 70-130 DEG C of reaction 1-10 hour, be then quickly cooled to room temperature, after emptying synthetic gas, use C
6-C
8alkane extraction product, the water that acetalation generates under reduced pressure removes, and contains
the ionic liquid of acid-rhodium dual-function catalyst continues next catalytic cycle after the dibasic alcohol adding reaction consumption and alkene, the single transformation rate of alkene is 50-100%, and overall selectivity (aldehyde adds acetal) is 80-99%, and the selectivity of acetal is 80-99%, and the mol ratio of positive structure acetal and isomery acetal is 5: 95-85: 15, contain
the ionic liquid of acid-rhodium dual-function catalyst can be recycled 10-20 time mutually, and the rhodium that each circulation is run off is the 0.01-0.1% of the total rhodium amount dropped into.
Embodiment
Embodiment 1
Rh-[1H] BF
4/ [bmim] BF
41-octene series connection hydroformylation-acetalation under/methanol system
Under argon gas or nitrogen atmosphere, by 4-diphenyl phosphine phenylglycine (3.87 × 10
-2mmol) be dissolved in 3mL methyl alcohol, then add equimolar HBF
4(40% aqueous solution), stirs 1 hour at 50 DEG C, 4-diphenyl phosphine phenylglycine a tetrafluoro borate ([1H] BF obtained
4) methanol solution can be directly used in the series connection hydroformylation-acetalation of 1-octene, specific as follows: under argon gas or nitrogen atmosphere, by above-mentioned [1H] BF
4methanol solution, [bmim] BF
4(1.0g), 1-octene (0.6mL, 3.82mmol) and Rh (acac) (CO)
2(1.0mg, 3.87 × 10
-3mmol) add in stainless steel autoclave, with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1: 1) be forced into 5.0MPa, 80 DEG C of reactions 2 hours, be then quickly cooled to room temperature, decompression removing methyl alcohol after emptying synthetic gas, use normal heptane extraction product, the water that acetalation generates under reduced pressure removes.The transformation efficiency of 1-octene is 99%, and overall selectivity (aldehyde adds acetal) is 97%, and the selectivity of acetal is 95%, and the mol ratio of positive structure acetal and isomery acetal is 75: 25.
Embodiment 2
Rh-[1H] PF
6/ [bmim] PF
61-octene series connection hydroformylation-acetalation under/methanol system
Under argon gas or nitrogen atmosphere, by 4-diphenyl phosphine phenylglycine (3.87 × 10
-2mmol) be dissolved in 3mL methyl alcohol, then add equimolar HPF
6(60% aqueous solution), stirs 1 hour at 50 DEG C, 4-diphenyl phosphine phenylglycine hexafluorophosphate ([1H] PF obtained
6) methanol solution can be directly used in the series connection hydroformylation-acetalation of 1-octene, specific as follows: under argon gas or nitrogen atmosphere, by above-mentioned [1H] PF
6methanol solution [bmim] PF
6(1.0g), 1-octene (0.6mL, 3.82mmol) and Rh (acac) (CO)
2(1.0mg, 3.87 × 10
-3mmol) add in stainless steel autoclave, with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1: 1) be forced into 5.0MPa, 80 DEG C of reactions 2 hours, be then quickly cooled to room temperature, decompression removing methyl alcohol after emptying synthetic gas, use normal heptane extraction product, the water that acetalation generates under reduced pressure removes.The transformation efficiency of 1-octene is 94%, and overall selectivity (aldehyde adds acetal) is 99%, and the selectivity of acetal is 95%, and the mol ratio of positive structure acetal and isomery acetal is 77: 23.
Embodiment 3
Rh-[1H] Tf
2n/ [bmim] Tf
21-octene series connection hydroformylation-acetalation under N/ methanol system
Under argon gas or nitrogen atmosphere, by 4-diphenyl phosphine phenylglycine (3.87 × 10
-2mmol) be dissolved in 3mL methyl alcohol, then add equimolar Tf
2nH, stirs 1 hour at 50 DEG C, two fluoroform sulfimide salt ([1H] Tf of the 4-diphenyl phosphine phenylglycine obtained
2n) methanol solution can be directly used in the series connection hydroformylation-acetalation of 1-octene, specific as follows: under argon gas or nitrogen atmosphere, by above-mentioned [1H] Tf
2the methanol solution of N, [bmim] Tf
2n (1.0g), 1-octene (0.6mL, 3.82mmol) and Rh (acac) (CO)
2(1.0mg, 3.87 × 10
-3mmol) add in stainless steel autoclave, with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1: 1) be forced into 5.0MPa, 80 DEG C of reactions 2 hours, be then quickly cooled to room temperature, decompression removing methyl alcohol after emptying synthetic gas, use normal heptane extraction product, the water that acetalation generates under reduced pressure removes.The transformation efficiency of 1-octene is 99%, and overall selectivity (aldehyde adds acetal) is 98%, and the selectivity of acetal is 92%, and the mol ratio of positive structure acetal and isomery acetal is 77: 23.
Embodiment 4
Rh-[1H] SO
3cH
3/ [bmim] BF
41-octene series connection hydroformylation-acetalation under/methanol system
Under argon gas or nitrogen atmosphere, by 4-diphenyl phosphine phenylglycine (3.87 × 10
-2mmol) be dissolved in 3mL methyl alcohol, then add equimolar CH
3sO
3h, stirs 1 hour at 50 DEG C, 4-diphenyl phosphine phenylglycine metilsulfate ([1H] SO obtained
3cH
3) methanol solution can be directly used in the series connection hydroformylation-acetalation of 1-octene, specific as follows: under argon gas or nitrogen atmosphere, by above-mentioned [1H] SO
3cH
3methanol solution, [bmim] BF
4(1.0g), 1-octene (0.6mL, 3.82mmol) and Rh (acac) (CO)
2(1.0mg, 3.87 × 10
-3mmol) add in stainless steel autoclave, with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1: 1) be forced into 5.0MPa, 80 DEG C of reactions 2 hours, be then quickly cooled to room temperature, decompression removing methyl alcohol after emptying synthetic gas, use normal heptane extraction product, the water that acetalation generates under reduced pressure removes.The transformation efficiency of 1-octene is 98%, and overall selectivity (aldehyde adds acetal) is 98%, and the selectivity of acetal is 94%, and the mol ratio of positive structure acetal and isomery acetal is 76: 24.
Embodiment 5
Rh-[1H] BF
4/ [bmim] BF
41-octene series connection hydroformylation-acetalation under/ethanol system
Under argon gas or nitrogen atmosphere, by 4-diphenyl phosphine phenylglycine (3.87 × 10
-2mmol) be dissolved in 5mL ethanol, then add equimolar HBF
4(40% aqueous solution), stirs 1 hour at 50 DEG C, 4-diphenyl phosphine phenylglycine a tetrafluoro borate ([1H] BF obtained
4) ethanolic soln can be directly used in the series connection hydroformylation-acetalation of 1-octene, specific as follows: under argon gas or nitrogen atmosphere, by above-mentioned [1H] BF
4ethanolic soln, [bmim] BF
4(1.0g), 1-octene (0.6mL, 3.82mmol) and Rh (acac) (CO)
2(1.0mg, 3.87 × 10
-3mmol) add in stainless steel autoclave, with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1: 1) be forced into 5.0MPa, 80 DEG C of reactions 2 hours, be then quickly cooled to room temperature, decompression removing ethanol after emptying synthetic gas, use normal heptane extraction product, the water that acetalation generates under reduced pressure removes.The transformation efficiency of 1-octene is 98%, and overall selectivity (aldehyde adds acetal) is 84%, and the selectivity of acetal is 91%, and the mol ratio of positive structure acetal and isomery acetal is 74: 26.
Embodiment 6
Rh-[1H] BF
4/ [bmim] BF
41-octene series connection hydroformylation-acetalation under/glycol system
Under argon gas or nitrogen atmosphere, by 4-diphenyl phosphine phenylglycine (3.87 × 10
-2mmol) be dissolved in 0.5mL ethylene glycol, then add equimolar HBF
4(40% aqueous solution), stirs 1 hour at 50 DEG C, 4-diphenyl phosphine phenylglycine a tetrafluoro borate ([1H] BF obtained
4) ethylene glycol solution can be directly used in the series connection hydroformylation-acetalation of 1-octene, specific as follows: under argon gas or nitrogen atmosphere, by above-mentioned [1H] BF
4ethylene glycol solution, [bmim] BF
4(1.0g), 1-octene (0.6mL, 3.82mmol) and Rh (acac) (CO)
2(1.0mg, 3.87 × 10
-3mmol) add in stainless steel autoclave, with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1: 1) 5.0MPa is forced into, 80 DEG C of reactions 2 hours, then room temperature is quickly cooled to, normal heptane extraction product is used after emptying synthetic gas, the water that acetalation generates under reduced pressure removes, and the transformation efficiency of 1-octene is 99%, and overall selectivity (aldehyde adds acetal) is 94%, the selectivity of acetal is 96%, and the mol ratio of positive structure acetal and isomery acetal is 76: 24.
Embodiment 7
Rh-[1H] BF
4/ [bmim] BF
41-octene series connection hydroformylation-acetalation under/1,2-PD system
Under argon gas or nitrogen atmosphere, by 4-diphenyl phosphine phenylglycine (3.87 × 10
-2mmol) be dissolved in the 1,2-PD of 0.5mL, then add equimolar HBF
4(40% aqueous solution), stirs 1 hour at 50 DEG C, 4-diphenyl phosphine phenylglycine a tetrafluoro borate ([1H] BF obtained
4) 1,2-PD solution can be directly used in the series connection hydroformylation-acetalation of 1-octene, specific as follows: under argon gas or nitrogen atmosphere, by above-mentioned [1H] BF
41,2-PD solution, [bmim] BF
4(1.0g), 1-octene (0.6mL, 3.82mmol) and Rh (acac) (CO)
2(1.0mg, 3.87 × 10
-3mmol) add in stainless steel autoclave, with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1: 1) 5.0MPa is forced into, 80 DEG C of reactions 2 hours, then room temperature is quickly cooled to, normal heptane extraction product is used after emptying synthetic gas, the water that acetalation generates under reduced pressure removes, and the transformation efficiency of 1-octene is 99%, and overall selectivity (aldehyde adds acetal) is 97%, the selectivity of acetal is 99%, and the mol ratio of positive structure acetal and isomery acetal is 77: 23.
Embodiment 8
Rh-[1H] BF
4/ [bmim] BF
41-decene series connection hydroformylation-acetalation under/methanol system
Under argon gas or nitrogen atmosphere, by 4-diphenyl phosphine phenylglycine (3.87 × 10
-2mmol) be dissolved in 6mL methyl alcohol, then add equimolar HBF
4(40% aqueous solution), stirs 1 hour at 50 DEG C, 4-diphenyl phosphine phenylglycine a tetrafluoro borate ([1H] BF obtained
4) methanol solution can be directly used in the series connection hydroformylation-acetalation of 1-decene, specific as follows: under argon gas or nitrogen atmosphere, by above-mentioned [1H] BF
4methanol solution, [bmim] BF
4(1.0g), 1-decene (3.80mmol) and Rh (acac) (CO)
2(1.0mg, 3.87 × 10
-3mmol) add in stainless steel autoclave, with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1: 1) be forced into 5.0MPa, 80 DEG C of reactions 2 hours, be then quickly cooled to room temperature, decompression removing methyl alcohol after emptying synthetic gas, use normal heptane extraction product, the water that acetalation generates under reduced pressure removes.The transformation efficiency of 1-decene is 99%, and overall selectivity (aldehyde adds acetal) is 90%, and the selectivity of acetal is 93%, and the mol ratio of positive structure acetal and isomery acetal is 70: 30.
Embodiment 9
Rh-[1H] BF
4/ [bmim] BF
41-laurylene series connection hydroformylation-acetalation under/methanol system
Under argon gas or nitrogen atmosphere, by 4-diphenyl phosphine phenylglycine (3.87 × 10
-2mmol) be dissolved in 11mL methyl alcohol, then add equimolar HBF
4(40% aqueous solution), stirs 1 hour at 50 DEG C, 4-diphenyl phosphine phenylglycine a tetrafluoro borate ([1H] BF obtained
4) methanol solution can be directly used in the series connection hydroformylation-acetalation of 1-laurylene, specific as follows: under argon gas or nitrogen atmosphere, by above-mentioned [1H] BF
4methanol solution, [bmim] BF
4(1.0g), 1-laurylene (3.83mmol) and Rh (acac) (CO)
2(1.0mg, 3.87 × 10
-3mmol) add in stainless steel autoclave, with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1: 1) be forced into 5.0MPa, 80 DEG C of reactions 2 hours, be then quickly cooled to room temperature, decompression removing methyl alcohol after emptying synthetic gas, use normal heptane extraction product, the water that acetalation generates under reduced pressure removes.The transformation efficiency of 1-laurylene is 99%, and overall selectivity (aldehyde adds acetal) is 88%, and the selectivity of acetal is 91%, and the mol ratio of positive structure acetal and isomery acetal is 70: 30.
Embodiment 10
Rh-[1H] BF
4/ [bmim] BF
4vinylbenzene series connection hydroformylation-acetalation under/methanol system
Under argon gas or nitrogen atmosphere, by 4-diphenyl phosphine phenylglycine (3.87 × 10
-2mmol) be dissolved in 3mL methyl alcohol, then add equimolar HBF
4(40% aqueous solution), stirs 1 hour at 50 DEG C, 4-diphenyl phosphine phenylglycine a tetrafluoro borate ([1H] BF obtained
4) methanol solution can be directly used in cinnamic series connection hydroformylation-acetalation, specific as follows: under argon gas or nitrogen atmosphere, by above-mentioned [1H] BF
4methanol solution, [bnim] BF
4(1.0g), vinylbenzene (3.93mmol) and Rh (acac) (CO)
2(1.0mg, 3.87 × 10
-3mmol) add in stainless steel autoclave, with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1: 1) be forced into 5.0MPa, 80 DEG C of reactions 2 hours, be then quickly cooled to room temperature, decompression removing methyl alcohol after emptying synthetic gas, use normal heptane extraction product, the water that acetalation generates under reduced pressure removes.Cinnamic transformation efficiency is 100%, and overall selectivity (aldehyde adds acetal) is 99%, and the selectivity of acetal is 99%, and the mol ratio of positive structure acetal and isomery acetal is 8: 92.
Embodiment 11
Rh-[1H] BF
4/ [bmim] BF
42-vinyl naphthalene series connection hydroformylation-acetalation under/methanol system
Under argon gas or nitrogen atmosphere, by 4-diphenyl phosphine phenylglycine (3.87 × 10
-2mmol) be dissolved in 10mL methyl alcohol, then add equimolar HBF
4(40% aqueous solution), stirs 1 hour at 50 DEG C, 4-diphenyl phosphine phenylglycine a tetrafluoro borate ([1H] BF obtained
4) methanol solution can be directly used in the series connection hydroformylation-acetalation of 2-vinyl naphthalene, specific as follows: under argon gas or nitrogen atmosphere, by above-mentioned [1H] BF
4methanol solution, [bmim] BF
4(1.0g), 2-vinyl naphthalene (3.89mmol) and Rh (acac) (CO)
2(1.0mg, 3.87 × 10
-3mmol) add in stainless steel autoclave, with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1: 1) be forced into 5.0MPa, 80 DEG C of reactions 2 hours, be then quickly cooled to room temperature, decompression removing methyl alcohol after emptying synthetic gas, use normal heptane extraction product, the water that acetalation generates under reduced pressure removes.The transformation efficiency of 2-vinyl naphthalene is 63%, and overall selectivity (aldehyde adds acetal) is 99%, and the selectivity of acetal is 95%, and the mol ratio of positive structure acetal and isomery acetal is 8: 92.
Embodiment 12
Rh-[1H] BF
4/ [bmim] BF
4under/methanol system, 1-octene series connection hydroformylation-acetalation catalyzer is investigated work-ing life
Under argon gas or nitrogen atmosphere, by 4-diphenyl phosphine phenylglycine (3.87 × 10
-2mmol) be dissolved in 3mL methyl alcohol, then add equimolar HBF
4(40% aqueous solution), stirs 1 hour at 50 DEG C, 4-diphenyl phosphine phenylglycine a tetrafluoro borate ([1H] BF obtained
4) methanol solution can be directly used in the series connection hydroformylation-acetalation of 1-octene, specific as follows: under argon gas or nitrogen atmosphere, by above-mentioned [1H] BF
4methanol solution, [bmim] BF
4(1.0g), 1-octene (0.6mL, 3.82mmol) and Rh (acac) (CO)
2(1.0mg, 3.87 × 10
-3mmol) add in stainless steel autoclave, with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1: 1) be forced into 5.0MPa, 80 DEG C of reactions 2 hours, be then quickly cooled to room temperature, decompression removing methyl alcohol after emptying synthetic gas, use normal heptane extraction product, the water that acetalation generates under reduced pressure removes.Contain
the ionic liquid of acid-rhodium dual-function catalyst continues next catalytic cycle after adding new methyl alcohol and 1-octene.Contain
the ionic liquid of acid-rhodium dual-function catalyst can be recycled 12 times mutually, and the rhodium that each circulation is run off is the 0.03-0.06% of the total rhodium amount dropped into, and the results are shown in Table 1.
Table 1Rh-[1H] BF
4/ [bmim] BF
4under/methanol system, 1-octene series connection hydroformylation-acetalation catalyzer is investigated work-ing life
aconverted olefin accounts for the per-cent dropping into total olefin;
bgenerate aldehyde and the acetal overall selectivity based on converted olefin;
cgenerate selectivity=(n-alkanal+2-methyl aldehyde)/(n-alkanal+2-methyl aldehyde+positive structure acetal+2-methyl acetal) of acetal
dthe mol ratio of positive structure acetal and isomery acetal;
ethe loss of Rh accounts for the per-cent dropping into total rhodium, adopts ICP-AES to analyze.
Embodiment 13
Rh-[1H] BF
4/ [bmim] BF
4under/1,2-PD system, 1-octene series connection hydroformylation-acetalation catalyzer is investigated work-ing life
Under argon gas or nitrogen atmosphere, by 4-diphenyl phosphine phenylglycine (3.87 × 10
-2mmol) be dissolved in the 1,2-PD of 0.5mL, then add equimolar HBF
4(40% aqueous solution), stirs 1 hour at 50 DEG C, 4-diphenyl phosphine phenylglycine a tetrafluoro borate ([1H] BF obtained
4) 1,2-PD solution can be directly used in the series connection hydroformylation-acetalation of 1-octene, specific as follows: under argon gas or nitrogen atmosphere, by above-mentioned [1H] BF
41,2-PD solution, [bmim] BF
4(1.0g), 1-octene (0.6mL, 3.82mmol) and Rh (acac) (CO)
2(1.0mg, 3.87 × 10
-3mmol) add in stainless steel autoclave, with nitrogen or argon replaces air 4-6 time, then use synthetic gas (H
2/ CO=1: 1) be forced into 5.0MPa, 80 DEG C of reactions 2 hours, be then quickly cooled to room temperature, use normal heptane extraction product after emptying synthetic gas, the water that acetalation generates under reduced pressure removes.Contain
the ionic liquid of acid-rhodium dual-function catalyst continues next catalytic cycle after the 1,2-PD adding consumption and 1-octene.Contain
the ionic liquid of acid-rhodium dual-function catalyst can be recycled 18 times mutually, and the rhodium that each circulation is run off is the 0.07-0.1% of the total rhodium amount dropped into, and the results are shown in Table 2.
Table 2Rh-[1H] BF
4/ [bmim] BF
4under/1,2-PD system, 1-octene series connection hydroformylation-acetalation catalyzer is investigated work-ing life
Claims (6)
1. olefin hydroformylation-acetalation one kettle way prepares a method for acetal, it is characterized in that: catalystic converter system be by
acid-rhodium dual-function catalyst, ionic liquid, alcohol and alkene composition,
acid-rhodium dual-function catalyst has simultaneously
acid catalysis center and rhodium catalysis center; it is prepared by ammonium salt [1H] X of 4-diphenyl phosphine phenylglycine 1 and rhodium catalyst precursor original position under hydroformylation-acetalation condition; wherein; the preparation method one of ammonium salt [1H] X of 4-diphenyl phosphine phenylglycine 1 is under argon gas or nitrogen atmosphere; 4-diphenyl phosphine phenylglycine is dissolved in methyl alcohol, ethanol, n-propyl alcohol or Virahol, then adds HBF
4, HPF
6, Tf
2nH, CH
3sO
3h, CF
3sO
3h or tosic acid, the mol ratio of alcohol and 4-diphenyl phosphine phenylglycine is 1000:1-10000:1, acid is 1:1-2:1 with the mol ratio of 4-diphenyl phosphine phenylglycine, stir 0.5-3 hour at 20-60 DEG C, the alcoholic solution of 4-diphenyl phosphine phenylglycine ammonium salt [1H] X obtained is directly used in olefin hydroformylation-acetalation; The preparation method two of ammonium salt [1H] X of 4-diphenyl phosphine phenylglycine 1 is under argon gas or nitrogen atmosphere, is dissolved in ethylene glycol, 1,2-PD or 1,3-PD by 4-diphenyl phosphine phenylglycine, then adds HBF
4, HPF
6, Tf
2nH, CH
3sO
3h, CF
3sO
3h or tosic acid, the mol ratio of alcohol and 4-diphenyl phosphine phenylglycine is 100:1-1000:1, acid is 1:1-2:1 with the mol ratio of 4-diphenyl phosphine phenylglycine, stir 0.5-3 hour at 20-60 DEG C, the alcoholic solution of 4-diphenyl phosphine phenylglycine ammonium salt [1H] X obtained is directly used in olefin hydroformylation-acetalation; The chemical structural formula of ammonium salt [1H] X of 4-diphenyl phosphine phenylglycine 1 is as follows:
In formula: X
-for BF
4 -, PF
6 -, Tf
2n
-, CH
3sO
3 -, CF
3sO
3 -or tosic acid root negatively charged ion.
2. prepare the method for acetal according to the olefin hydroformylation-acetalation one kettle way of claim 1, it is characterized in that rhodium catalyst precursor is Rh (acac) (CO)
2(rhodium dicarbonyl acetylacetonate), RhCl
33H
2o, [Rh (COD)
2] BF
4(COD:1,5-cyclooctadiene) or [Rh (COD) Cl]
2.
3. prepare the method for acetal according to the olefin hydroformylation-acetalation one kettle way of claim 1, it is characterized in that the ionic liquid used is 1-methyl-3-butyl imidazole a tetrafluoro borate ([bmim] BF
4), 1-methyl-3-butyl imidazole hexafluorophosphate ([bmim] PF
6) or two fluoroform sulfimide salt ([bmim] Tf of 1-methyl-3-butyl imidazole
2n).
4. prepare the method for acetal according to the olefin hydroformylation-acetalation one kettle way of claim 1, it is characterized in that the alkene used is C
6-C
14linear alpha-olefin, vinylbenzene, p-methylstyrene, o-methyl styrene, p-tert-butylstyrene, to methoxy styrene, to chloro-styrene, chloro styrene or 2-vinyl naphthalene.
5. the method for acetal is prepared according to the olefin hydroformylation-acetalation one kettle way of claim 1, it is characterized in that: under argon gas or nitrogen atmosphere, by the alcoholic solution of [1H] X prepared according to method in claim 1 one, ionic liquid, alkene and rhodium catalyst precursor add in stainless steel autoclave, the mol ratio making rhodium in 1 and rhodium catalyst precursor is 3:1-100:1, the mass ratio of ionic liquid and rhodium catalyst precursor is 100:1-2000:1, in alkene and rhodium catalyst precursor, the mol ratio of rhodium is 100:1-10000:1, with nitrogen or argon replaces air 4-6 time, then 1.0-7.0MPa is forced into synthetic gas, the ratio of synthetic gas is H
2/ CO=1:1, at 70-130 DEG C of reaction 1-10 hour, is then quickly cooled to room temperature, and after emptying synthetic gas, decompression removing alcohol, uses C
6-C
8alkane extraction product, the water that acetalation generates under reduced pressure removes, and contains
the ionic liquid of acid-rhodium dual-function catalyst continues next catalytic cycle after adding new alcohol and alkene, the single transformation rate of alkene is 60-100%, and the overall selectivity that aldehyde adds acetal is 80-99%, and the selectivity of acetal is 90-99%, and the mol ratio of positive structure acetal and isomery acetal is 5:95-85:15, contain
the ionic liquid of acid-rhodium dual-function catalyst can be recycled 10-20 time mutually, and the rhodium that each circulation is run off is the 0.01-0.1% of the total rhodium amount dropped into.
6. the method for acetal is prepared according to the olefin hydroformylation-acetalation one kettle way of claim 1, it is characterized in that: under argon gas or nitrogen atmosphere, by the alcoholic solution of [1H] X prepared according to method two in claim 1, ionic liquid, alkene and rhodium catalyst precursor add in stainless steel autoclave, the mol ratio making rhodium in 1 and rhodium catalyst precursor is 3:1-100:1, the mass ratio of ionic liquid and rhodium catalyst precursor is 100:1-2000:1, in alkene and rhodium catalyst precursor, the mol ratio of rhodium is 100:1-10000:1, with nitrogen or argon replaces air 4-6 time, then 1.0-7.0MPa is forced into synthetic gas, the ratio of synthetic gas is H
2/ CO=1:1, at 70-130 DEG C of reaction 1-10 hour, is then quickly cooled to room temperature, uses C after emptying synthetic gas
6-C
8alkane extraction product, the water that acetalation generates under reduced pressure removes, and contains
the ionic liquid of acid-rhodium dual-function catalyst continues next catalytic cycle after the dibasic alcohol adding reaction consumption and alkene, the single transformation rate of alkene is 50-100%, and the overall selectivity that aldehyde adds acetal is 80-99%, and the selectivity of acetal is 80-99%, and the mol ratio of positive structure acetal and isomery acetal is 5:95-85:15, contain
the ionic liquid of acid-rhodium dual-function catalyst can be recycled 10-20 time mutually, and the rhodium that each circulation is run off is the 0.01-0.1% of the total rhodium amount dropped into.
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