CN101348472A - Method for preparing epoxide - Google Patents
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- CN101348472A CN101348472A CNA2007100439574A CN200710043957A CN101348472A CN 101348472 A CN101348472 A CN 101348472A CN A2007100439574 A CNA2007100439574 A CN A2007100439574A CN 200710043957 A CN200710043957 A CN 200710043957A CN 101348472 A CN101348472 A CN 101348472A
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Abstract
The invention relates to a method for preparing an epoxide and mainly resolves the problems in the prior art such as the low activity of catalysts for production of the epoxide, poor effect of mass transference, and high cost of production. The invention well resolves the problems through adopting the technical proposal which selects cheap organic amine as a template with shorter crystallization time, carries titanium through posterior synthesis in the presence of inertia gas, grafts inorganic titanium to silicon dioxide framework with a hexagonal mesoporous structure to form a substance of active titanium with four coordinating structure, and carries out alkylation treatment to produce a catalyst of the epoxide. The method provided by the invention can be applied to the industrialized production of the epoxide.
Description
Technical field
The present invention relates to be used to prepare the method for epoxide.
Background technology
Epoxide is the important organic chemical industry's intermediate of a class, and the method for industrial production epoxide mainly contains chlorohydrination and conjugated oxidation at present.Chlorohydrination is owing to produce a large amount of chlorine-contained wastewaters in process of production, and environmental pollution and equipment corrosion are serious; Conjugated oxidation has overcome shortcomings such as the pollution of chlorohydrination and corrosion, but long flow path, investment is big, co-product is many, and joint product market has influenced the production of propylene oxide to a certain extent.
As everyone knows, titaniferous porous silica material has good catalytic activity to the selective oxidation of hydro carbons, can be used as the catalyzer that the alkene selective oxidation prepares epoxide.
Patent US4410501 discloses the synthetic method of TS-1 molecular sieve first.At first, the aqueous solution, organic titanate and the organosilicon acid esters with TPAOH is the titaniferous colloidal silica solution of feedstock production.Then, directly synthetic again by hydrothermal crystallizing.The invention of this new catalytic material is laid a good foundation for the friendly technology with development environment of the hydrocarbon oxidization of research highly selective, but because TS-1 is the micro-pore zeolite with MFI structure, its aperture has only 0.55 nanometer, the oxidizing reaction that can not catalysis organic macromolecule (as tetrahydrobenzene and vinylbenzene etc.) participates in, when being oxygenant with the organo-peroxide in addition, TS-1 does not almost have catalytic activity.
It is catalyzer that patent US3923843 and US4367342 disclose with titaniferous amorphous silica, and ethylbenzene hydroperoxide (EBHP) can be a propylene oxide with Selective Oxidation of Propylene.But because its specific surface area of amorphous silica carrier and the pore volume that are adopted are little, the charge capacity of titanium is difficult to improve, activity of such catalysts is low, the internal diffusion performance of catalyzer is also poor simultaneously, therefore, to be difficult to competent be the catalysis epoxidation system of oxygenant with other superoxide (as isopropyl benzene hydroperoxide) to such catalyzer.
It is oxygenant that patent CN1500004A and CN 1248579A disclose with isopropyl benzene hydroperoxide (CHP) or ethylbenzene hydroperoxide (EBHP), and the Ti-MCM41 catalyzer can become propylene oxide with Selective Oxidation of Propylene.But because the Ti-MCM41 catalyzer adopts expensive quaternary ammonium salt to make template in building-up process, need long crystallization process simultaneously, the production efficiency of catalyzer is low, thereby causes the manufacturing cost height of catalyzer, and the industrial economy of propylene oxide is subjected to remarkably influenced.
It is the novel titanium-containing molecular sieve catalyst (Ti-HMS) with mesoporous feature of oxygenant selective oxidation 2,6 di t butyl phenol and benzene with the hydrogen peroxide that Nature magazine (1994,368,321) has been introduced a kind of.The Ti-HMS catalyzer is that the mixing solutions with water, ethanol and Virahol is a solvent, with isopropyl titanate and tetraethoxy be raw material, to adopt positive amino dodecane be template, synthetic at ambient temperature.Compare with Ti-MCM41, Ti-HMS has better Technological Economy.But the document be not to do any research aspect the oxidizer catalytic olefin oxide with the organo-peroxide to the Ti-HMS catalyzer.
Summary of the invention
Technical problem to be solved by this invention be produce in the prior art that the catalyst activity of epoxide is low, mass transfer effect difference and the high problem of production cost, a kind of new method that is used to prepare epoxide is provided.This method has catalyst activity and selectivity height, and mass transfer effect reaches the low characteristics of production cost well.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method that is used to prepare epoxide, in fixed-bed reactor, with alkene and organo-peroxide is raw material, reaction system is the inert non-polar compound is solvent, is 25～200 ℃ in temperature of reaction, and the reaction absolute pressure is 0.1～10MPa, the mol ratio of alkene and organo-peroxide is 1～20: 1, and the weight space velocity of organo-peroxide is 0.1～20 hour
-1Condition under react epoxide, wherein used catalyzer is Ti-HMS, its preparation may further comprise the steps:
A) with the silicon ester be the silicon source, general formula is RNH
2Organic amine be template, organic alcohol and water is a solvent, wherein R is the chain alkylene that contains 7～36 carbon atoms, with molar ratio computing RNH
2/ Si=0.01～1: 1, water/pure volume ratio is 0.01～5: 1, and above-mentioned reaction mixture was at room temperature stirred crystallization 0.5～48 hour, and crystallized product is through separation, washing, drying, and 300～1000 ℃ of roastings obtained HMS in 0.5～48 hour;
B) with after the above-mentioned HMS moulding, under 25～600 ℃, be carrier gas with the rare gas element, fed inorganic titanium compound 0.5～48 hour, obtain Ti-HMS, wherein with molar ratio computing Si/Ti=5～200: 1;
C) above-mentioned Ti-HMS is activated 0.5～48 hour at 300～1000 ℃, obtain catalyst Precursors;
D) the above-mentioned catalyst Precursors that obtains is carried out gas-solid phase reaction with organosilicon in inert gas environment, handle catalyzer is carried out silanization, obtain Ti-HMS catalyzer through the silanization processing, wherein organosilyl consumption is 10～70% of a catalyst Precursors weight, the silanization temperature is 50～600 ℃, and the silanization time is 0.5～48 hour.
In the technique scheme, described alkene preferred version is alkene, cycloolefin or fragrant alkene; Described organo-peroxide preferred version is ethylbenzene hydroperoxide, isopropyl benzene hydroperoxide, tertbutyl peroxide or cyclohexyl hydroperoxide; It is described that reaction system is inert non-polar compound preferred version is ethylbenzene, isopropyl benzene, Trimethylmethane or hexanaphthene.The temperature of reaction preferable range is 40～130 ℃, and reaction absolute pressure preferable range is 0.1～5.0MPa, and the mol ratio preferable range of alkene and organo-peroxide is 2～15: 1, and the weight space velocity preferable range of organo-peroxide is 0.5～10 hour
-1A) preferred version of silicon ester described in the step is methyl silicate, tetraethoxy, positive silicic acid n-propyl, positive isopropyl silicate or butyl silicate; Described pure preferred version is at least a in methyl alcohol, ethanol, n-propyl alcohol, Virahol, vinyl alcohol, allyl alcohol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, amylalcohol, hexalin, ethylene glycol or the propylene glycol; The R preferred version is the chain alkylene that contains 10～20 carbon atoms; With molar ratio computing RNH
2/ Si preferable range is 0.1～5: 1, and water/pure volume ratio preferable range is 0.1～2: 1, and crystallization time preferable range is 1～24 hour.B) preferred version of inorganic titanium compound described in step preferred version is titanium tetrachloride, titanous chloride, titanium tetrabromide, titanium tribromide, titanium tetra iodide or titanium triiodide, is 10～100 with molar ratio computing Si/Ti preferable range wherein; Described rare gas element preferred version is N
2, Ar, He or CO
2Carrying titanium temperature preferable range is 50～250 ℃, and carrying titanium time preferable range is 1～24 hour.C) the activation temperature preferable range is 400～800 ℃ in the step, and the soak time preferable range is 1～24 hour.D) in the step organosilicon preferred version for being selected from halosilanes, at least a in silazane or the silylamine, wherein the halosilanes preferred version is for being selected from trimethylchlorosilane, chlorotriethyl silane, the tripropyl chlorosilane, the tributyl chlorosilane, chlorodimethyl silane, dimethyldichlorosilane(DMCS), the 3,5-dimethylphenyl chlorosilane, the dimethyl ethyl chlorosilane, dimethyl n propyl chloride silane, dimethyl isopropyl chloride silane, normal-butyl dimethylchlorosilane or aminomethyl phenyl chlorosilane, more preferably scheme is for being selected from trimethylchlorosilane, chlorotriethyl silane, chlorodimethyl silane, dimethyldichlorosilane(DMCS), 3,5-dimethylphenyl chlorosilane or dimethyl ethyl chlorosilane; The silazane preferred version is for being selected from hexamethyldisilazane, 1,1,3,3-tetramethyl-disilazane, 1,3-two (chloromethyl) tetramethyl-disilazane, 1,3-divinyl-1,1,3,3-tetramethyl-disilazane or 1,3-phenylbenzene tetramethyl-disilazane, more preferably scheme is for being selected from hexamethyldisilazane or 1,1,3, the 3-tetramethyl-disilazane; The silylamine preferred version is for being selected from N-trimethyl-silyl-imidazole, N-t-butyldimethylsilyl imidazoles, N-dimethylethylsilyl imidazoles, N-dimethyl n propyl group silyl imidazoles, N-dimethyl sec.-propyl silyl imidazoles, N-trimethyl silyl dimethyl amine or N-trimethyl silyl diethylamide, and more preferably scheme is for being selected from N-trimethyl-silyl-imidazole, N-dimethylethylsilyl imidazoles, N-trimethyl silyl dimethyl amine or N-trimethyl silyl diethylamide; Described rare gas element preferred version is for being selected from N
2, Ar, He or CO
2Silanization temperature preferable range is 50～400 ℃, and silanization time preferable range is 1～24 hour.
In support of the catalyst HMS building-up process, preferably in reaction mixture, add acid or alkali, the mol ratio of acid or alkali and silicon ester is 0.001～10: 1.Wherein acid is selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetate or propionic acid, and alkali is selected from sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood or ammoniacal liquor.
Catalyzer among the present invention is at 960 ± 10cm of infrared absorpting light spectra
-1All have charateristic avsorption band with 210 ± 10nm place at uv-visible absorption spectra figure, this indicate titanium grafting in silicon dioxide skeleton and formed active titanium species with four-coordination structure.
Because the catalyzer for preparing among the present invention is a kind of typical heterogeneous catalyst, so, in adopting the epoxide reaction liquid that this method produced, not containing catalyzer substantially, product is not subjected to catalyst contamination.
Synthetic Ti-HMS among the present invention, owing to adopt cheap organic amine to make template, crystallization time is short, and directly carries titanium with back synthetic method in inert atmosphere, thus the production efficiency height of catalyzer, manufacturing cost significantly reduces.In addition, the catalyst Precursors of handling without silanization among the present invention is because abundant silicon hydroxyl and titanium hydroxyl are contained in its surface, so possess hydrophilic property and acidity, yield and the selectivity of catalyzer to epoxide in this remarkably influenced.In order to improve the epoxidation performance of catalyzer, catalyst Precursors is carried out silanization handle, the hydroxyl that its surface is existed is converted into the alkyl siloxy, strengthens hydrophobic nature, reduces acid.The raising of catalyzer hydrophobic nature can reduce the absorption of polarity oxidation products at catalyst surface, also can avoid the loss of active constituent titanium on the catalyzer.Synthetic specific surface area of catalyst and pore volume are big among the present invention, and the charge capacity of titanium can be guaranteed, so the activity of such catalysts height, the internal diffusion performance of catalyzer might as well simultaneously.When therefore the synthetic catalyzer is used to prepare epoxide among the present invention, the catalyst activity height, the selectivity of product height has been obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
In room temperature with under stirring, 10 gram cetylamines, 5 gram amino dodecanes are joined 80 milliliters of H
2In the mixing solutions of O, 60 milliliters of ethanol and 5 milliliters of (1M) hydrochloric acid, be stirred to solution and be a phase.To be dissolved in 65.0 in 30 milliliters of ethanol grams tetraethoxy and join in the above-mentioned mixing solutions, stir after 30 minutes crystallization 24 hours.Filter resulting decorating film, wash with water to remove remaining Cl
-Solid after the washing after 12 hours, 600 ℃ of roastings 4 hours, is promptly got the HMS with hexagonal mesoporous structure in 110 ℃ of oven dry.
Powdered samples compression molding (forming pressure is 20MPa) back crushing and screening with above-mentioned preparation, get 20-40 purpose particle 10.0 grams and put into quartz tube reactor, under nitrogen atmosphere in 120 ℃ of oven dry elevated temperature to 300 ℃ after 2 hours, with nitrogen with 1.2 gram TiCl
4Saturation steam is brought into, elevated temperature to 700 ℃ roasting subsequently 2 hours.After reducing temperature to 220 ℃, feed 1.5 gram saturated vapors, fed nitrogen purging then 2 hours.Then under this temperature, the saturation steam of bringing 4.0 gram hexamethyldisilazanes with nitrogen into carries out the silanization processing, uses nitrogen purging then 2 hours, promptly makes the Ti-HMS catalyzer of handling through silanization, and its specific surface area is 820 meters
2/ gram, pore volume is 0.87 centimetre
3/ gram, mean pore size is
[embodiment 2]
Except TiCl
4Amount be 1.5 the gram outside, all the other conditions are identical with [embodiment 1].The specific surface area of the Ti-HMS catalyzer that makes is 800 meters
2/ gram, pore volume is 0.85 centimetre
3/ gram, mean pore size is
[embodiment 3]
Except TiCl
4Amount be 0.9 the gram outside, all the other conditions are identical with [embodiment 1].The specific surface area of the Ti-HMS catalyzer that makes is 850 meters
2/ gram, pore volume is 0.9 centimetre
3/ gram, mean pore size is
[embodiment 4]
Except template was 16.0 gram cetylamines, all the other conditions were identical with [embodiment 1].The specific surface area of the Ti-HMS catalyzer that makes is 800 meters
2/ gram, pore volume is 0.90 centimetre
3/ gram, mean pore size is
[embodiment 5]
Except template was 12.5 gram amino dodecanes, all the other conditions were identical with [embodiment 1].The specific surface area of the Ti-HMS catalyzer that makes is 850 meters
2/ gram, pore volume is 0.92 centimetre
3/ gram, mean pore size is
[comparative example 1]
In room temperature with under stirring, 4.3 gram tetrabutyl titanates are joined the ethanolic soln that forms tetrabutyl titanate in 20 milliliters of ethanol, restrain commercially available silica gel (80-120 order, 340 meters of the specific surface areas that drying treatment are crossed with 20.0
2/ gram, 0.71 centimetre of pore volume
3/ gram, mean pore size
) join in 60 milliliters of ethanol.Under nitrogen atmosphere, the ethanolic soln of tetrabutyl titanate is added drop-wise in the ethanol that contains commercially available silica gel, at room temperature stir 2 hours after-filtration of this mixture, with washing with alcohol filtrate three times.Solid in air atmosphere after 110 ℃ of above-mentioned filtrations of oven dry 12 hours 600 ℃ of roastings 4 hours, promptly gets titaniferous SiO 2 catalyst.In one 100 milliliters there-necked flask, add 50 milliliters of cumene solutions that contain 4.0 gram hexamethyldisilazanes, the titaniferous silica sample of the above-mentioned preparation of 10.0 grams is joined in the flask, under stirring and refluxing, elevated temperature to 150 ℃, and reaction 4 hours under this temperature.Under this temperature, the hexamethyldisilazane of evaporated in vacuo remnants and isopropyl benzene solvent promptly make the TiO that handles through silanization then
2/ SiO
2Catalyzer.Its specific surface area of the catalyzer that so makes is 270 meters
2/ gram, pore volume is 0.65 centimetre
3/ gram, mean pore size is
[comparative example 2]
Take by weighing commercially available silica gel (20-40 order, 340 meters of specific surface areas that 20.0 gram dryings were handled
2/ gram, 0.71 centimetre of pore volume
3/ gram, mean pore size
) be immersed in 60 milliliters of octane solvents.Under stirring and nitrogen atmosphere, will be dissolved with 2.4 gram TiCl
420 milliliters of octane mixtures be added drop-wise in the above-mentioned paste mixture, be warming up to 100 ℃ after constant temperature stirring and refluxing 2 hours, elevated temperature to 150 ℃ solvent evaporated under vacuum condition then.The solid of above-mentioned acquisition is put in the quartz tube reactor, in nitrogen atmosphere, elevated temperature to 700 ℃, and this roasting temperature 2 hours, reduce the temperature to 300 ℃ after, feed saturated steam 3.0 grams, nitrogen purging 2 hours.Further reduce temperature to 220 ℃, the nitrogen that will contain 6.0 gram hexamethyldisilazane saturation steams under this temperature were used nitrogen purging 2 hours then by beds, promptly made the TiO that handles through silanization
2/ SiO
2Catalyzer.Its specific surface area of the catalyzer that so makes is 285 meters
2/ gram, pore volume is 0.67 centimetre
3/ gram, mean pore size is
[embodiment 6～10]
Preparing epoxypropane by epoxidation of propene (PO)
It is 10 millimeters stainless steel fixed-bed reactor that catalyzer 2.5 gram (20-40 order) of [embodiment 1～5] is put into internal diameter, feeds the cumene solution and the propylene of 35.0 (weight) % isopropyl benzene hydroperoxide (CHP), and wherein the weight space velocity of CHP is 4.2 hours
-1, the mol ratio of propylene/CHP is 9.0.The temperature of beds is 90 ℃, and reaction pressure is 3.0MPa.Get the epoxidation performance evaluation data of the average response result of 73～144 hour time period as catalyzer, reaction result sees Table 1.
[comparative example 3～4]
The catalyzer of [comparative example 1～2] is checked and rated according to [embodiment 6～10], and reaction result sees Table 1.
Table 1
[embodiment 11～15]
Preparing epoxypropane by epoxidation of propene (PO)
It is 10 millimeters stainless steel fixed-bed reactor that catalyzer 2.5 gram (20-40 order) of [embodiment 1～5] is put into internal diameter, feeds the ethylbenzene solution and the propylene of 20.0 (weight) % ethylbenzene hydroperoxide (EBHP), and wherein the weight space velocity of EBHP is 4.5 hours
-1, the mol ratio of propylene/EBHP is 8.0.The temperature of beds is 80 ℃, and reaction pressure is 3.0MPa.Get the epoxidation performance evaluation data of the average response result of 73～144 hour time period as catalyzer, reaction result sees Table 2.
[comparative example 5～6]
The catalyzer of [comparative example 1～2] is checked and rated according to [embodiment 11～15], and reaction result sees Table 2.
Table 2
[embodiment 16～20]
The cyclohexene ring oxidation prepares epoxy cyclohexane (CHO)
It is 10 millimeters stainless steel fixed-bed reactor that catalyzer 2.5 gram (20-40 order) of [embodiment 1～5] is put into internal diameter, feed the cumene solution and the tetrahydrobenzene of 35.0 (weight) % isopropyl benzene hydroperoxide (CHP), wherein the weight space velocity of CHP is 5.0 hours
-1, the mol ratio of tetrahydrobenzene/CHP is 2.0.The temperature of beds is 60 ℃, and reaction pressure is 0.5MPa.Get the epoxidation performance evaluation data of the average response result of 73～144 hour time period as catalyzer, reaction result sees Table 3.
[comparative example 7～8]
The catalyzer of [comparative example 1～2] is checked and rated according to [embodiment 16～20], and reaction result sees Table 3.
Table 3
[embodiment 21～25]
Epoxidation of styrene prepares Styryl oxide (SMO)
It is 10 millimeters stainless steel fixed-bed reactor that catalyzer 2.5 gram (20-40 order) of [embodiment 1～5] is put into internal diameter, feed the cumene solution and the vinylbenzene of 35.0 (weight) % isopropyl benzene hydroperoxide (CHP), wherein the weight space velocity of CHP is 3.0 hours
-1, the mol ratio of vinylbenzene/CHP is 2.0.The temperature of beds is 80 ℃, and reaction pressure is 0.5MPa.Get the epoxidation performance evaluation data of the average response result of 73～144 hour time period as catalyzer, reaction result sees Table 4.
[comparative example 9～10]
The catalyzer of [comparative example 1～2] is checked and rated according to [embodiment 21～25], and reaction result sees Table 4.
Table 4
Claims (10)
1, a kind of method that is used to prepare epoxide, in fixed-bed reactor, with alkene and organo-peroxide is raw material, reaction system is the inert non-polar compound is solvent, in temperature of reaction is 25～200 ℃, the reaction absolute pressure is 0.1～10MPa, and the mol ratio of alkene and organo-peroxide is 1～20: 1, and the weight space velocity of organo-peroxide is 0.1～20 hour
-1Condition under react epoxide, wherein used catalyzer is Ti-HMS, its preparation may further comprise the steps:
A) with the silicon ester be the silicon source, general formula is RNH
2Organic amine be template, organic alcohol and water is a solvent, wherein R is the chain alkylene that contains 7～36 carbon atoms, with molar ratio computing RNH
2/ Si=0.01～1: 1, water/pure volume ratio is 0.01～5: 1, and above-mentioned reaction mixture was at room temperature stirred crystallization 0.5～48 hour, and crystallized product is through separation, washing, drying, and 300～1000 ℃ of roastings obtained HMS in 0.5～48 hour;
B) with after the above-mentioned HMS moulding, under 25～600 ℃, be carrier gas with the rare gas element, fed inorganic titanium compound 0.5～48 hour, obtain Ti-HMS, wherein with molar ratio computing Si/Ti=5～200: 1;
C) above-mentioned Ti-HMS is activated 0.5～48 hour at 300～1000 ℃, obtain catalyst Precursors;
D) the above-mentioned catalyst Precursors that obtains is carried out gas-solid phase reaction with organosilicon in inert gas environment, handle catalyzer is carried out silanization, obtain Ti-HMS catalyzer through the silanization processing, wherein organosilyl consumption is 10～70% of a catalyst Precursors weight, the silanization temperature is 50～600 ℃, and the silanization time is 0.5～48 hour.
2,, it is characterized in that described alkene is alkene, cycloolefin or fragrant alkene according to the described method that is used to prepare epoxide of claim 1; Described organo-peroxide is ethylbenzene hydroperoxide, isopropyl benzene hydroperoxide, tertbutyl peroxide or cyclohexyl hydroperoxide; It is described that reaction system is the inert non-polar compound is ethylbenzene, isopropyl benzene, Trimethylmethane or hexanaphthene.
3, according to the described method that is used to prepare epoxide of claim 1, it is characterized in that temperature of reaction is 40～130 ℃, the reaction absolute pressure is 0.1～5.0MPa, and the mol ratio of alkene and organo-peroxide is 2～15: 1, and the weight space velocity of organo-peroxide is 0.5～10 hour
-1
4,, it is characterized in that a) silicon ester described in the step is methyl silicate, tetraethoxy, positive silicic acid n-propyl, positive isopropyl silicate or butyl silicate according to the described method that is used to prepare epoxide of claim 1; Described alcohol is at least a in methyl alcohol, ethanol, n-propyl alcohol, Virahol, vinyl alcohol, allyl alcohol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, amylalcohol, hexalin, ethylene glycol or the propylene glycol; R is the chain alkylene that contains 10～20 carbon atoms; With molar ratio computing RNH
2/ Si=0.1～5: 1, water/pure volume ratio is 0.1～2: 1, the crystallization time is 1～24 hour.
5, according to the described method that is used to prepare epoxide of claim 1, it is characterized in that b) inorganic titanium compound described in the step is titanium tetrachloride, titanous chloride, titanium tetrabromide, titanium tribromide, titanium tetra iodide or titanium triiodide, described rare gas element is N
2, Ar, He or CO
2, be 10～100 wherein with molar ratio computing Si/Ti; Carrying the titanium temperature is 50～250 ℃, and carrying the titanium time is 1～24 hour.
6, according to the described method that is used to prepare epoxide of claim 1, it is characterized in that c) activation temperature is 400～800 ℃ in the step, soak time is 1～24 hour.
7, according to the described method that is used to prepare epoxide of claim 1, it is characterized in that d) organosilicon described in the step is selected from least a in halosilanes, silazane or the silylamine; Described rare gas element is selected from N
2, Ar, He or CO
2The silanization temperature is 50～400 ℃, and the silanization time is 1～24 hour.
8,, it is characterized in that halosilanes is selected from trimethylchlorosilane, chlorotriethyl silane, tripropyl chlorosilane, tributyl chlorosilane, chlorodimethyl silane, dimethyldichlorosilane(DMCS), 3,5-dimethylphenyl chlorosilane, dimethyl ethyl chlorosilane, dimethyl n propyl chloride silane, dimethyl isopropyl chloride silane, normal-butyl dimethylchlorosilane or aminomethyl phenyl chlorosilane according to the described method that is used to prepare epoxide of claim 7; Silazane is selected from hexamethyldisilazane, 1,1,3,3-tetramethyl-disilazane, 1,3-two (chloromethyl) tetramethyl-disilazane, 1,3-divinyl-1,1,3,3-tetramethyl-disilazane or 1,3-phenylbenzene tetramethyl-disilazane; Silylamine is selected from N-trimethyl-silyl-imidazole, N-t-butyldimethylsilyl imidazoles, N-dimethylethylsilyl imidazoles, N-dimethyl n propyl group silyl imidazoles, N-dimethyl sec.-propyl silyl imidazoles, N-trimethyl silyl dimethyl amine or N-trimethyl silyl diethylamide.
9, the described according to Claim 8 method that is used to prepare epoxide is characterized in that halosilanes is selected from trimethylchlorosilane, chlorotriethyl silane, chlorodimethyl silane, dimethyldichlorosilane(DMCS), 3,5-dimethylphenyl chlorosilane or dimethyl ethyl chlorosilane; Silazane is selected from hexamethyldisilazane or 1,1,3, the 3-tetramethyl-disilazane; Silylamine is selected from N-trimethyl-silyl-imidazole, N-dimethylethylsilyl imidazoles, N-trimethyl silyl dimethyl amine or N-trimethyl silyl diethylamide.
10, according to the described method that is used to prepare epoxide of claim 1, it is characterized in that a) also containing acid or alkali in the step reaction mixture, the mol ratio of acid or alkali and silicon ester is 0.001～10: 1, wherein acid is selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetate or propionic acid, and alkali is selected from sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood or ammoniacal liquor.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| SG73663A1 (en) * | 1998-08-04 | 2000-06-20 | Sumitomo Chemical Co | A process for producing propylene oxide |
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