CN101555236A - High-selectivity epoxidation method of olefin catalyzed by nano-SiO* material and H*O* liquid phase - Google Patents

High-selectivity epoxidation method of olefin catalyzed by nano-SiO* material and H*O* liquid phase Download PDF

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CN101555236A
CN101555236A CNA2009100621701A CN200910062170A CN101555236A CN 101555236 A CN101555236 A CN 101555236A CN A2009100621701 A CNA2009100621701 A CN A2009100621701A CN 200910062170 A CN200910062170 A CN 200910062170A CN 101555236 A CN101555236 A CN 101555236A
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鲁新环
汤增荣
夏清华
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Hubei University
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Abstract

本发明涉及不使用任何含过渡金属类的催化剂而仅使用催化剂通过多相催化氧化制备环氧化物的化学反应过程，具体地说是一种纳米SiO2材料催化的烯烃与H2O2液相高选择性环氧化方法，使用纳米SiO2材料、或经过表面改性的带有机功能基的活化SiO2材料、或者沸石分子筛直接作为反应的催化剂，和反应底物、溶剂形成“SiO2—烯烃—溶剂—H2O2/H2O”多相催化环氧化反应体系中催化广泛烯烃环氧化反应，用作环氧化氧化试剂是市售H2O2，反应温度控制在0～100℃，反应时间为0.5～24h。本发明的优点为：不使用任何含过渡金属类的催化剂，原料的转化率高，目标产物的选择性好，反应时间短，效率高、反应条件温和，操作易于控制、成本低，整个过程环境友好。The present invention relates to a chemical reaction process for preparing epoxides through heterogeneous catalytic oxidation without using any catalysts containing transition metals, specifically a nano- SiO2 material catalyzed olefin and H2O2 liquid phase Highly selective epoxidation method, using nano-SiO 2 materials, or surface-modified activated SiO 2 materials with organic functional groups, or zeolite molecular sieves directly as reaction catalysts, and reaction substrates and solvents to form "SiO 2 — Olefin-Solvent-H 2 O 2 /H 2 O" heterogeneous catalytic epoxidation reaction system catalyzes a wide range of olefin epoxidation reactions. The epoxidation oxidation reagent is commercially available H 2 O 2 , and the reaction temperature is controlled at 0 ~100°C, the reaction time is 0.5~24h. The advantages of the present invention are: no catalyst containing transition metals is used, the conversion rate of raw materials is high, the selectivity of the target product is good, the reaction time is short, the efficiency is high, the reaction conditions are mild, the operation is easy to control, the cost is low, and the whole process environment friendly.

Description

Nanometer SiO 2Material catalyzed alkene and H 2O 2Liquid phase highly selective epoxidizing method
Technical field
The present invention relates to not use and anyly contain the catalyzer of transition metal-type and only use organic catalyst to prepare the chemical reaction process of epoxide, specifically a kind of nanometer SiO by heterogeneous catalytic oxidation 2Catalytic alkene of material and 30%H 2O 2Liquid phase highly selective epoxidizing method.
Background technology
The alkene epoxidation product is extremely wide organic raw material and an intermediate of a class purposes, is widely used in fields such as petrochemical complex, fine chemistry industry and organic synthesis.Yet except that oxyethane, the production method of present industrial most of epoxy compounds such as propylene oxide, Styryl oxide etc. still is traditional environmentally harmful halogenohydrin method and Halcon method (claiming the indirect oxidation method again).
The high-selectivity oxidation of hydro carbons be 21st century one of most important task [(a) C.L.Hill, Nature 1999,401,436; (b) D.E.de Vos; B.F.Sels; P.A.Jacobs, Adv.Catal.2001,46,1], the catalytic epoxidation of olefin(e) compound under mild conditions is the research emphasis in the field of fine chemical always.For the catalysis epoxidation of alkenes compounds, even phase catalytic process has its significant disadvantages, and separation, recovery and the recirculation of Here it is catalyzer is unusual difficulty.Scientist is making great efforts design always and is preparing suitable heterogeneous catalyst, and this is because such catalyst system is easy to overcome typical case's difficulty that even phase system run into [Z.W.Xi etal., Science 2001,292,1139].Heterogeneous catalyst since its have easily isolating characteristics from reaction system and in chemistry and fine chemistry industry process, play an important role.As everyone knows, the more little catalytic activity that they show of the granularity of heterogeneous catalyst is high more, the catalyzer of nanoscale is owing to have bigger specific surface area, surface exposure has a large amount of avtive spots, reactant molecule can be gone up at nearly " molecular level " with the catalyst activity position fully to be contacted, thereby demonstrate the catalytic activity that is superior to corresponding block materials far away, relevant report is also very many.Kai Fa catalysis epoxidation technology is used 30%H in recent years 2O 2As oxygenant is very general, cheap and easy to get comparatively speaking as oxygenant because of it, and the active o content height, reacted by product only is a water, the feature of environmental protection is good, but oxidation activity is low, needs to add high performance catalyst [K.Jahnisch, V.Hessel, H.Lowe, M.Baerns, Angew.Chem.Int.Ed.2004,43,406].For example Chinese patent CN1172922CGO announced a kind of in the presence of titanium-containing molecular sieve catalyst and a kind of salt the epoxidizing method of alkene and hydroperoxidation, and Chinese patent CN1330642C announced in the presence of a kind of zeolite based catalysts and a kind of solvent, reacted the method for preparing epoxide by alkene and superoxide.In addition, it is reported that phosphorus heteropoly tungstic acid catalyzer can be by reaction effective catalyzing propone of control and H under condition of phase transition 2O 2Epoxidation system oxirane ring propane; SiO 2The metal Schiff-base title complex of load effectively catalyzed ethylene epoxidation generates 1,2-oxyethane; Use cis-MoO 2(L) (solv) composite catalyst epoxidation vinyl benzene under mild conditions of forming of [L=salicyl salicylyl hydrazine] and Y molecular sieve; The Schiff-base title complex of vanadium can effectively styrene catalyzed and tetrahydrobenzene and H 2O 2The epoxidation of oxygenant [(a) S.N.Rao, K.N.Munshi, N.N.Rao, J.Mol.Catal.A:Chem.2000,156,205; (b) D.M.Boghaei; S.Mohebi, J.Mol.Catal.A:Chem.2002,179,41; (c) T.Punniyamurthy; S.Velusamy; J.Iqbal, Chem.Rev.2005,105,2329.].Yet these traditional systems will obtain high catalytic activity, and the reagent that is used for epoxidation reaction of olefines mainly contains peroxy acid, peroxy tert-butyl alcohol, hypochlorite, iodosobenzene, additive+H 2O 2Deng as oxygenant.
Utilizing titanium-silicon molecular sieve catalyst, can the functional quality mark be 30% industrial H 2O 2Make oxygenant, environmentally friendly, so the appearance of titanium containing zeolite catalyst TS-1 and being applied in is described as the milestone of the even phase process heterogenize of tradition at that time; So far this catalyst system has expanded to TS-1, Ti-β, Ti-MWW, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, embedded type Ti-SiO 2Tsing-Hua University etc. all relates to this class research [(a) B.Notari, Adv.Catal.1996,41,23 in, domestic Guo's news, Wu Peng, Li Can, summer; (b) Q.H.Xia, X.Chen, T.Tatsumi, J.Mol.Catal.A:Chem.2001,176,179; (c) P.Wu, T.Tatsumi, Chem.Commun.2001,1714; (d) X.W.Guo, X.S.Wang, Catal.Today 2002,74, and 65; (e) Q.H.Yang, Can Li, J.Catal.1999,183,128.].Comparable best performance different even phase complex compound and the mimetic enzyme catalysis system of intending of the catalytic activity of this catalyst system; And its advantage also be special obviously because these heterogeneous catalysts can and recycle by repeatedly filtered and recycled, and can use 30%H 2O 2As oxygenant, oxidation efficiency height, few, the pollution-free nothing of by product are corroded and are met requirements of green environmental protection, have higher using value.But for the large-scale technological process of chemical industry, the synthetic cost of titanium-containing zeolite is still than higher, and the zeolite molecular sieve in different apertures has substrate molecule and selects the shape selectivity significantly (for example, the TS-1 molecular sieve bore diameter approximately
Figure A20091006217000061
To more macromolecular catalytic reaction poor activity), caused correlation technique to be restricted, so that be difficult to industrialization in the application of field of fine chemical.
The catalytic activity of above-mentioned epoxidation catalyst system is all higher, but the porous synthetic materials active centre that has all related to transition metal complex or containing metal Ti, Mg, Al, the Preparation of catalysts cost is higher, recycle difficulty and easily inactivation, easily cause environmental pollution, too not different aspect the explanation of catalytic mechanism: i.e. transition metal ion and H yet 2O 2Effect forms active intermediate.Silicon-dioxide is as the framework ingredient of inert catalyst carrier and molecular sieve, be widely used in the preparation of heterogeneous catalyst and porous zeolite molecular screen material synthetic, but mention that without any research the silicon-dioxide and other porous silicon-base material that do not contain transition metal have catalytic oxidation activity.Now, we find first, at " SiO 2-alkene-solvent-H 2O 2/ H 2O " in the heterogeneous catalytic reaction system formed, do not contain the nanometer SiO of transition metal 2Material is (through SEM-EDX, ICP, AAS analyzes and not to contain transition metal) adding play a part crucial for significantly improving substrate conversion efficiency and epoxidation selectivity, PRELIMINARY RESULTS shows for functional olefin, cycloolefin and linear alpha-olefin function well, can finely overcome the restriction of traditional zeolitic material duct size shape selectivity, and centrifugation repeatedly, washing, dry, reclaim and use, and substrate conversion efficiency, the epoxidation selectivity all can keep, this is one makes us surprised, interesting discovery, this system is simple, cheapness meets present catalysis technique development trend.
Summary of the invention
The present invention is for overcoming ubiquitous main drawback in the above-mentioned epoxidation systems, and proposes a kind of method of epoxidation of olefins, i.e. nanometer SiO 2Catalytic alkene of material and H 2O 2Liquid phase highly selective epoxidizing method.
Nanometer SiO 2Catalytic alkene and H 2O 2Liquid phase highly selective epoxidizing method, it is to be with nanometer SiO with it 2The activation SiO that has the machine functional group of material or process surface modification 2Material or zeolite molecular sieve directly form " SiO as catalyst for reaction and reaction substrate alkene, solvent 2-alkene-solvent-H 2O 2/ H 2O " EPOXIDATION OF ALKENES CATALYZED BY in the heterogeneous catalyst epoxidation reaction system is H as the epoxidation oxygenant 2O 2Temperature of reaction is controlled at 0～100 ℃, reaction times is 0.5～24h, and described alkene is a kind of in the alkene such as vinylbenzene, tetrahydrobenzene, cyclooctene, norbornylene, α-Pai Xi, beta-pinene, cinnamyl chlorine, methyl acrylate, ethyl propenoate, butyl acrylate, vinylcarbinol, vinyl cyanide, 1-octene.
This method comprises:
(1) different size of particles SiO 2Catalytic alkene and H 2O 2Liquid phase highly selective epoxidizing method;
(2) different sources, different specific surface area, different-grain diameter SiO 2Catalytic alkene and H 2O 2Liquid phase highly selective epoxidizing method;
(3) various SiO 2Handle through the silicate class of different band organic functions base or the suitable modification of other silylating reagent on the powdered material surface, the activation SiO of a series of surfaces band silane functionality group that makes 2Catalytic alkene of material and H 2O 2Liquid phase highly selective epoxidizing method;
(4) the different specific surface areas of various low-cost preparations, the catalytic alkene of zeolite molecular sieve material and the H in different apertures 2O 2Liquid phase highly selective epoxidizing method.
Detailed description of the present invention
In the method for the invention, make nanometer SiO 2Catalytic alkene of material and H 2O 2Liquid phase selective epoxidation reaction, form the epoxidation product of corresponding highly selective.Through a series of catalyzed reactions and relevant characterization research, SiO 2Material catalyzed alkene compound and H 2O 2Epoxidation mechanism may be summarized to be: the promoted bimolecular epoxidation of surface adsorption effect (Surface Adsorption assisted biMolecular Epoxidation (SAME)), promptly these have than higher specific surface area (usually greater than 200m 2/ g) silica-base material surface all has amphipathic (hydrophilic-oleophylic), can be simultaneously with the active oxidizer molecular adsorption of olefin substrate molecule in the organic phase and aqueous phase to together, overcome interfacial tension and made it the initial ring oxidizing reaction.
The high-specific surface area that the present invention uses, the SiO of nanometer particle size 2Material can obtain from following approach: the commodity of the different sizes such as aerosil-200, aerosil-300 of specialized companies such as external Aldrich, the Degussa that (1) is directly bought, Alfa, the specific surface area of these materials is between 200～350m 2/ g, particle diameter is between 10～20nm; (2) directly buy the like product of domestic manufacturer, be commonly called as white carbon black or fumed silica (burn and get), be used for starting material usually as the heteroatoms zeolite molecular sieve of hydro-thermal synthesis of high purity by organic silicon high-temperature; (3) laboratory utilizes ultrasonic, high speed shear, microemulsified environment technology for hydrolyzing from organosilicon, through low temperature hydrolysis, spraying drying, the homemade nanometer SiO of roasting 2Material (granularity is less than 20nm); (4) SiO of surface modification 2Material: the silicate class or other silylating reagent that have the organic functions base below the use (have (EtO) 3Si-C 3H 6NH 2, (MeO) 3Si-C 3H 6NH 2, CH 3(EtO) 2Si-C 3H 6NH 2, (EtO) 3Si-(CH 2) 3-NHC 2H 4NH 2, CH 3Si (OCH 3) 3, (CH 3) 3Si-Cl, HMDS, CH 3(MeO) 2Si-C 3H 6NHC 2H 4NH 2Deng) direct and powder nanometer SiO 2Thereby the material reaction makes its surface carry out suitable modification and handles, and makes the activation SiO that a series of surfaces have the machine functional group 2Material; (5) with the different specific surface areas of the low-cost preparation of simple method, the molecular screen material in different apertures, as materials such as 4A, ZSM-5, mordenite, beta, SBA-15 series, Y, MCM-41 series, MCM-22, SAPOs series, AlPOs series; (6) various types of silicon glue material is as (100-300 orders) such as silica gel for chromatography, the drier gels that dewaters.
In the method for the invention, catalyzed alkene and H 2O 2The reaction solvent of liquid phase selective epoxidation reaction selects all is common solvent, cheap, and easily-controlled reaction conditions.Wherein solvent is one of following: CH 3OH, EtOH, Bu tOH, MeCOMe, MeCOEt, pimelinketone, CH 3CN, DMF, DMA, CHCl 3, CH 2Cl 2, DMSO, hexanaphthene, THF, Ether etc.In addition, cooperate with reaction solvent jointly as epoxidation reaction system additive be that use always, cheap various salts, the mass concentration scope by obtained aqueous solution provides a reaction medium that is more suitable for alkene epoxidation for salts solution and the reaction solvent acting in conjunction of 0.01～1mol/L.Wherein salt is one of following: K 2CO 3, Na 2CO 3, KHCO 3, NaHCO 3, CH 3COONa, CH 3COOK, NaH 2PO 4, Na 2HPO 4, Na 3PO 4, soluble tartrate, soluble tartrate, tartrate receive, microsolubility CaSO 4And MgSO 4Etc. single alkali metal/alkaline-earth metal or mixing salt.
Described H 2O 2With the mol ratio of alkene be 0.5～5.
The volume ratio of the aqueous solution of described solvent and salt is: 3～1/3.
A kind of with among 4A, ZSM-5, mordenite, beta, SBA-15 series, Y, MCM-41 series, MCM-22, SAPOs series and the AlPOs of described catalyst zeolite molecular screening.
Described temperature of reaction is 0～80 ℃
The described reaction times is 0.5～6h.
In the method for the invention, reaction process is very simple, and the epoxidation of the various alkene highly selectivies of catalysis expeditiously, the suitable alkene of selecting the end alkene of straight or branched, interior alkene, the interior alkene of ring-type and band functional group of alkene, patent of the present invention has mainly been chosen alkene such as styrenic, cyclenes hydro carbons, esters of acrylic acid, ketene, linear alpha-olefin class.
The present invention has following advantage:
(1) do not use the catalyzer of any transition metal-type.The present invention only uses commercialization or the homemade nanometer SiO of simple method 2The activation SiO that has the machine functional group of material or process surface modification 2Material or common cheaply zeolite molecular sieve are directly as catalyst for reaction, can bring significant effect, avoid expensive Ti-Si zeolite, the synthetic and last handling process of hydro-thermal of hydrotalcite catalyst, avoided loaded down with trivial details organic synthesis and purifying, the waste of avoiding the transition metal resource and the pollution etc. of organic complex catalyzer.These SiO 2After continue to be used to EPOXIDATION OF ALKENES CATALYZED BY after the simple aftertreatment, activation, recycling is good, saves cost greatly in reaction for material.
(2) conversion of raw material height, good selectivity of target products.The prior art conversion of raw material generally about 60-80%, exists to transform not exclusively, and other byproducts is arranged, and brings difficulty to separation.The present invention under mild conditions, when the broad variety olefin catalytic oxidation is generated epoxide, conversion of raw material height, even can transform fully, and product is the target epoxidation product only, do not have other byproducts, the selectivity of reaction is good, the yield height.
(3) reaction times weak point, the efficient height.Under condition of the present invention, the reaction times that the catalyzed oxidation functional olefines generates epoxide is 0.5～24h, and the preferable reaction times is 0.5～6h, and the method for preparing epoxide with other catalyzed oxidations is compared, has the reaction times weak point, the advantage that reaction efficiency is high.
(4) reaction conditions gentleness, operation is easy to control.The present invention is reflected in the organic solvent and carries out, temperature of reaction is controlled at 0～100 ℃, and temperature is to influence reaction times and important factor optionally, in this catalytic oxidation system, 10 ℃ of the every risings of temperature, speed of reaction just increases by 0.5～2 times, but temperature is too high, can increase energy expenditure, also can cause the selectivity variation that generates target product, make products distribution complicated, by product increases, and therefore must select suitable temperature.
(5) cost is low.Prior art mainly adopts clorox, peroxy acid and alkyl peroxide as oxygenant, and production cost is higher; In the process of reaction, the by product that they generate can cause certain harm and pollution to environment; And they are all unstable, easily decompose, and have transportation, the uneasy congruent shortcoming that stores and use.It is commercially available 30%H that the present invention is used as the epoxidation oxidising agent 2O 2, raw material is cheap and easy to get.Compare as epoxidation reagent with a series of organo-peroxides or clorox etc., have safe in utilizationly, be convenient to advantage such as transportation storage etc.Utilize this invention to provide to such an extent that epoxidizing method does not need specific installation when preparing epoxide, have the reaction conditions gentleness, easy to operate, the characteristics that cost is relatively low have better industrial application prospects.
(6) whole process is environmentally friendly, and reacted organic solvent can pass through the recycling of distillatory method, is a kind of green chemical synthesis method.The raw material that this method consumed is alkene, H 2O 2, product is single epoxide, and flow process is simple, and the oxidant consumption amount is very low, is a new way that is suitable for industrial scale operation.
Embodiment
Below by several specific embodiments technical scheme of the present invention is further described.Following examples do not constitute limitation of the invention.
Embodiment 1:
In the round-bottomed flask of 25ml, successively add solvent acetonitrile, the 5ml 0.2mol/L K of 5ml 2CO 3The aqueous solution, 20mg nanometer SiO 2, 0.21g vinylbenzene (2.0mmol), 0.34g H 2O 2(the n hydrogen peroxide: n vinylbenzene=1.5: 1), reactor is warming up to 60 ℃ of reaction 6h (round-bottomed flask is joined prolong) under quick magnetic agitation then, and SiO is reclaimed in the extraction back for 3.0mmol, 30% aqueous solution 2, washing, vacuum-drying.Solution carries out quantitative analysis with chromatogram.Styrene conversion rate 95.0mol%, epoxide selectivity 99.8%.
Embodiment 2:
In the round-bottomed flask of 50ml, successively add solvent butyl alcohol-tert, the 10ml0.1mol/L NaHCO of 10ml 3The aqueous solution, 50mg nanometer SiO 2, 1.36g norbornylene (10mmol), 1.36g H 2O 2(the n hydrogen peroxide: n vinylbenzene=1.2: 1), reactor is warming up to 60 ℃ of reaction 6h (round-bottomed flask is joined prolong) under quick magnetic agitation then, and SiO is reclaimed in centrifugal back for 12mmol, 30% aqueous solution 2, washing, vacuum-drying.Solution carries out quantitative analysis with chromatogram.Norbornylene transformation efficiency 97.2mol%, epoxide selectivity 100%.
Embodiment 3
In the round-bottomed flask of 500ml, successively add solvent methanol, the 100ml 0.2mol/L Na of 100ml 3PO 4The aqueous solution, 100mg nanometer SiO 2, 11.0g cyclooctene (100mmol), 17.0g H 2O 2(the n hydrogen peroxide: n vinylbenzene=1.5: 1), reactor is warming up to 60 ℃ of reaction 6h (round-bottomed flask is joined prolong) under quick magnetic agitation then, filters the back and reclaims SiO for 150mmol, 30% aqueous solution 2, washing, vacuum-drying.Solution carries out quantitative analysis with chromatogram.Cyclooctene transformation efficiency 95.3mol%, epoxide selectivity 100%.
Embodiment 4
In the round-bottomed flask of 100ml, successively add solvent acetonitrile, the 20ml0.2mol/L CH of 20ml 3The COOK aqueous solution, 150mg ZSM-5 (SiO 2/ Al 2O 3=25), 1.04g vinylbenzene (10mmol), 1.36g H 2O 2(the n hydrogen peroxide: n vinylbenzene=1.2: 1), reactor is warming up to 60 ℃ of reaction 6h (round-bottomed flask is joined prolong) under quick magnetic agitation then, and ZSM-5, washing, vacuum-drying are reclaimed in centrifugal back for 12mmol, 30% aqueous solution.Solution carries out quantitative analysis with chromatogram.Styrene conversion rate 92.5mol%, epoxide selectivity 99.6%.
Embodiment 5
In the round-bottomed flask of 100ml, successively add solvent acetonitrile, the 20ml0.2mol/L MgSO of 20ml 4The aqueous solution, 150mg SBA-15,1.10g cyclooctene (10mmol), 1.36g H 2O 2(the n hydrogen peroxide: n vinylbenzene=1.2: 1), reactor is warming up to 60 ℃ of reaction 6h (round-bottomed flask is joined prolong) under quick magnetic agitation then, and SBA-15, washing, vacuum-drying are reclaimed in centrifugal back for 12mmol, 30% aqueous solution.Solution carries out quantitative analysis with chromatogram.Cyclooctene transformation efficiency 98.3mol%, epoxide selectivity 100%.
Embodiment 6～22
Form with form provides representational embodiment below, preferred commercialization of catalyzer or the homemade nanometer SiO of simple method 2The activation SiO that has the machine functional group of material or process surface modification 2Material or common cheaply zeolite molecular sieve, alkene such as alkene optimization styrene, tetrahydrobenzene, cyclooctene, norbornylene, α-Pai Xi, beta-pinene, cinnamyl chlorine, methyl acrylate, ethyl propenoate, butyl acrylate, vinylcarbinol, vinyl cyanide, 1-octene.Embodiment 6 is blank reaction experiment example, does not promptly add catalyst S iO 2, its experimental technique and step are followed embodiment 1-5; The experimental technique of embodiment 7～22 and step are followed embodiment 1-5 equally, 100mg SiO 2Or zeolite molecular sieve, the solvent acetonitrile of 50ml, 50ml salts solution (concentration range is 0.05～1mol/L), these as a result example do not constitute limitation of the invention.
Embodiment Alkene N hydrogen peroxide: n alkene Olefin conversion (mol%) Epoxy selectivity (%)
6 Vinylbenzene 1.5 17.1 76.4
7 Vinylbenzene 1.0 85.2 99.8
8 Vinylbenzene 1.5 100 100
9 Tetrahydrobenzene 1.0 82.3 100
10 Tetrahydrobenzene 1.5 95.4 100
11 Cyclooctene 1.0 90.0 100
12 Cyclooctene 1.5 99.2 100
13 Norbornylene 1.0 97.2 100
14 α-Pai Xi 1.5 81.5 95.2
15 Beta-pinene 1.5 80.2 90.1
16 β-cinnamyl chlorine 1.5 85.3 91.5
17 Methyl acrylate 1.5 91.5 100
18 Ethyl propenoate 1.5 95.6 100
19 Butyl acrylate 1.0 92.3 100
20 Vinylcarbinol 1.5 73.2 80.4
21 Vinyl cyanide 1.5 76.5 96.5
22 The 1-octene 1.5 99.7 100
Show by above-mentioned example as a result, according to reaction conditions provided by the present invention, can be optionally substrate widely be oxidized to epoxide, this method has the reaction conditions gentleness, operation is easy to control, the feed stock conversion height, good selectivity of target products, the reaction times is short, the efficient height, cost is low, and the characteristics of whole process environment-friendly and green have application promise in clinical practice.

Claims (9)

1、一种纳米SiO2材料催化烯烃与H2O2液相高选择性环氧化方法，它是将纳米SiO2材料、或经过表面改性的带有机功能基的活化SiO2材料、或者沸石分子筛直接作为反应的催化剂，和反应底物烯烃、溶剂形成SiO2-烯烃-溶剂-H2O2/H2O多相催化环氧化反应体系中催化烯烃环氧化反应，用作环氧化氧化剂是H2O2，反应温度控制在0～100℃，反应时间为0.5～24h，所述烯烃为苯乙烯、环己烯、环辛烯、降冰片烯、α-蒎烯、β-蒎烯、肉桂基氯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯醇、丙烯腈、1-辛烯等烯烃中的一种。1. A nano-SiO 2 material catalyzes olefin and H 2 O 2 liquid-phase high-selectivity epoxidation method, it is nano-SiO 2 material, or activated SiO 2 material with organic functional groups through surface modification, or The zeolite molecular sieve is directly used as the catalyst of the reaction, and the reaction substrate olefin and the solvent form SiO 2 -alkene-solvent-H 2 O 2 /H 2 O heterogeneous catalytic epoxidation reaction system to catalyze the epoxidation reaction of olefins, and is used as an epoxidation reaction system. The oxidation oxidizing agent is H 2 O 2 , the reaction temperature is controlled at 0-100°C, and the reaction time is 0.5-24 hours. The olefins are styrene, cyclohexene, cyclooctene, norbornene, α-pinene, β - One of olefins such as pinene, cinnamyl chloride, methyl acrylate, ethyl acrylate, butyl acrylate, allyl alcohol, acrylonitrile, and 1-octene. 2、如权利要求1所述纳米SiO2材料催化烯烃与H2O2液相高选择性环氧化方法，其特征是所述的催化剂沸石分子筛选用4A、ZSM-5、丝光沸石、beta、SBA-15系列、Y、MCM-41系列、MCM-22、SAPOs系列和AlPOs中的一种。2. The nano-SiO 2 material catalyzed olefin and H 2 O 2 liquid-phase highly selective epoxidation method as claimed in claim 1, characterized in that the catalyst zeolite molecular screening is 4A, ZSM-5, mordenite, beta, One of SBA-15 series, Y, MCM-41 series, MCM-22, SAPOs series and AlPOs. 3、如权利要求1所述纳米SiO2材料催化的烯烃与H2O2液相高选择性环氧化方法，其特征是：所述的有机溶剂为CH3OH、EtOH、ButOH、MeCOMe、MeCOEt、环己酮、CH3CN、DMF、DMA、CHCl3、CH2Cl2、DMSO、环己烷、THF和Ether中的一种。3. The liquid-phase highly selective epoxidation method of olefins and H 2 O 2 catalyzed by nano-SiO 2 materials as claimed in claim 1, characterized in that: the organic solvent is CH 3 OH, EtOH, But OH, One of MeCOMe, MeCOEt, cyclohexanone, CH 3 CN, DMF, DMA, CHCl 3 , CH 2 Cl 2 , DMSO, cyclohexane, THF and Ether. 4、如权利要求1所述纳米SiO2材料催化烯烃与H2O2液相高选择性环氧化方法，其特征是：在反应体系中与反应溶剂配合共同作为环氧化反应体系中还添加有盐类添加剂，其中添加剂选择K2CO3、Na2CO3、KHCO3、NaHCO3、CH3COONa、CH3COOK、NaH2PO4、Na2HPO4、Na3PO4、酒石酸钾、酒石酸钾、酒石酸纳、微溶性CaSO4和MgSO4中的单一碱金属或碱土金属或混合盐类。4. The nano- SiO2 material catalyzed liquid-phase high-selectivity epoxidation method of olefins and H2O2 as claimed in claim 1, which is characterized in that: in the reaction system, it cooperates with the reaction solvent as the epoxidation reaction system. Salt additives are added, among which the additives are K 2 CO 3 , Na 2 CO 3 , KHCO 3 , NaHCO 3 , CH 3 COONa, CH 3 COOK, NaH 2 PO 4 , Na 2 HPO 4 , Na 3 PO 4 , potassium tartrate , Potassium tartrate, sodium tartrate, single alkali metal or alkaline earth metal or mixed salts in slightly soluble CaSO 4 and MgSO 4 . 5、如权利要求1所述纳米SiO2材料催化烯烃与H2O2液相高选择性环氧化方法，其特征在于：所述反应温度为0～80℃。5. The nano-SiO 2 material catalyzed liquid-phase high-selectivity epoxidation method of olefins and H 2 O 2 as claimed in claim 1, characterized in that: the reaction temperature is 0-80°C. 6、如权利要求1所述纳米SiO2材料催化烯烃与H2O2液相高选择性环氧化方法，其特征是：所述反应时间为0.5～6h。6. The nano-SiO 2 material catalyzed liquid-phase high-selectivity epoxidation method of olefins and H 2 O 2 as claimed in claim 1, characterized in that: the reaction time is 0.5-6 hours. 7、如权利要求1所述纳米SiO2材料催化烯烃与H2O2液相高选择性环氧化方法，其特征是：所述盐类添加剂是盐的水溶液，水溶液的质量浓度范围为0.01～1mol/L。7. The nano- SiO2 material catalyzed liquid-phase highly selective epoxidation method of olefins and H2O2 according to claim 1, characterized in that: the salt additive is an aqueous solution of salt, and the mass concentration range of the aqueous solution is 0.01 ~1mol/L. 8、如权利要求1所述纳米SiO2材料催化烯烃与H2O2液相高选择性环氧化方法，其特征是：所述H2O2和烯烃的摩尔比为0.5～5。8. The nano-SiO 2 material catalyzed liquid-phase highly selective epoxidation method of olefins and H 2 O 2 as claimed in claim 1, characterized in that: the molar ratio of H 2 O 2 to olefins is 0.5-5. 9、如权利要求6所述纳米SiO2材料催化烯烃与H2O2液相高选择性环氧化方法，其特征是：所述溶剂和盐的水溶液的体积比为：3～1/3。9. The nano-SiO 2 material catalyzed liquid-phase high-selectivity epoxidation method of olefins and H 2 O 2 as claimed in claim 6, characterized in that: the volume ratio of the solvent and the aqueous salt solution is: 3-1/3 .
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