CN105268486A - Ethylidene diacetate catalyst and application thereof - Google Patents
Ethylidene diacetate catalyst and application thereof Download PDFInfo
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- CN105268486A CN105268486A CN201410329022.2A CN201410329022A CN105268486A CN 105268486 A CN105268486 A CN 105268486A CN 201410329022 A CN201410329022 A CN 201410329022A CN 105268486 A CN105268486 A CN 105268486A
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Abstract
The invention relates to an ethylidene diacetate catalyst and application thereof. The catalyst mainly overcomes the problems of low activity and selectivity of ethylidene diacetate catalysts in the prior art. The ethylidene diacetate catalyst provided by the invention comprises a main catalyst and a cocatalyst, wherein the main catalyst comprises a supporter and an active component, the active component is a compound of rhodium, the cocatalyst is an iodide, and the supporter is a polymer which is at least one selected from the group consisting of self-crosslinked poly(N-vinyl pyrrolidone), poly(styrene-maleic anhydride), ammonified poly(styrene-maleic anhydride) and a benzylamine anion resin polymer. The ethylidene diacetate catalyst provided by the invention perfectly overcomes the above-mentioned problems and can be used for industrial production of vinyl acetate.
Description
Technical field
The present invention relates to ethylidene diacetate catalyst, preparation method and application.
Background technology
Vinyl acetate (VAc) is one of maximum 50 kinds of industrial chemicals of world wide production, by autohemagglutination or with other monomer copolymerization, polyvinyl alcohol (PVA), polyvinyl acetate (PVAc) emulsion, vinyl acetate-ethylene copolymerization emulsions (VAE) or the derivative such as copolymer resins (EVA), vinyl acetate-chloride copolymer (EVC) can be generated.These derivatives are widely used in cementing agent, coating, ink, leather processing, fiber process, emulsifying agent, the aspect such as water-solubility membrane and soil conditioner of adhesive, building coating, paper or fabric.
Ethene vapor phase method and acetylene in gas phase method technique is all adopted inside and outside the producing country of vinyl acetate, belong to petrochemical process route, after C1 chemistry rises, the eighties in 20th century, U.S. Ha Erkang (Halcon) company and BP (BP) company successively propose the new technology-carbonyl process synthesizing vinyl acetate being prepared vinyl acetate by methyl alcohol and synthesis gas.This technique does not rely on petrochemical materials, but by the carbonylation of methyl acetate and synthesis gas, synthetic intermediate ethylidene diacetate (EDDA), then produce vinyl acetate and acetic acid through thermal cracking.The novel part of whole technique is the hydroformylation reaction of methyl acetate, and catalyst radium chloride also uses beta-picoline and iodomethane modification, and carbon monoxide intercalation reaction is the key point of whole technology.
By the preparation method of methyl acetate synthesis ethylidene diacetate by US4,429,150 (title for: Manufactureofethylidenediacetate), namely with methyl acetate or methyl ether, carbon monoxide and hydrogen for raw material, catalyst synthesizes ethylidene diacetate under adopting VIII halide or acetate and phosphorous polar solvent to exist.US5,354,886 (title is: Catalystsoninorganiccarriersforproducingethylidenediacet ate) are mentioned RhCl
3or rhodium compound load makes loaded catalyst on diatomite, titanium oxide, magnesia, aluminium oxide and zinc oxide.With methyl acetate, carbon monoxide and hydrogen for raw material, under polar solvent conditions, Reactive Synthesis ethylidene diacetate under above-mentioned catalyst.All there is the low and selective not high problem of ethylidene diacetate yield preparing in ethylidene diacetate process in said method.
Summary of the invention
One of technical problem to be solved by this invention is the low and selective low problem of ethylidene diacetate yield, and provide a kind of new ethylidene diacetate catalyst, it is high to the selective high feature of ethylidene diacetate that this catalyst has ethylidene diacetate yield.
Two of technical problem to be solved by this invention is the preparation methods adopting one of above-mentioned technical problem described catalyst.
Three of technical problem to be solved by this invention is the synthetic methods of the ethylidene diacetate adopting one of above-mentioned technical problem described catalyst.
In order to one of solve the problems of the technologies described above, the technical solution used in the present invention is as follows: ethylidene diacetate catalyst, and described catalyst comprises major catalyst and co-catalyst, and described major catalyst comprises carrier, active component; Described activity group adopts the compound of rhodium; Described co-catalyst is iodide; Described carrier is polymer; Described polymer is selected from least one in crosslinked poly-(NVP) (being called for short PNVP), crosslinked poly-(phenylethylene-maleic anhydride) (being called for short PMAn), crosslinked ammonification poly-(phenylethylene-maleic anhydride) (being called for short APMAn) and crosslinked benzylamine negative resin polymer; Described polymer is preferably through oxidation processes.
The compound of rhodium described in technique scheme is preferably RhCl
3.Described iodide are preferably iodomethane.The degree of cross linking of described polymer is preferably 1 ~ 60%.
For solve the problems of the technologies described above two, technical scheme of the present invention is as follows: major catalyst preparation method described in the technical scheme of one of above-mentioned technical problem, comprises the steps:
1. described polymer support is carried out oxidation processes, drying obtains oxidation processes carrier;
2. the composition of catalyst is pressed by RhCl
3compound is mixed with aqueous impregnation on described oxidation processes carrier;
3. standing, dry, obtain described major catalyst.
The baking temperature that in technique scheme, step is 1. and 3. described independently preferably 80 ~ 120 DEG C.Be more preferably 100 ~ 120 DEG C.
The preparation key of catalyst of the present invention is the preparation of major catalyst, after obtaining major catalyst, to contact can obtain catalyst of the present invention by making major catalyst with described co-catalyst.The mode that major catalyst contacts with co-catalyst is not particularly limited, and is also not particularly limited the opportunity of contact making both.Both such as can be made before catalyst of the present invention is used for chemical reaction contact to form described catalyst, and in the reaction system that both can also be made to apply at catalyst of the present invention, contact makes catalyst in-situ preparation.
Another key of the present invention has carried out oxidation processes to polymer, at least one in the preferred hydrogen peroxide of oxidant of oxidation processes, nitric acid, hypochlorous acid, chloric acid and perchloric acid.More preferably hydrogen peroxide and perchloric acid hybrid oxidant.
The present inventor finds, in technique scheme, the catalyst that the APMAn of hydrogen peroxide and perchloric acid hybrid oxidant oxidation processes and benzylamine negative resin polymer support obtain is used by activity component impregnation no matter to be selective at the same time or EDDA yield all reaches best.
For solve the problems of the technologies described above three, technical scheme of the present invention is as follows: the synthetic method of ethylidene diacetate, with methyl acetate, carbon monoxide and hydrogen for raw material, take acetic acid as solvent, in the presence of a catalyst reaction generate ethylidene diacetate.
Key of the present invention is the selection of catalyst, those skilled in the art will know that the proportioning determining suitable reaction temperature, reaction time, reaction pressure and material how according to actual needs.But the temperature of reacting in technique scheme is preferably 130 ~ 200 DEG C; The pressure of reaction is preferably 3.0 ~ 10.0MPa; The time of reaction is preferably 3.0 ~ 10.0h.The mol ratio of carbon monoxide and hydrogen is preferably 0.1 ~ 10.0.
Product of the present invention through cooling, decompression, be separated after adopt gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) to analyze, by the following conversion ratio of formulae discovery methyl acetate and the yield of ethylidene diacetate and selective:
Compared with prior art, key of the present invention is that the carrier of catalyst employs oxidation processes post-consumer polymer, is conducive to improving the activity of major catalyst and stability, thus improves the yield of ethylidene diacetate and selective.
Experimental result shows, the ethylidene diacetate yield prepared by the present invention reaches 61.04%, selectively reaches 84.81%, and adopts that the prior art ethylidene diacetate of diatomite or silica is selective only has 79.38% on year-on-year basis; Achieve good technique effect.Especially catalyst carrier use hydrogen peroxide and perchloric acid hybrid oxidant to APMAn and benzylamine negative resin polymer carry out oxidation processes work in coordination with time, achieve more outstanding technique effect, can be used in the industrial production of vinyl acetate.Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
The preparation of polymer support: according to Shang Yuanyan etc. (Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiaoling. the preparation [J] of monodisperse porous St/DVB copolymerization microsphere. Journal of Functional Polymers, 2005,18, the preparation method of polymer 7-11.) mentioned, the preparation process of benzylamine negative resin is as follows:
First be that the PVA aqueous solution of 0.5wt% adds in the there-necked flask of 500ml capacity by 250ml concentration, in aqueous phase, add the NaCl of aqueous phase quality 2%, be warming up to 50 DEG C.Get 13ml styrene (St) and mix with 7ml divinylbenzene (DVB) that to be made into the degree of cross linking be 35% monomer phase, benzoyl peroxide (BPO) initator adding amount of monomer 0.5% (mass fraction) makes it fully to dissolve the solidifying conjunction that occurs to suspend and is obtained by reacting polystyrene kind ball.After the activation of kind of ball warp, swelling drying and ClCH
2oCH
3, (CH
3)
2after NH reaction, obtain polymer support precursor I through removal of impurities, washing, drying.
Be that 5wt% aqueous hydrogen peroxide solution mixes by polymer support precursor I and the concentration of double weight, carry out oxidation processes 4h, oxidizing temperature keeps 35 DEG C, obtains benzylamine negative resin carrier 100 DEG C of dryings.
The preparation of major catalyst: by the RhCl containing 7.50gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is fully mixed by 1.0L benzylamine negative resin carrier with above-mentioned maceration extract, leaves standstill the 30 DEG C of dryings of 3h vacuum, obtains described major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The Rh content of this catalyst is 7.36g/L after measured.The yield of ethylidene diacetate is 61.04% as calculated, selective is 84.81%, for convenience of explanation and compare, by the yield of the preparation condition of polymer support preparation and oxidation processes condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[comparative example 1]
For the comparative example of [embodiment 1].
The preparation of major catalyst: by the RhCl containing 7.50gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, by 1.0L diameter be the spherical sio2 carrier impregnation of 5.6mm in above-mentioned maceration extract, leave standstill 3h in 30 DEG C of dryings, obtain described major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The Rh content of this catalyst is 7.37g/L after measured.The yield of ethylidene diacetate is 50.83% as calculated, selective is 79.47%, for convenience of explanation and compare, by the yield of the preparation condition of polymer support preparation and oxidation processes condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[comparative example 2]
For the comparative example of [embodiment 1].
The preparation of polymer support: according to Shang Yuanyan etc. (Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiaoling. the preparation [J] of monodisperse porous St/DVB copolymerization microsphere. Journal of Functional Polymers, 2005,18, the preparation method of polymer 7-11.) mentioned, the preparation process of benzylamine negative resin is as follows:
First be that the PVA aqueous solution of 0.5wt% adds in the there-necked flask of 500ml capacity by 250ml concentration, in aqueous phase, add the NaCl of aqueous phase quality 2%, be warming up to 50 DEG C.Get 13ml styrene (St) and mix with 7ml divinylbenzene (DVB) that to be made into the degree of cross linking be 35% monomer phase, benzoyl peroxide (BPO) initator adding amount of monomer 0.5% (mass fraction) makes it fully to dissolve the solidifying conjunction that occurs to suspend and is obtained by reacting polystyrene kind ball.After the activation of kind of ball warp, swelling drying and ClCH
2oCH
3, (CH3)
2after NH reaction, obtain polymer support precursor I through removal of impurities, washing, drying.
The preparation of major catalyst: be dissolved in pure water by the RhCl33H2O containing 7.50gRh, obtain maceration extract 500ml, 1.0L polymer support precursor I fully mixed with above-mentioned maceration extract, leaves standstill the 30 DEG C of dryings of 3h vacuum, obtains described major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The Rh content of this catalyst is 7.37g/L after measured.The yield of ethylidene diacetate is 53.73% as calculated, selective is 80.21%, for convenience of explanation and compare, by the yield of the preparation condition of polymer support preparation and oxidation processes condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[comparative example 3]
For the comparative example of [embodiment 1].
The preparation of carrier: be the spherical SiO of 5.6mm by 1.0L diameter
2be that 5wt% aqueous hydrogen peroxide solution mixes with the concentration of double weight, carry out oxidation processes 4h, oxidizing temperature keeps 35 DEG C, the carrier after 100 DEG C of dryings obtain oxidation processes.
The preparation of major catalyst: by the RhCl containing 7.50gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, by SiO after 1.0L oxidation processes
2carrier fully mixes with maceration extract, leaves standstill 3h in 30 DEG C of dryings, obtains described major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol catalyst, 0.02mol iodomethane and 0.15mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The Rh content of this catalyst is 7.37g/L after measured.The yield of ethylidene diacetate is 50.92% as calculated, selective is 79.38%, for convenience of explanation and compare, by the yield of the preparation condition of polymer support preparation and oxidation processes condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
By finding out compared with embodiment 1, the catalyst carrier that the present invention adopts, oxidant is used to use conventional silica supports to the Performance Ratio of polymer support oxidation processes rear catalyst, than the carrier only using the process of polymer support not oxidised, more excellent than the performance of the catalyst only made with the carrier of oxidant to Normal silica, selective and the yield of ethylidene diacetate all wants high, this is from embodiment 1, the data of comparative example 1 ~ 3 can be found out, the polymer support described after using oxidizing process has better peptizaiton to catalyst activity component.
[embodiment 2]
The preparation of polymer support: according to Shang Yuanyan etc. (Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiaoling. the preparation [J] of monodisperse porous St/DVB copolymerization microsphere. Journal of Functional Polymers, 2005,18,7-11.) preparation method of polymer that mentions, PNVP preparation process is as follows:
First be that the PVA aqueous solution of 0.5wt% adds in the there-necked flask of 500ml capacity by 250ml concentration, in aqueous phase, add the NaCl of aqueous phase quality 2%, be warming up to 50 DEG C.Get 13ml vinylpyrrolidone (PVP) and mix with 7ml divinylbenzene (DVB) that to be made into the degree of cross linking be 35% monomer phase, azodiisobutyronitrile (AIBN) initator adding amount of monomer 0.5% (mass fraction) makes it fully to dissolve to occur to suspend to coagulate and closes reaction, obtains polymer support precursor I through removal of impurities, washing, drying.
Be that 5wt% aqueous hydrogen peroxide solution mixes by polymer support precursor I and the concentration of double weight, carry out oxidation processes 4h, oxidizing temperature keeps 35 DEG C, obtains PNVP polymer support 100 DEG C of dryings.
The preparation of major catalyst: by the RhCl containing 7.50gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is fully mixed by 1.0LPNVP polymer support with above-mentioned maceration extract, leaves standstill the 30 DEG C of dryings of 3h vacuum, obtains described major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol catalyst, 0.02mol iodomethane and 0.15mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The Rh content of this catalyst is 7.36g/L after measured.The yield of ethylidene diacetate is 61.25% as calculated, selective is 84.79%, for convenience of explanation and compare, by the yield of the preparation condition of polymer support preparation and oxidation processes condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 3]
The preparation of polymer support: according to Shang Yuanyan etc. (Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiaoling. the preparation [J] of monodisperse porous St/DVB copolymerization microsphere. Journal of Functional Polymers, 2005,18,7-11.) preparation method of polymer that mentions, PMAn preparation process is as follows:
First be that the PVA aqueous solution of 0.5wt% adds in the there-necked flask of 500ml capacity by 250ml concentration, in aqueous phase, add the NaCl of aqueous phase quality 2%, be warming up to 50 DEG C.Get 13ml styrene (St) and mix with 7ml divinylbenzene (DVB) that to be made into the degree of cross linking be 35% monomer phase, again to above-mentioned monomer mutually in add 2.35g maleic anhydride, benzoyl peroxide (BPO) initator adding amount of monomer 0.5% (mass fraction) after stirring makes it fully to dissolve to occur to suspend to coagulate and closes reaction, obtains polymer support precursor I through removal of impurities, washing, drying.
Be that 5wt% aqueous hydrogen peroxide solution mixes by polymer support precursor I and the concentration of double weight, carry out oxidation processes 4h, oxidizing temperature keeps 35 DEG C, obtains PMAn polymer support 100 DEG C of dryings.
The preparation of major catalyst: by the RhCl containing 7.50gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is fully mixed by 1.0LPMAn polymer support with above-mentioned maceration extract, leaves standstill the 30 DEG C of dryings of 3h vacuum, obtains described major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol catalyst, 0.02mol iodomethane and 0.15mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The Rh content of this catalyst is 7.36g/L after measured.The yield of ethylidene diacetate is 61.38% as calculated, selective is 84.64%, for convenience of explanation and compare, by the yield of the preparation condition of polymer support preparation and oxidation processes condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 4]
The preparation of polymer support: according to Shang Yuanyan etc. (Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiaoling. the preparation [J] of monodisperse porous St/DVB copolymerization microsphere. Journal of Functional Polymers, 2005,18,7-11.) preparation method of polymer that mentions, APMAn preparation process is as follows:
First be that the PVA aqueous solution of 0.5wt% adds in the there-necked flask of 500ml capacity by 250ml concentration, in aqueous phase, add the NaCl of aqueous phase quality 2%, be warming up to 50 DEG C.Get 13ml styrene (St) and mix with 7ml divinylbenzene (DVB) that to be made into the degree of cross linking be 35% monomer phase, again to above-mentioned monomer mutually in add 2.35g maleic anhydride, benzoyl peroxide (BPO) initator adding amount of monomer 0.5% (mass fraction) after stirring makes it fully to dissolve to occur to suspend to coagulate and closes reaction, after reaction terminates, in its flask, instill the ammoniacal liquor that 50ml concentration is 27wt%, obtain polymer support precursor I through removal of impurities, washing, drying.
Be that 5wt% aqueous hydrogen peroxide solution mixes by polymer support precursor I and the concentration of double weight, carry out oxidation processes 4h, oxidizing temperature keeps 35 DEG C, obtains APMAn polymer support 100 DEG C of dryings.
The preparation of major catalyst: by the RhCl containing 7.50gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is fully mixed by 1.0LAPMAn polymer support with above-mentioned maceration extract, leaves standstill the 30 DEG C of dryings of 3h vacuum, obtains described major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The Rh content of this catalyst is 7.35g/L after measured.The yield of ethylidene diacetate is 61.74% as calculated, selective is 85.04%, for convenience of explanation and compare, by the yield of the preparation condition of polymer support preparation and oxidation processes condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 5]
The preparation of polymer support: according to Shang Yuanyan etc. (Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiaoling. the preparation [J] of monodisperse porous St/DVB copolymerization microsphere. Journal of Functional Polymers, 2005,18, the preparation method of polymer 7-11.) mentioned, the preparation process of benzylamine negative resin is as follows:
First be that the PVA aqueous solution of 0.5wt% adds in the there-necked flask of 500ml capacity by 250ml concentration, in aqueous phase, add the NaCl of aqueous phase quality 2%, be warming up to 50 DEG C.Get 13ml styrene (St) and mix with 7ml divinylbenzene (DVB) that to be made into the degree of cross linking be 35% monomer phase, benzoyl peroxide (BPO) initator adding amount of monomer 0.5% (mass fraction) makes it fully to dissolve the solidifying conjunction that occurs to suspend and is obtained by reacting polystyrene kind ball.After the activation of kind of ball warp, swelling drying and ClCH
2oCH
3, (CH
3)
2after NH reaction, obtain polymer support precursor I through removal of impurities, washing, drying.
The aqueous solution of nitric acid being 5wt% by polymer support precursor I and the concentration of double weight mixes, and carry out oxidation processes 4h, oxidizing temperature keeps 35 DEG C, obtains benzylamine negative resin carrier 100 DEG C of dryings.
The preparation of major catalyst: by the RhCl containing 7.50gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is fully mixed by 1.0L benzylamine negative resin carrier with above-mentioned maceration extract, leaves standstill the 30 DEG C of dryings of 3h vacuum, obtains described major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The Rh content of this catalyst is 7.36g/L after measured.The yield of ethylidene diacetate is 61.05% as calculated, selective is 84.79%, for convenience of explanation and compare, by the yield of the preparation condition of polymer support preparation and oxidation processes condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 6]
The preparation of polymer support: according to Shang Yuanyan etc. (Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiaoling. the preparation [J] of monodisperse porous St/DVB copolymerization microsphere. Journal of Functional Polymers, 2005,18, the preparation method of polymer 7-11.) mentioned, the preparation process of benzylamine negative resin is as follows:
First be that the PVA aqueous solution of 0.5wt% adds in the there-necked flask of 500ml capacity by 250ml concentration, in aqueous phase, add the NaCl of aqueous phase quality 2%, be warming up to 50 DEG C.Get 13ml styrene (St) and mix with 7ml divinylbenzene (DVB) that to be made into the degree of cross linking be 35% monomer phase, benzoyl peroxide (BPO) initator adding amount of monomer 0.5% (mass fraction) makes it fully to dissolve the solidifying conjunction that occurs to suspend and is obtained by reacting polystyrene kind ball.After the activation of kind of ball warp, swelling drying and ClCH
2oCH
3, (CH
3)
2after NH reaction, obtain polymer support precursor I through removal of impurities, washing, drying.
By the hypochlorous acid aqueous solution that the concentration of polymer support precursor I and double weight is 2wt%, carry out oxidation processes 4h, oxidizing temperature keeps 35 DEG C, obtains benzylamine negative resin carrier 100 DEG C of dryings.
The preparation of major catalyst: by the RhCl containing 7.50gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is fully mixed by 1.0L benzylamine negative resin carrier with above-mentioned maceration extract, leaves standstill the 30 DEG C of dryings of 3h vacuum, obtains described major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The Rh content of this catalyst is 7.36g/L after measured.The yield of ethylidene diacetate is 61.12% as calculated, selective is 84.53%, for convenience of explanation and compare, by the yield of the preparation condition of polymer support preparation and oxidation processes condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 7]
The preparation of polymer support: according to Shang Yuanyan etc. (Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiaoling. the preparation [J] of monodisperse porous St/DVB copolymerization microsphere. Journal of Functional Polymers, 2005,18, the preparation method of polymer 7-11.) mentioned, the preparation process of benzylamine negative resin is as follows:
First be that the PVA aqueous solution of 0.5wt% adds in the there-necked flask of 500ml capacity by 250ml concentration, in aqueous phase, add the NaCl of aqueous phase quality 2%, be warming up to 50 DEG C.Get 13ml styrene (St) and mix with 7ml divinylbenzene (DVB) that to be made into the degree of cross linking be 35% monomer phase, benzoyl peroxide (BPO) initator adding amount of monomer 0.5% (mass fraction) makes it fully to dissolve the solidifying conjunction that occurs to suspend and is obtained by reacting polystyrene kind ball.After the activation of kind of ball warp, swelling drying and ClCH
2oCH
3, (CH
3)
2after NH reaction, obtain polymer support precursor I through removal of impurities, washing, drying.
The chloric acid aqueous solution being 5wt% by polymer support precursor I and the concentration of double weight mixes, and carry out oxidation processes 4h, oxidizing temperature keeps 35 DEG C, obtains benzylamine negative resin carrier 100 DEG C of dryings.
The preparation of major catalyst: by the RhCl containing 7.50gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is fully mixed by 1.0L benzylamine negative resin carrier with above-mentioned maceration extract, leaves standstill the 30 DEG C of dryings of 3h vacuum, obtains described major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The Rh content of this catalyst is 7.36g/L after measured.The yield of ethylidene diacetate is 61.01% as calculated, selective is 84.49%, for convenience of explanation and compare, by the yield of the preparation condition of polymer support preparation and oxidation processes condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 8]
The preparation of polymer support: according to Shang Yuanyan etc. (Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiaoling. the preparation [J] of monodisperse porous St/DVB copolymerization microsphere. Journal of Functional Polymers, 2005,18, the preparation method of polymer 7-11.) mentioned, the preparation process of benzylamine negative resin is as follows:
First be that the PVA aqueous solution of 0.5wt% adds in the there-necked flask of 500ml capacity by 250ml concentration, in aqueous phase, add the NaCl of aqueous phase quality 2%, be warming up to 50 DEG C.Get 13ml styrene (St) and mix with 7ml divinylbenzene (DVB) that to be made into the degree of cross linking be 35% monomer phase, benzoyl peroxide (BPO) initator adding amount of monomer 0.5% (mass fraction) makes it fully to dissolve the solidifying conjunction that occurs to suspend and is obtained by reacting polystyrene kind ball.After the activation of kind of ball warp, swelling drying and ClCH
2oCH
3, (CH
3)
2after NH reaction, obtain polymer support precursor I through removal of impurities, washing, drying.
The high chloro acid solution being 2wt% by polymer support precursor I and the concentration of double weight mixes, and carry out oxidation processes 4h, oxidizing temperature keeps 35 DEG C, obtains benzylamine negative resin carrier 100 DEG C of dryings.
The preparation of major catalyst: by the RhCl containing 7.50gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is fully mixed by 1.0L benzylamine negative resin carrier with above-mentioned maceration extract, leaves standstill the 30 DEG C of dryings of 3h vacuum, obtains described major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The Rh content of this catalyst is 7.36g/L after measured.The yield of ethylidene diacetate is 61.56% as calculated, selective is 84.93%, for convenience of explanation and compare, by the yield of the preparation condition of polymer support preparation and oxidation processes condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 9]
The preparation of polymer support: according to Shang Yuanyan etc. (Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiaoling. the preparation [J] of monodisperse porous St/DVB copolymerization microsphere. Journal of Functional Polymers, 2005,18,7-11.) preparation method of polymer that mentions, APMAn preparation process is as follows:
First be that the PVA aqueous solution of 0.5wt% adds in the there-necked flask of 500ml capacity by 250ml concentration, the NaCl adding aqueous phase quality 2% in aqueous phase is warming up to 50 DEG C.Get 18ml styrene (St) and mix with 2ml divinylbenzene (DVB) that to be made into the degree of cross linking be 1% monomer phase, again to above-mentioned monomer mutually in add 2.35g maleic anhydride, benzoyl peroxide (BPO) initator adding amount of monomer 0.5% (mass fraction) after stirring makes it fully to dissolve to occur to suspend to coagulate and closes reaction, after reaction terminates, in its flask, instill the ammoniacal liquor that 50ml concentration is 27wt%, obtain polymer support precursor I through removal of impurities, washing, drying.
Be that 5wt% aqueous hydrogen peroxide solution mixes by polymer support precursor I and the concentration of double weight, carry out oxidation processes 4h, oxidizing temperature keeps 35 DEG C, obtains APMAn polymer support 100 DEG C of dryings.
The preparation of major catalyst: by the RhCl containing 7.50gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is fully mixed by 1.0LAPMAn polymer support with above-mentioned maceration extract, leaves standstill the 30 DEG C of dryings of 3h vacuum, obtains described major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The Rh content of this catalyst is 7.36g/L after measured.The yield of ethylidene diacetate is 61.07% as calculated, selective is 84.62%, for convenience of explanation and compare, by the yield of the preparation condition of polymer support preparation and oxidation processes condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 10]
The preparation of polymer support: according to Shang Yuanyan etc. (Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiaoling. the preparation [J] of monodisperse porous St/DVB copolymerization microsphere. Journal of Functional Polymers, 2005,18,7-11.) preparation method of polymer that mentions, APMAn preparation process is as follows:
First be that the PVA aqueous solution of 0.5wt% adds in the there-necked flask of 500ml capacity by 250ml concentration, in aqueous phase, add the NaCl of aqueous phase quality 2%, be warming up to 50 DEG C.Get 8ml styrene (St) and mix with 12ml divinylbenzene (DVB) that to be made into the degree of cross linking be 60% monomer phase, again to above-mentioned monomer mutually in add 2.35g maleic anhydride, benzoyl peroxide (BPO) initator adding amount of monomer 0.5% (mass fraction) after stirring makes it fully to dissolve to occur to suspend to coagulate and closes reaction, after reaction terminates, in its flask, instill the ammoniacal liquor that 50ml concentration is 27wt%, obtain polymer support precursor I through removal of impurities, washing, drying.
Be that 5wt% aqueous hydrogen peroxide solution mixes by polymer support precursor I and the concentration of double weight, carry out oxidation processes 4h, oxidizing temperature keeps 35 DEG C, obtains APMAn polymer support 100 DEG C of dryings.
The preparation of major catalyst: by the RhCl containing 7.50gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is fully mixed by 1.0LAPMAn polymer support with above-mentioned maceration extract, leaves standstill the 30 DEG C of dryings of 3h vacuum, obtains described major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The Rh content of this catalyst is 7.36g/L after measured.The yield of ethylidene diacetate is 60.98% as calculated, selective is 84.82%, for convenience of explanation and compare, by the yield of the preparation condition of polymer support preparation and oxidation processes condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 11]
The preparation of polymer support: according to Shang Yuanyan etc. (Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiaoling. the preparation [J] of monodisperse porous St/DVB copolymerization microsphere. Journal of Functional Polymers, 2005,18, the preparation method of polymer 7-11.) mentioned, the preparation process of benzylamine negative resin is as follows:
First be that the PVA aqueous solution of 0.5wt% adds in the there-necked flask of 500ml capacity by 250ml concentration, the NaCl adding aqueous phase quality 2% in aqueous phase is warming up to 50 DEG C.Get 13ml styrene (St) and mix with 7ml divinylbenzene (DVB) that to be made into the degree of cross linking be 35% monomer phase, benzoyl peroxide (BPO) initator adding amount of monomer 0.5% (mass fraction) makes it fully to dissolve the solidifying conjunction that occurs to suspend and is obtained by reacting polystyrene kind ball.After the activation of kind of ball warp, swelling drying and ClCH
2oCH
3, (CH
3)
2after NH reaction, obtain polymer support precursor I through removal of impurities, washing, drying.
By the hydrogen peroxide of polymer support precursor I and double weight and perchloric acid mixed aqueous solution, (wherein the concentration of hydrogen peroxide is 2.5wt%, the concentration of perchloric acid is 2.5wt%) mixing, carry out oxidation processes 4h, oxidizing temperature keeps 35 DEG C, obtains benzylamine negative resin carrier 100 DEG C of dryings.
The preparation of major catalyst: by the RhCl containing 7.50gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is fully mixed by 1.0L benzylamine negative resin carrier with above-mentioned maceration extract, leaves standstill the 30 DEG C of dryings of 3h vacuum, obtains described major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The Rh content of this catalyst is 7.36g/L after measured.The yield of ethylidene diacetate is 62.77% as calculated, selective is 85.91%, for convenience of explanation and compare, by the yield of the preparation condition of polymer support preparation and oxidation processes condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
Found out on year-on-year basis by embodiment 11 and embodiment 1 and embodiment 8, in the selective and yield improving EDDA, hydrogen peroxide and perchloric acid oxidation's atmosphere have synergy.
[embodiment 12]
The preparation of polymer support: according to Shang Yuanyan etc. (Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiaoling. the preparation [J] of monodisperse porous St/DVB copolymerization microsphere. Journal of Functional Polymers, 2005,18, the preparation method of polymer 7-11.) mentioned, the preparation process of benzylamine negative resin is as follows:
First be that the PVA aqueous solution of 0.5wt% adds in the there-necked flask of 500ml capacity by 250ml concentration, in aqueous phase, add the NaCl of aqueous phase quality 2%, be warming up to 50 DEG C.Get 13ml styrene (St) and mix with 7ml divinylbenzene (DVB) that to be made into the degree of cross linking be 35% monomer phase, benzoyl peroxide (BPO) initator adding amount of monomer 0.5% (mass fraction) makes it fully to dissolve the solidifying conjunction that occurs to suspend and is obtained by reacting polystyrene kind ball.After the activation of kind of ball warp, swelling drying and ClCH
2oCH
3, (CH
3)
2after NH reaction, obtain polymer support precursor I through removal of impurities, washing, drying.
Be that 5wt% aqueous hydrogen peroxide solution mixes by polymer support precursor I and the concentration of double weight, carry out oxidation processes 4h, oxidizing temperature keeps 35 DEG C, obtains benzylamine negative resin carrier 100 DEG C of dryings.
The preparation of polymer support: according to Shang Yuanyan etc. (Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiaoling. the preparation [J] of monodisperse porous St/DVB copolymerization microsphere. Journal of Functional Polymers, 2005,18,7-11.) preparation method of polymer that mentions, APMAn preparation process is as follows:
First be that the PVA aqueous solution of 0.5wt% adds in the there-necked flask of 500ml capacity by 250ml concentration, in aqueous phase, add the NaCl of aqueous phase quality 2%, be warming up to 50 DEG C.Get 13ml styrene (St) and mix with 7ml divinylbenzene (DVB) that to be made into the degree of cross linking be 35% monomer phase, again to above-mentioned monomer mutually in add 2.35g maleic anhydride, benzoyl peroxide (BPO) initator adding amount of monomer 0.5% (mass fraction) after stirring makes it fully to dissolve to occur to suspend to coagulate and closes reaction, after reaction terminates, in its flask, instill the ammoniacal liquor that 50ml concentration is 27wt%, obtain polymer support precursor I through removal of impurities, washing, drying.
Be that 5wt% aqueous hydrogen peroxide solution mixes by polymer support precursor I and the concentration of double weight, carry out oxidation processes 4h, oxidizing temperature keeps 35 DEG C, obtains APMAn polymer support 100 DEG C of dryings.
The preparation of major catalyst: by the RhCl containing 7.50gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, 0.6L benzylamine negative resin carrier, 0.4LAPMAn polymer support is fully mixed with above-mentioned maceration extract, leaves standstill the 30 DEG C of dryings of 3h vacuum, obtains described major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The Rh content of this catalyst is 7.36g/L after measured.The yield of ethylidene diacetate is 62.64% as calculated, selective is 85.97%, for convenience of explanation and compare, by the yield of the preparation condition of polymer support preparation and oxidation processes condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
Found out on year-on-year basis by embodiment 12 and embodiment 1 and embodiment 4, in the selective and yield improving EDDA, benzylamine negative resin carrier and APMAn polymer support have synergy.
[embodiment 13]
The preparation of polymer support: according to Shang Yuanyan etc. (Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiaoling. the preparation [J] of monodisperse porous St/DVB copolymerization microsphere. Journal of Functional Polymers, 2005,18, the preparation method of polymer 7-11.) mentioned, the preparation process of benzylamine negative resin is as follows:
First be that the PVA aqueous solution of 0.5wt% adds in the there-necked flask of 500ml capacity by 250ml concentration, in aqueous phase, add the NaCl of aqueous phase quality 2%, be warming up to 50 DEG C.Get 13ml styrene (St) and mix with 7ml divinylbenzene (DVB) that to be made into the degree of cross linking be 35% monomer phase, benzoyl peroxide (BPO) initator adding amount of monomer 0.5% (mass fraction) makes it fully to dissolve the solidifying conjunction that occurs to suspend and is obtained by reacting polystyrene kind ball.After the activation of kind of ball warp, swelling drying and ClCH
2oCH
3, (CH
3)
2after NH reaction, obtain polymer support precursor I through removal of impurities, washing, drying.
By the hydrogen peroxide of polymer support precursor I and double weight and perchloric acid mixed aqueous solution, (wherein the concentration of hydrogen peroxide is 2.5wt%, the concentration of perchloric acid is 2.5wt%) mixing, carry out oxidation processes 4h, oxidizing temperature keeps 35 DEG C, obtains benzylamine negative resin carrier 100 DEG C of dryings.
The preparation of polymer support: according to Shang Yuanyan etc. (Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiaoling. the preparation [J] of monodisperse porous St/DVB copolymerization microsphere. Journal of Functional Polymers, 2005,18,7-11.) preparation method of polymer that mentions, APMAn preparation process is as follows:
First be that the PVA aqueous solution of 0.5wt% adds in the there-necked flask of 500ml capacity by 250ml concentration, in aqueous phase, add the NaCl of aqueous phase quality 2%, be warming up to 50 DEG C.Get 13ml styrene (St) and mix with 7ml divinylbenzene (DVB) that to be made into the degree of cross linking be 35% monomer phase, again to above-mentioned monomer mutually in add 2.35g maleic anhydride, benzoyl peroxide (BPO) initator adding amount of monomer 0.5% (mass fraction) after stirring makes it fully to dissolve to occur to suspend to coagulate and closes reaction, after reaction terminates, in its flask, instill the ammoniacal liquor that 50ml concentration is 27wt%, obtain polymer support precursor I through removal of impurities, washing, drying.
By the hydrogen peroxide of polymer support precursor I and double weight and perchloric acid mixed aqueous solution, (wherein the concentration of hydrogen peroxide is 2.5wt%, the concentration of perchloric acid is 2.5wt%) mixing, carry out oxidation processes 4h, oxidizing temperature keeps 35 DEG C, obtains APMAn polymer support 100 DEG C of dryings.
The preparation of major catalyst: by the RhCl containing 7.50gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, 0.6L benzylamine negative resin carrier, 0.4LAPMAn polymer support is fully mixed with above-mentioned maceration extract, leaves standstill the 30 DEG C of dryings of 3h vacuum, obtains described major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The Rh content of this catalyst is 7.36g/L after measured.The yield of ethylidene diacetate is 66.80% as calculated, selective is 88.11%, for convenience of explanation and compare, by the yield of the preparation condition of polymer support preparation and oxidation processes condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
Found out on year-on-year basis by embodiment 13 and embodiment 11 and embodiment 12, in the selective and yield improving EDDA, benzylamine negative resin carrier, APMAn polymer support and hydrogen peroxide, perchloric acid oxidation's atmosphere have synergy.
[embodiment 14]
The preparation of polymer support: according to Shang Yuanyan etc. (Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiaoling. the preparation [J] of monodisperse porous St/DVB copolymerization microsphere. Journal of Functional Polymers, 2005,18, the preparation method of polymer 7-11.) mentioned, the preparation process of benzylamine negative resin is as follows:
First be that the PVA aqueous solution of 0.5wt% adds in the there-necked flask of 500ml capacity by 250ml concentration, in aqueous phase, add the NaCl of aqueous phase quality 2%, be warming up to 50 DEG C.Get 13ml styrene (St) and mix with 7ml divinylbenzene (DVB) that to be made into the degree of cross linking be 35% monomer phase, benzoyl peroxide (BPO) initator adding amount of monomer 0.5% (mass fraction) makes it fully to dissolve the solidifying conjunction that occurs to suspend and is obtained by reacting polystyrene kind ball.After the activation of kind of ball warp, swelling drying and ClCH
2oCH
3, (CH
3)
2after NH reaction, obtain polymer support precursor I through removal of impurities, washing, drying.
Be that 5wt% aqueous hydrogen peroxide solution mixes by polymer support precursor I and the concentration of double weight, carry out oxidation processes 4h, oxidizing temperature keeps 35 DEG C, obtains benzylamine negative resin carrier 100 DEG C of dryings.
The preparation of major catalyst: by the RhCl containing 7.50gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is fully mixed by 1.0L benzylamine negative resin carrier with above-mentioned maceration extract, leaves standstill the 30 DEG C of dryings of 3h vacuum, obtains described major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 3.0MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 130 DEG C, and the mol ratio of carbon monoxide and hydrogen is 1:10, after sustained response 3.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The Rh content of this catalyst is 7.37g/L after measured.The yield of ethylidene diacetate is 54.16% as calculated, selective is 79.01%, for convenience of explanation and compare, by the yield of the preparation condition of polymer support preparation and oxidation processes condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 15]
The preparation of polymer support: according to Shang Yuanyan etc. (Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiaoling. the preparation [J] of monodisperse porous St/DVB copolymerization microsphere. Journal of Functional Polymers, 2005,18, the preparation method of polymer 7-11.) mentioned, the preparation process of benzylamine negative resin is as follows:
First be that the PVA aqueous solution of 0.5wt% adds in the there-necked flask of 500ml capacity by 250ml concentration, in aqueous phase, add the NaCl of aqueous phase quality 2%, be warming up to 50 DEG C.Get 13ml styrene (St) and mix with 7ml divinylbenzene (DVB) that to be made into the degree of cross linking be 35% monomer phase, benzoyl peroxide (BPO) initator adding amount of monomer 0.5% (mass fraction) makes it fully to dissolve the solidifying conjunction that occurs to suspend and is obtained by reacting polystyrene kind ball.After the activation of kind of ball warp, swelling drying and ClCH
2oCH
3, (CH
3)
2after NH reaction, obtain polymer support precursor I through removal of impurities, washing, drying.
Be that 5wt% aqueous hydrogen peroxide solution mixes by polymer support precursor I and the concentration of double weight, carry out oxidation processes 4h, oxidizing temperature keeps 35 DEG C, obtains benzylamine negative resin carrier 100 DEG C of dryings.
The preparation of major catalyst: by the RhCl containing 7.50gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is fully mixed by 1.0L benzylamine negative resin carrier with above-mentioned maceration extract, leaves standstill the 30 DEG C of dryings of 3h vacuum, obtains described major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 10.0MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, controlling reaction temperature is 200 DEG C, the mol ratio of carbon monoxide and hydrogen is 10:1, after sustained response 10.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The Rh content of this catalyst is 7.36g/L after measured.The yield of ethylidene diacetate is 61.98% as calculated, selective is 84.25%, for convenience of explanation and compare, by the yield of the preparation condition of polymer support preparation and oxidation processes condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
Table 1
Table 2 (continued)
table 2 (Continued)
| Yield Y (EDDA), % | Sel(EDDA)，％ | |
| Embodiment 1 | 61.04 | 84.81 |
| Comparative example 1 | 50.83 | 79.47 |
| Comparative example 2 | 53.73 | 80.21 |
| Comparative example 3 | 50.92 | 79.38 |
| Embodiment 2 | 61.25 | 84.79 |
| Embodiment 3 | 61.38 | 84.64 |
| Embodiment 4 | 61.74 | 85.04 |
| Embodiment 5 | 61.05 | 84.79 |
| Embodiment 6 | 61.12 | 84.53 |
| Embodiment 7 | 61.01 | 84.49 |
| Embodiment 8 | 61.56 | 84.93 |
| Embodiment 9 | 61.07 | 84.62 |
| Embodiment 10 | 60.98 | 84.82 |
| Embodiment 11 | 62.77 | 85.91 |
| Embodiment 12 | 62.64 | 85.97 |
| Embodiment 13 | 66.80 | 88.11 |
| Embodiment 14 | 54.16 | 79.01 |
| Embodiment 15 | 61.98 | 84.25 |
Claims (10)
1. ethylidene diacetate catalyst, described catalyst comprises major catalyst and co-catalyst, and described major catalyst comprises carrier, active component; Described activity group adopts the compound of rhodium; Described co-catalyst is iodide; Described carrier is polymer; Described polymer is selected from least one in crosslinked poly-(NVP), crosslinked poly-(phenylethylene-maleic anhydride), crosslinked ammonification poly-(phenylethylene-maleic anhydride) and crosslinked benzylamine negative resin polymer.
2. catalyst according to claim 1, is characterized in that the compound of described rhodium is RhCl
3.
3. catalyst according to claim 1, is characterized in that described iodide are iodomethane.
4. catalyst according to claim 1, is characterized in that the degree of cross linking of described polymer is 1 ~ 60%.
5., by the preparation method of catalyst according to claim 1, comprise the steps:
1. described polymer support is carried out oxidation processes, drying obtains the carrier through oxidation processes;
2. the composition of catalyst is pressed by RhCl
3compound is mixed with aqueous impregnation described on the carrier of oxidation processes;
3. standing, dry, obtain described major catalyst.
6. the preparation method of catalyst according to claim 5, is characterized in that the 1. and 3. described baking temperature of step independently elects 80 ~ 120 DEG C as.
7. the synthetic method of ethylidene diacetate, with methyl acetate, carbon monoxide and hydrogen for raw material, take acetic acid as solvent, under catalyst according to any one of Claims 1 to 4 exists, synthesize ethylidene diacetate.
8. synthetic method according to claim 7, it is characterized in that the temperature of reacting is 130 ~ 200 DEG C, the pressure of reaction is 3.0 ~ 10.0MPa.
9. synthetic method according to claim 7, is characterized in that the time of reacting is 3.0 ~ 10.0h.
10. synthetic method according to claim 7, is characterized in that carbon monoxide and hydrogen volume ratio are 0.1 ~ 10.
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| CN1086741A (en) * | 1992-08-31 | 1994-05-18 | 赫希斯特人造丝公司 | Polymeric carbonylation catalyst system |
| CN1834083A (en) * | 2005-03-14 | 2006-09-20 | 北京化工大学 | Prepn. of vinyl acetate by carbinol and synthetic gas |
| US20120077669A1 (en) * | 2010-09-29 | 2012-03-29 | Basf Corporation | Polymer-Assisted Synthesis Of A Supported Metal Catalyst |
| CN103553913A (en) * | 2013-10-28 | 2014-02-05 | 中国石油化工股份有限公司 | Synthetic method of ethylidene diacetate |
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