CN101955419B - Method for selective catalytic hydrogenation for 9,9-bi(methoxymethylated) fluorine (BMMF) - Google Patents
Method for selective catalytic hydrogenation for 9,9-bi(methoxymethylated) fluorine (BMMF) Download PDFInfo
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- CN101955419B CN101955419B CN2010101439978A CN201010143997A CN101955419B CN 101955419 B CN101955419 B CN 101955419B CN 2010101439978 A CN2010101439978 A CN 2010101439978A CN 201010143997 A CN201010143997 A CN 201010143997A CN 101955419 B CN101955419 B CN 101955419B
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Abstract
The invention relates to a method for selective catalytic hydrogenation for 9,9-bi(methoxymethylated) fluorine (BMMF), which comprises the following steps: adding BMMF, solvent and a modified skeleton nickel catalyst in an autoclave, wherein the mass ratio of the solvent to the BMMF is 1:1-10:1, the dosage of the modified skeleton nickel catalyst is 1-20wt% of that of the BMMF; replacing air after closing the autoclave; then introducing a certain amount of hydrogen; putting the autoclave into oil bath, and heating slowly to the reaction temperature, wherein the reaction temperature is 100-250DEG C; and adjusting a hydrogen valve so as to enable the system pressure to be 0.5-4.0MPa and keeping for 0.5-5h, wherein the selectivity of cis-H6BMMF can be up to 98%. The method has the characteristics of simple operation, good repeatability, high product stereoselectivity and the like.
Description
Technical field
The invention belongs to the Application Areas of shortening, is a kind of 9, the method for 9-bis-(methoxymethyl) fluorenes (BMMF) selective catalytic hydrogenation.The method can make the cis-1,2,3,4 of highly-solid selectively, 4a, 9a-hexahydro--9,9-bis-(methoxymethyl) fluorenes (cis-H
6bMMF).
Background technology
Since Natta in 1954 finds to use TiCl
4, TiCl
3/ AlR
3or AlR
2since Cl can prepare high isotatic polypropylene, Ziegler-Natta catalyst has obtained significant progress, and the efficiency of catalyzer is more and more higher, and preparation technology is also more and more consummate.The Ziegler-Natta catalyst of new generation that the diether compound of usining synthesizes as electron donor, in the situation that, without additional electron donor, can obtain the polypropylene of highly active catalyzer and high isotactic.Owing to not needing external electron donor in polymerization process, reduced the complicacy of reaction system, be conducive to study active sites and polymerization mechanism, and the high reactivity of catalyzer and the high isotactic that obtains polymkeric substance are very valuable in application, therefore the research as the diether compounds of this class catalyzer electron donor has caused that people pay attention to widely.
9,9-bis-(methoxymethyl) fluorenes (BMMF) is the Typical Representative of two ethers electron donors, make the Ziegler-Natta catalyst of electron donor with it, in the situation that do not add external electron donor, the catalyzing propone polymerization obtains the polymkeric substance of high isotactic, and catalyzer has high reactivity and highly-solid selectively.EP0728724 has reported the synthetic method of 9,9-bis-(methoxymethyl) fluorenes.Under the protection of N2 gas, adopt tetrahydrofuran (THF) to make solvent, 9,9-bis-(methylol) fluorenes and iodomethane reaction are generated to 9,9-bis-(methoxymethyl) fluorenes, reaction is to carry out under the existence of highly basic NaH, needs strict water-less environment.And severe reaction conditions, synthetic cost is high, and the industrialization difficulty is large.
Li Jiahui etc. have studied under the effect of phase-transfer catalyst 4-n-butyl ammonium hydrogen sulfate, 9, add methyl-sulfate and toluene mixture in the system that 9-bis-(methylol) fluorenes, 50%NaOH solution and toluene exist, fully reaction obtains product by separation, distillation, recrystallization.Utilize the method for this phase-transfer catalysis to obtain 9,9-bis-(methoxymethyl) fluorenes yield is more than 80%.It is easy and simple to handle that the phase-transfer catalysis etherificate prepares diether compounds, raw materials used cheap, is a kind of method of being convenient to suitability for industrialized production.
High wise the grade studied with 1, the performance of the catalyst for polymerization of propylene that the 3-diether is internal electron donor, obtain having the catalyzer that is internal electron donor with 9,9-bis-(methoxymethyl) fluorenes of different orientation property by different methods, and carried out application test.Test-results shows, can make the polymkeric substance of the relative molecular mass narrow distribution with different degree of isotacticity by diether catalyst, the activity of diether catalyst is high, can reach 230kg/g, for the 2-4 of existing commercial catalysts doubly, hydrogen response, also higher than existing commercial catalysts, has been saved the consumption of catalyzer.
Woods spring flower etc. be take industrial fluorenes as raw material, has synthesized 9 through the formaldehyde hydroxymethylation, 9-bis-(methylol) fluorenes, take NaH as catalyzer again, with CH3I, alkylated reaction occurring has obtained target product 9,9-bis-(methoxymethyl) fluorenes, yield reaches more than 80%.Product application is worth high, and synthesis technique is simple, is suitable for exploitation and the application of fine chemistry industry enterprise to this type of diether compounds, has wide prospects for commercial application.
Chinese patent CN1336359 has related to the technique of synthetic 9,9-bis-(methoxymethyl) fluorenes of a kind of three-phase phase-transfer catalytic.This technique is after fluorenes and formaldehyde are carried out to methylolation in dimethyl sulfoxide (DMSO), sodium ethylate, through component distillation, recovery extraction agent, filtration, recrystallization, make 9,9-bis-(methylol) fluorenes, again by it in solvent, phase-transfer catalyst and alkali lye, drip methyl-sulfate and methylated, through washing, component distillation, solvent recuperation, filtration, recrystallization, drying, make high purity 9,9-bis-(methoxymethyl) fluorenes.This technique has that reaction conditions mitigation, intermediate product and the finished product are easily separated, cost is low, pollute the characteristics such as little.
Xu Zhaohui etc. have studied under the effect of Tetrabutyl amonium bromide phase-transfer catalyst, take toluene as solvent, 9,9-bis-(methylol) fluorenes, NaOH, methylcarbonate are raw material, synthesized novel electron donor 9 by alkylated reaction, 9-bis-(methoxymethyl) fluorenes, under the condition of optimizing, the yield of target product reaches 69.1%, and purity is 99.3%.This reaction conditions gentleness, be easy to industrial production.
Xiong Bin etc. have reported 9, the synthetic method of 9-bis-(methoxymethyl) fluorenes, the method is carried out in two steps: at first, under the effect of sodium ethylate catalyzer, fluorenes and polyformaldehyde reaction have synthesized intermediate 9, and 9-bis-(methylol) fluorenes, then take Tetrabutyl amonium bromide as phase-transfer catalyst, synthesized 9,9-bis-(methoxymethyl) fluorenes with methyl chloride generation alkylated reaction again.
At present, as 9 of the internal electron donor of Ziegler-Natta catalyst, 9-bis-(methoxymethyl) fluorenes has dropped into industrial production.But for its high-selective and hydrogenating product cis-1,2,3,4,4a, 9a-hexahydro--9,9-bis-(methoxymethyl) (cis-H
6bMMF) fluorenes there is not yet the research report.
Summary of the invention
Purpose of the present invention just is to provide a kind of novel method of simple and easy, repeatability is good, the product stereoselectivity the is high standby novel diether compound of Hydrogenation.
Technical solution of the present invention is: a kind of 9, the method of 9-bis-(methoxymethyl) fluorenes (BMMF) selective catalytic hydrogenation, the method is that modified skeletal nickel catalyst is prepared to cis-1 for the BMMF selective hydrogenation, 2,3,4,4a, 9a-hexahydro--9,9-bis-(methoxymethyl) fluorenes (cis-H
6bMMF).Its method steps is:
Add BMMF, solvent, modified skeletal nickel catalyst in autoclave, the mass ratio of solvent and BMMF is 1: 1-10: 1, the 1-20wt% that the modified skeletal nickel catalyst consumption is BMMF, airtight rear substitution air, then be filled with a certain amount of hydrogen, put into oil bath and slowly be heated to temperature of reaction, temperature of reaction is 100-250 ℃, adjusts hydrogen valve, makes system pressure reach 0.5-4.0MPa, then hold-time 0.5-5h, cis-H
6the selectivity of BMMF can be up to 98%.
Described modified skeletal nickel catalyst, its presoma is comprised of Primary Catalysts and promotor, and Primary Catalysts is nickel, and promotor is comprised of Al and M, and integral body is expressed as NiAlM, and wherein component M is one or more the mixture in Fe, Mn, Mo or Cr; The weight percent of the pressed powder of Ni, Al, M is Ni:30-60%, Al:30-70%, M:0-10%, and catalyst precursor launches according to a conventional method.In temperature of reaction, be 100-150 ℃, under the condition that reaction pressure is 1.0-3.5MPa, reaction effect is better.The present invention's solvent used is one or more the mixture in glycol dimethyl ether, dioxane, normal hexane, hexanaphthene, methylene dichloride, tetrahydrofuran (THF), ether, methyl ethyl ether, methyl-formiate, ethyl formate, ethyl acetate or methyl acetate.
The presoma alloy of skeletal nickel catalyst is used quench technique to make: a certain proportion of Ni, Al and appropriate interpolation component M are heated to melting, and after its fusing forms uniform alloy, the bronze drum by melt by high speed rotating, make alloy with approximately 10
6ks
-1speed carry out cooling, thereby obtain thin of quenching alloy.Then become 200-300 purpose fine particle with ball mill grinding, obtain the quenching powdered alloy.
Skeletal nickel catalyst presoma alloy NiAlM activation method: powdered alloy is slowly joined in the aqueous solution of excessive w (NaOH)=20%, the while vigorous stirring, and continue reaction 1h under 100 ℃.After activation finishes, with deoxidation deionized water repetitive scrubbing, to neutral, obtain modified skeletal nickel catalyst.
The invention has the beneficial effects as follows, use the method for skeleton nickel catalyzed hydrogenation to synthesize a kind of novel diether compound, for exploitation, make new advances, efficiently Ziegler-Natta catalyst electron donor new approach is provided, use modified raney ni catalysis 9,9-bis-(methoxymethyl) fluorenes (BMMF) hydrogenation, obtain the cis-1,2 of highly-solid selectively, 3,4,4a, 9a-hexahydro--9,9-bis-(methoxymethyl) fluorenes (cis-H
6bMMF), selectivity is up to 98%.That the method has is simple to operate, repeatability good, product stereoselectivity high.
The accompanying drawing explanation
Fig. 1 and Fig. 2 are product cis-1,2,3,4,4a, 9a-hexahydro--9,9-bis-(methoxymethyl) fluorenes (cis-H
6bMMF) single crystal structure figure.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated,
Embodiment 1
Put into 2.03 gram BMMF in the autoclave that is 75 milliliters at volume, 20 milliliters of hexanaphthenes, the modified skeletal nickel catalyst after 0.25 gram activation, closed reactor, nitrogen replacement 3 times, hydrogen exchange 3 times, then be filled with the hydrogen of 0.5MPa, put into oil bath and slowly be heated to 120 ℃, adjust hydrogen valve, make system pressure reach 2.0MPa, reaction 320min, cooling rear employing gas-chromatography is analyzed, and feed stock conversion is 100%, product cis-H
6the selectivity of BMMF is 96.6%.
Embodiment 2
Put into 2.03 gram BMMF in the autoclave that is 75 milliliters at volume, 20 milliliters of tetrahydrofuran (THF)s, the modified skeletal nickel catalyst after 0.25 gram activation, closed reactor, nitrogen replacement 3 times, hydrogen exchange 3 times, then be filled with the hydrogen of 0.5MPa, put into oil bath and slowly be heated to 140 ℃, adjust hydrogen valve, make system pressure reach 2.0MPa, reaction 30min, cooling rear employing gas-chromatography is analyzed, and feed stock conversion is 100%, product cis-H
6the selectivity of BMMF is 96.1%.
Embodiment 3
Put into 2.03 gram BMMF in the autoclave that is 75 milliliters at volume, 20 ml n-hexanes, the modified skeletal nickel catalyst after 0.25 gram activation, closed reactor, nitrogen replacement 3 times, hydrogen exchange 3 times, then be filled with the hydrogen of 0.5MPa, put into oil bath and slowly be heated to 130 ℃, adjust hydrogen valve, make system pressure reach 2.0MPa, reaction 60min, cooling rear employing gas-chromatography is analyzed, and feed stock conversion is 100%, product cis-H
6the selectivity of BMMF is 96.2%.
Embodiment 4
Put into 2.03 gram BMMF in the autoclave that is 75 milliliters at volume, 20 milliliters of Isosorbide-5-Nitrae-dioxane, 0.25 the modified skeletal nickel catalyst after the gram activation, closed reactor, nitrogen replacement 3 times, hydrogen exchange 3 times, then be filled with the hydrogen of 0.5MPa, puts into oil bath and slowly be heated to 130 ℃, adjust hydrogen valve, make system pressure reach 1.0MPa, reaction 85min, cooling rear employing gas-chromatography is analyzed, feed stock conversion is 100%, product cis-H
6the selectivity of BMMF is 96.7%.
Embodiment 5
Put into 2.54 gram BMMF in the autoclave that is 75 milliliters at volume, 20 milliliters of hexanaphthenes, the modified skeletal nickel catalyst after 0.25 gram activation, closed reactor, nitrogen replacement 3 times, hydrogen exchange 3 times, then be filled with the hydrogen of 0.5MPa, put into oil bath and slowly be heated to 130 ℃, adjust hydrogen valve, make system pressure reach 1.5MPa, reaction 60min, cooling rear employing gas-chromatography is analyzed, and feed stock conversion is 99.2%, product cis-H
6the selectivity of BMMF is 97.5%.
Embodiment 6
Put into 20 gram BMMF in the autoclave that is 500 milliliters at volume, 250 milliliters of hexanaphthenes, the modified skeletal nickel catalyst after 1.78 gram activation, closed reactor, nitrogen replacement 3 times, hydrogen exchange 3 times, then be filled with the hydrogen of 0.5MPa, slowly be heated to 120 ℃, adjust hydrogen valve, make system pressure reach 1.5MPa, reaction 180min, cooling rear employing gas-chromatography is analyzed, and feed stock conversion is 100%, product cis-H
6the selectivity of BMMF is 98.0%.
Claims (4)
1. one kind 9, the method of 9-bis-(methoxymethyl) fluorenes (BMMF) selective catalytic hydrogenation, it is characterized in that, the method is that modified skeletal nickel catalyst is prepared to cis-1,2,3 for the BMMF selective hydrogenation, 4,4a, 9a-hexahydro--9,9-bis-(methoxymethyl) fluorenes (cis-H
6bMMF), its method steps is:
Add BMMF, solvent, modified skeletal nickel catalyst in autoclave, the mass ratio of solvent and BMMF is 1: 1-10: 1, the 1-20wt% that the modified skeletal nickel catalyst consumption is BMMF, airtight rear substitution air, then be filled with a certain amount of hydrogen, puts into oil bath and slowly be heated to temperature of reaction, temperature of reaction is 50-250 ℃, adjust hydrogen valve, make system pressure reach 0.5-4.0MPa, then hold-time 0.5-5h;
Wherein, modified skeletal nickel catalyst, its presoma is comprised of Primary Catalysts and promotor, and Primary Catalysts is nickel, and promotor is comprised of Al and M, and integral body is expressed as NiAlM, and wherein component M is one or more the mixture in Fe, Mn, Mo or Cr; The weight percent of the pressed powder of Ni, Al, M is Ni:30-60%, Al:30-70%, M:0-10%, and catalyst precursor launches according to a conventional method.
2. according to claim 1 a kind of 9, the method for 9-bis-(methoxymethyl) fluorenes (BMMF) selective catalytic hydrogenation is characterized in that described temperature of reaction is 100-150 ℃.
3. according to claim 1 a kind of 9, the method for 9-bis-(methoxymethyl) fluorenes (BMMF) selective catalytic hydrogenation is characterized in that described reaction pressure is 1.0-3.5MPa.
4. according to claim 1 a kind of 9, the method of 9-bis-(methoxymethyl) fluorenes (BMMF) selective catalytic hydrogenation, it is characterized in that, described solvent is one or more the mixture in glycol dimethyl ether, dioxane, normal hexane, hexanaphthene, methylene dichloride, tetrahydrofuran (THF), ether, methyl ethyl ether, methyl-formiate, ethyl formate, ethyl acetate or methyl acetate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4971937A (en) * | 1988-09-30 | 1990-11-20 | Himont Incorporated | Components and catalysts for the polymerization of olefins |
| EP0728724A1 (en) * | 1995-02-21 | 1996-08-28 | Montell North America Inc. | Diethers suitable for use in the preparation of Ziegler-Natta catalysts |
| CN101560273A (en) * | 2009-04-24 | 2009-10-21 | 营口市向阳催化剂有限责任公司 | Olefinic polymerization catalyst, preparation method and polymerization method |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4971937A (en) * | 1988-09-30 | 1990-11-20 | Himont Incorporated | Components and catalysts for the polymerization of olefins |
| EP0728724A1 (en) * | 1995-02-21 | 1996-08-28 | Montell North America Inc. | Diethers suitable for use in the preparation of Ziegler-Natta catalysts |
| CN101560273A (en) * | 2009-04-24 | 2009-10-21 | 营口市向阳催化剂有限责任公司 | Olefinic polymerization catalyst, preparation method and polymerization method |
Non-Patent Citations (2)
| Title |
|---|
| 丙烯聚合Z-N催化剂中的给电子体及其作用机理;徐宏彬等;《合成树脂及塑料》;20041231;第21卷(第2期);第75-78页 * |
| 徐宏彬等.丙烯聚合Z-N催化剂中的给电子体及其作用机理.《合成树脂及塑料》.2004,第21卷(第2期),第75-78页. |
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