CN109772451A - Olefin epoxidation process - Google Patents
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Abstract
The step of the present invention relates to a kind of olefin epoxidation process, are included under epoxidation reaction condition, and alkene and oxidant and ion-exchange resin catalyst contact；The ion-exchange resin catalyst has following structure general formula:Wherein,For macroporous type nanocomposite resin matrix；M‑For anion, it is selected from phosphotungstic acid root, phosphomolybdic acid root, silico-tungstic acid root, silicomolybdic acid root, arsenowolframic acid root, arsenic molybdate, germanotungstic acid root, germanium molybdate, tungstovanadophosphoric acid root or molybdovanaphosphoric acid root；POSS is cage-type silsesquioxane unit；
Description
Technical field
The present invention relates to a kind of olefin epoxidation process.
Background technique
Intermediate of the epoxide as a kind of important industrial chemicals and organic reaction, is widely used in petroleum
The various fields such as work, fine chemistry industry, organic synthesis, pharmacy, fragrance.The epoxides of light alkene is important substantially organic original
Material, such as ethylene oxide, propylene oxide, they play very important effect in the industrial productions such as polyester and polyethers.It is advanced
The epoxides of alkene is then the important intermediate of fine chemistry industry, such as 7-oxa-bicyclo[4.1.0, octylene oxide and norbornene epoxidation
Object etc..Epoxidation reaction of olefines is one of the main path for industrially preparing epoxide.Due to most olefin epoxides
Change is required to catalyst, therefore selecting environmental-friendly, simple process, lower-cost catalyst is the pass of alkene epoxidation technology
Key.
Alkene epoxidation catalysis reaction is generally divided into homogeneous catalysis and heterogeneous catalysis two major classes.Representative homogeneous catalysis
Agent system includes that various metals (such as molybdenum, tungsten, manganese) complex, polyoxometallate and its derivative (mainly include various types of
Isopolyacid, heteropoly acid and its salt of type).Wherein homogeneous molybdenum match catalyst has been successfully applied in epoxidation of propylene industry
(Halcom method).
Due to good dissolubility, heteropoly acid can be used as homogeneous catalyst use.Though activity is good, high-efficient, selectivity is good,
But it is difficult to recycle, high production cost, environmental problem is prominent.Therefore easily separated recycling, reusable heterogeneous catalysis are found
Agent, which then seems, to be even more important.
Xi Zuwei etc. reports quaternary phosphorus tungsten heteropoly compound Q3[PW4O16] (Q=quaternary ammonium salt, such as [π-C5H5N+
(CH2)15CH3Cl] etc.), with H2O2Or generated in-situ H2O2It can efficient catalytic propylene, ring under the conditions of relatively mild for oxygen source
The epoxidation of a variety of alkene such as alkene, 1- octene, styrene, the conversion ratio of alkene and the selection rate of epoxides are mostly 90%
Left and right.For alkene relative to hydrogen peroxide excess, catalyst itself is insoluble, but and H in the reaction system in reaction process2O2
It is soon dissolved in after reaction in the solution of reaction, homogeneously carries out EPOXIDATION OF ALKENES CATALYZED BY；Work as H2O2After ruing out of, catalyst
Can from reaction system Precipitation, be recovered by filtration and can be recycled (XiZ, zhou N, Sun Y, et al.Science,
2001,292:1139-1141.)。
Majid Moghadam etc. is prepared for heteropolyacid-based Mo-salen heterogeneous catalysis, Mo-salen homogeneous catalysis
Agent, and they are respectively applied in the epoxidation reaction of olefines of tertbutanol peroxide participation, experiment discovery is heteropolyacid-based non-equal
Phase catalyst have higher epoxide yield (Moghadam, M., Mirkhani, V., Tangestaninejad, S.,
Mohammadpoor Baltork,I.,Javadi,M.M.Polyhedron,2014,29,648-654)。
Jacobs is reported { PO4[WO(O2)2]4}3-It is fixed on the ring that propenyl and terpenes are used on ion exchange resin
Oxidation reaction, catalyst circulation still keep very high catalytic activity (VillaA, Sels B, De V D, et al.J after several times
Org Chem,999,64(19):7267-7270).Neumann is by { PO4[WO(O2)2]4}3-It is immobilized on by phenyl and quaternary ammonium group
On the silicate xerogel that group is modified with covalent bond, it is immobilized after catalyst can be used in the case where room temperature, organic solvent-free
30% H2O2Make alkene epoxidation (Neumann R, Miller H.Chem Commun, 1995 (22): 2277-2278).
12- phosphomolybdic acid is immobilized on mesoporous material SBA-15 and SBA-3 by Karimi et al. respectively, passes through carrier surface
Acid-base reaction occurs for Si-OH and phosphomolybdic acid, is realized in the form of ion pair immobilized.Wherein SBA-15 is because of opposite large specific surface area,
Aperture is big, and the performance in cyclo-octene epoxidation reaction is better than the performance of SBA-3.But the stability of such catalyst is not
Good, repeat performance is bad, need to further graft on matrix aminopropyl using surface modification, increase between ion pair
It interacts (Karimi Z.Mahjoub A R.Harati S M.Inorg Chim Acta, 2011,376:1-9).
It is carrier that Kholdeeva et al., which is reported using MIL-101, by [PW11CoO39]5-Or [PW11TiO40]5-By quiet
Electric power, which acts on, obtains corresponding catalyst in the immobilized nanocages to carrier, wherein Ti-POM/MIL-101 can effectively be catalyzed with
Hydrogen peroxide is the carypohyllene epoxidation of oxygen source and the selective epoxidation of australene, and Co-POM/MIL-101 is then with oxygen
Good activity is shown in selective epoxidation reaction for the australene of oxygen source.But this kind of catalyst can only be mild
It is reacted under reaction condition, otherwise the structure of carrier MIL-101 can decompose (Maksimchuk N V.Timofeeva M
N.Kholdeeva O A, et al.J Catal, 2008,257:315-323).
The catalytic activity of immobilized AlCl_3 catalyst depends not only on the performance of heteropoly acid itself, additionally depends on the various property of carrier
Can, such as heat resistance, solvent resistance, porosity etc..It can be seen that designing a kind of with easily separated, high activity, recycling
The epoxidation reaction of olefines catalyst of function admirable is of crucial importance.
Summary of the invention
The present invention provides a kind of olefin epoxidation process.The method includes under epoxidation reaction condition, alkene and oxygen
The step of agent and ion-exchange resin catalyst contact；The ion-exchange resin catalyst has following structure general formula:
Wherein,For macroporous type nanocomposite resin matrix；
M-For anion, selected from phosphotungstic acid root, phosphomolybdic acid root, silico-tungstic acid root, silicomolybdic acid root, arsenowolframic acid root, arsenic molybdate,
Germanotungstic acid root, germanium molybdate, tungstovanadophosphoric acid root or molybdovanaphosphoric acid root；
POSS is cage-type silsesquioxane unit, and general formula is (- SiO1.5)m；M is 6,8,10 or 12；
For glyoxaline cation unit；
Linking group of the R between POSS unit and glyoxaline cation unit, R are alkylidene or arylene；
The macroporous type nanocomposite resin matrix is styrene monomer, comonomer, nano material and pore-foaming agent warp
The nanometer macroporous type copolymer that in-situ copolymerization obtains；The nano material is selected from single-layer graphene, multi-layer graphene, graphite oxide
At least one of alkene, graphite alkene.
According to an aspect of the present invention, content of the POSS unit in the ion exchange resin is 2~8 weight %.
According to an aspect of the present invention, M-For phosphotungstic acid radical ion.
According to an aspect of the present invention, alkylidene is selected from methylene, ethylidene or propylidene；Arylene is selected from sub- benzene
Base, naphthylene or sub- benzyl.
According to an aspect of the present invention, the styrene monomer is selected from styrene, α-methylstyrene or 4- butyl
At least one of styrene, optimization styrene.
According to an aspect of the present invention, the comonomer be selected from ethyleneglycol dimethyacrylate, diallyl benzene,
At least one of divinyl phenylmethane or divinylbenzene, preferably divinylbenzene.
According to an aspect of the present invention, the pore-foaming agent is selected from aliphatic hydrocarbon, polystyrene, gasoline, poly- (propylene glycol), gathers
At least one of (ethylene glycol), dimethyl silicone polymer, fatty acid or paraffin, preferably polystyrene.
According to an aspect of the present invention, the dosage of styrene monomer is 85~95 parts, the dosage of comonomer is 2~
5 parts, the dosage of nano material is 0.1~3 part, and the dosage of pore-foaming agent is 10~100 parts.
According to an aspect of the present invention, the preferred multi-layer graphene of the nano material.
According to an aspect of the present invention, the alkene be selected from styrene, 1- butylene, cyclopentene, cyclohexene, cyclo-octene,
Any one of n-hexylene, positive octene, dipentene, australene.
According to an aspect of the present invention, the oxidant appointing in hydrogen peroxide, alkyl hydroperoxide compounds
What is a kind of.For example, tert-butyl hydroperoxide.
According to an aspect of the present invention, it is 1 that the epoxidation reaction condition, which includes: the molar ratio of alkene and oxidant:
10~10:1, catalyst amount be alkene quality 0.1~15%, 40~100 DEG C of reaction temperature, the reaction time 1~24 hour.
The preparation method of heretofore described ion-exchange resin catalyst, comprising the following steps:
A) auxiliary agent is made into the water solution A that weight percent concentration is 0.5~2%, styrene monomer, copolymerization is single
Body, nano material, initiator and pore-foaming agent wiring solution-forming B；Wherein, the styrene monomer is selected from styrene, Alpha-Methyl benzene
At least one of ethylene or 4- butylstyrene；The comonomer is selected from ethyleneglycol dimethyacrylate, diallyl
At least one of benzene, divinyl phenylmethane or divinylbenzene；The nano material is selected from single-layer graphene, multilayer stone
At least one of black alkene, graphene oxide, graphite alkene；The initiator is selected from benzoyl peroxide, azodiisobutyronitrile, mistake
Aoxidize at least one of lauroyl or isopropyl benzene hydroperoxide；The pore-foaming agent is selected from aliphatic hydrocarbon, polystyrene, gasoline, gathers
At least one of (propylene glycol), poly(ethylene glycol), dimethyl silicone polymer, fatty acid or paraffin；The auxiliary agent is selected from poly- second
At least one of enol, gelatin, starch, methylcellulose, bentonite or calcium carbonate；Based on parts by weight, styrene monomer
Dosage be 85~95 parts, the dosage of comonomer is 2~5 parts, and the dosage of nano material is 0.1~3 part, the dosage of initiator
It is 0.1~10 part；The dosage of pore-foaming agent is 10~100 parts；The dosage of auxiliary agent is the 150~400% of monomer dosage；
B) by solution B 60~75 DEG C prepolymerization 0.5~2.5 hour, solution B is mixed with solution A then, is warming up to 70
~90 DEG C are reacted 5~15 hours, then are warming up to 90~100 DEG C and are reacted 5~15 hours；After reaction, through extracting, washing, mistake
Filter, dry, sieving, obtain 0.35~0.60 millimeter of particle size range of compound macroporous microsphere；
C) make the compound macroporous microsphere chloromethylation: being added in compound macroporous microsphere and be equivalent to compound macroporous microsphere weight
The chloromethylation reagents of amount 200~500%, and it is equivalent to the zinc chloride catalyst of compound macroporous microsphere weight 20~70%,
It is reacted 8~30 hours at 30~60 DEG C, is filtered, washed to obtain compound macropore chlorine ball；The chloromethylation reagents are selected from chlorine
At least one of methyl ether, dichloroethyl ether or Isosorbide-5-Nitrae-dichloro methyl butyl ether；
D) it by the compound macropore chlorine ball, the mixture of imidazoles and acetonitrile, is reacted at 60~90 DEG C, obtains compound imidazoles
Microballoon；In the mixture, the molar ratio of compound macropore chlorine ball, imidazoles and acetonitrile is 1:(1~2): (30~150)；
E) by the POSS compound of the compound imidazoles microballoon and halogenated alkyl according to imidazole functionalities and halogenated functional group
Equimolar mixing, is dissolved in tetrahydrofuran, 24~72 hours at 100 DEG C, filters after reaction, and washing obtains compound miaow
Azoles/POSS microballoon；The POSS compound of the halogenated alkyl is selected from eight chloromethyl POSS, eight chloroethyl POSS, eight chloropropyls
At least one of POSS；
F) the compound imidazoles/POSS microballoon brine, wherein compound imidazoles/POSS microballoon and salting liquid rub
You are than being (1:1)~(1:10)；The concentration of salting liquid is 0.1~1mol/L；It is washed with deionized after washing to pH=
7, obtain the ion exchange resin.The salting liquid is selected from phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid, arsenowolframic acid, arsenic molybdenum
At least one of acid, germanotungstic acid, germanium molybdic acid, tungstovanadophosphoric acid, molybdovanaphosphoric acid salting liquid.
Beneficial effects of the present invention: the ion-exchange resin catalyst in the present invention contains two different nano materials: receiving
Rice carbon material and cage-type silsesquioxane (Polyhedral oligomeric silsesquioxanes, abbreviation POSS).Nanometer
Carbon material and monomer, comonomer are introduced into resin matrix by in-situ polymerization under initiator effect, improve resin base
The glass transition temperature of body；Simultaneously because the introducing of nano-carbon material, increases the resistance to swelling energy of resin matrix.And POSS
Comprising the inorganic supporting structure being made of Si and O, the good heat resistance of ion exchange resin is imparted, thermal stability significantly mentions
It is high.The preferred solution of the invention is the macroporous type copolymer in situ of the styrene of chloromethylation, divinylbenzene and multi-layer graphene
Resin matrix is reacted with imidazoles, obtains compound imidazoles microballoon, and then the POSS compound by imidazole group and halogenated alkyl is anti-
It answers, finally carries out ion-exchange reactions with salting liquid again, the macroporous type ion exchange containing two kinds of different nano materials is prepared
Resin.It is reacted by the in-situ copolymerization between graphene and monomer, comonomer and realizes the covalent of graphene and polymeric matrix
In conjunction with, and pass through the knot between halogenated alkyl POSS compound and the chemical reaction realization POSS and resin matrix of imidazole group
It closes.
The gel-type ion-exchange resin catalyst containing two kinds of different nano materials in the present invention is for alkene and oxidation
The epoxidation reaction of agent, has the advantage that
(1) catalytic activity is high；
(2) the easily separated recycling of catalyst, stability is good, reusable.
The present invention will be further described below by way of examples, it should be noted however that protection model of the invention
It encloses not that this is limited by this, but is determined by the appended claims.
It should be strongly noted that two or more aspects (or embodiment) disclosed in the context of the present specification
Any combination, the technical solution formed therefrom it can belong to a part of this specification original disclosure each other, while
It falls under the scope of the present invention.
Specific embodiment
The preparation of [embodiment 1] ion-exchange resin catalyst
47.0 grams of styrene, 2.3 grams of divinylbenzenes, 30 grams of polystyrene and 1.6 are added in 500 milliliters of three-necked flasks
Gram benzoyl peroxide initiator, is stirred to react 1.5 hours at 60 DEG C；Then 0.6 gram of multi-layer graphene is added, continues to stir
Progress prepolymerization in 1 hour.The 260 ml deionized water solution for being dissolved with 2.0 grams of gelatin are added.Mixing speed is adjusted, simultaneously
80 DEG C are gradually warming up to, is reacted 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 8 hours.Reaction
After, supernatant liquid is poured out, is washed with 85 DEG C of hot water, then washed with cold water, is then filtered, is put into 80 DEG C of bakings in baking oven
It is dry, sieving, compound macroporous microsphere A1 of the collection cut size within the scope of 0.35~0.60mm.
Compound macroporous microsphere chloromethylation: in the three-necked flask of 500ml, be added 40 grams of compound macroporous microsphere A1 and
200ml chloromethyl ether is stored at room temperature 3 hours, starts to stir, and it is catalyst that 15 grams of zinc chloride, which are added, and it is small to be warming up to 50 DEG C of reactions 12
When, it is cooled to room temperature after chloromethylation, filters out chlorination mother solution, washed repeatedly with methanol, dry 8 hours, obtain at 100 DEG C
To compound macropore chlorine ball A1.
30 grams of compound macropore chlorine ball A1 (chlorinity 3.3mmolCl/g), imidazoles are added in 500ml there-necked flask
(99.0mmol) and 200ml acetonitrile, reacts 24 hours at 80 DEG C, are cooled to room temperature, and filter, successively use ethyl acetate,
The HCl of 0.1mol/L, deionized water, methanol washing, then 60 DEG C of vacuum bakings obtain compound imidazoles microballoon A1 in 12 hours.
In 500ml three-necked flask, the compound imidazoles microballoon A2 of 30 grams of addition (imidazole group content is 3.0mmol/g), 9.4
Gram eight chloromethyl silsesquioxanes and 300ml tetrahydrofuran filter after reaction 24 hours at 100 DEG C, with tetrahydro furan
Mutter, deionized water is successively washed, obtain compound imidazoles/POSS microballoon A1.
In 1000ml three-necked flask, it is 0.1mol/L's that 30 grams of compound imidazoles/POSS microballoon A1,500ml concentration, which is added,
Progress ion-exchange reactions 24 hours is stirred at room temperature in the deionized water solution of sodium phosphotungstate；It is then washed with deionized straight
To washing lotion pH=7, the ion-exchange resin catalyst of the different nano materials of of the invention two kinds is obtained after vacuum drying, is denoted as
Cat-A1, wherein POSS unit content is 4.0%, and structural formula is as follows:
The preparation of [embodiment 2] ion-exchange resin catalyst
In 500 milliliters of three-necked flasks be added containing initiator monomer mixture solution (60.0 grams of styrene, 1.0 grams
Divinylbenzene, 60 grams of polystyrene, 1.6 grams of multi-layer graphenes and 1.0 grams of benzoyl peroxides, the solution are stirred prior to 70 DEG C
Reaction 0.5 hour), blender is started, the mixed solution of 200 ml deionized waters and 4 grams of polyvinyl alcohol is added, is warming up to 85
DEG C, it reacts 3 hours, then be warming up to 90 DEG C, reacts 9 hours, be finally warming up to 100 DEG C, react 10 hours.After reaction, incline
Supernatant liquid is poured out, is washed with 85 DEG C of hot water, then washed with cold water, is then filtered, 80 DEG C of drying in baking oven is put into, is sieved, receive
Collect compound macroporous microsphere B1 of the partial size within the scope of 0.35~0.60 millimeter.
The chloromethylation of complex microsphere: in 500 milliliters of three-necked flask, 50 grams of complex microsphere B1 and 200 milliliters are added
Dichloroethyl ether is stored at room temperature 6 hours, and it is catalyst that 30 grams of zinc chloride, which are added, starts to stir, and is warming up to 50 DEG C and is reacted 24 hours, chlorine
It is cooled to room temperature after methylation, filters out chlorination mother solution, washed repeatedly with methanol, dried 8 hours, answered at 100 DEG C
Close macropore chlorine ball B1.
50 grams of compound macropore chlorine ball B (chlorinity 4.3mmolCl/g), imidazoles are added in 500ml there-necked flask
(215.0mmol) and 300ml acetonitrile, reacts 16 hours at 80 DEG C, are cooled to room temperature, and filter, successively use ethyl acetate,
The HCl of 0.1mol/L, deionized water, methanol washing, then 60 DEG C of vacuum bakings obtain compound imidazoles microballoon B1 in 12 hours.
In 1000ml three-necked flask, 50 grams of compound imidazoles microballoon B1 (imidazole group content is 3.8mmol/g) are added,
19.3 gram of eight chloromethyl silsesquioxane and 500ml tetrahydrofuran filter after reaction 72 hours at 100 DEG C, with four
Hydrogen furans, deionized water are successively washed, and compound imidazoles/POSS microballoon B1 is obtained.
In 1000ml three-necked flask, it is 1.0mol/L's that 40 grams of compound imidazoles/POSS microballoon B1,400ml concentration, which is added,
Progress ion-exchange reactions 12 hours is stirred at room temperature in the deionized water solution of sodium phosphotungstate；It is then washed with deionized straight
To washing lotion pH=7, the ion-exchange resin catalyst of the different nano materials of of the invention two kinds is obtained after vacuum drying, is denoted as
Cat-B1, wherein POSS unit content is 4.3%, and structural formula is as follows:
The preparation of [embodiment 3] ion-exchange resin catalyst
In 500 milliliters of three-necked flasks be added containing initiator monomer mixture solution (42.5 grams of styrene, 2.5 grams
Divinylbenzene, 10 grams of polystyrene, 0.1 gram of multi-layer graphene and 2.0 grams of benzoyl peroxides, the solution are stirred prior to 70 DEG C
Reaction 1.5 hours), the mixed solution of 200 ml deionized waters and 4 grams of polyvinyl alcohol is added, is warming up to 85 DEG C, reacts 3 hours,
It is warming up to 90 DEG C again, reacts 9 hours, is finally warming up to 100 DEG C, reacts 10 hours.After reaction, supernatant liquid is poured out,
Washed with 85 DEG C of hot water, then washed with cold water, then filtered, be put into baking oven 80 DEG C of drying, sieving, collection cut size 0.35~
Compound macroporous microsphere C1 within the scope of 0.60 millimeter.
The chloromethylation of complex microsphere: in 250 milliliters of three-necked flask, 20 grams of complex microsphere C1 and 100 milliliters are added
Isosorbide-5-Nitrae-dichloro methyl butyl ether is stored at room temperature 6 hours, and it is catalyst that 8 grams of zinc chloride, which are added, starts to stir, and is warming up to 30 DEG C instead
It answers 10 hours, is cooled to room temperature after chloromethylation, filters out chlorination mother solution, washed repeatedly with methanol, dry 8 at 100 DEG C
Hour, obtain compound macropore chlorine ball C1.
20 grams of compound macropore chlorine ball C1 (chlorinity 1.4mmolCl/g), imidazoles are added in 250ml there-necked flask
(28.0mmol) and 150ml acetonitrile, reacts 16 hours at 90 DEG C, are cooled to room temperature, and filter, successively use ethyl acetate,
The HCl of 0.1mol/L, deionized water, methanol washing, then 60 DEG C of vacuum bakings obtain compound imidazoles microballoon C1 in 12 hours.
In 250ml three-necked flask, the compound imidazoles microballoon C1 of 20 grams of addition (imidazole group content is 1.3mmol/g), 3.0
Gram eight chloroethyl silsesquioxanes and 150ml tetrahydrofuran filter after reaction 72 hours at 100 DEG C, with tetrahydro furan
Mutter, deionized water is successively washed, obtain compound imidazoles/POSS microballoon C1.
In 500ml three-necked flask, the phosphorus that 20 grams of compound imidazoles/POSS microballoon C1,300ml concentration is 0.5mol/L is added
Progress ion-exchange reactions 12 hours is stirred at room temperature in the deionized water solution of sodium tungstate；Then be washed with deionized until
Washing lotion pH=7 obtains the ion-exchange resin catalyst of the different nano materials of of the invention two kinds, is denoted as Cat- after vacuum drying
C1, wherein POSS unit content is 3.0%, and structural formula is as follows:
The preparation of [embodiment 4] ion-exchange resin catalyst
47.0 grams of styrene, 2.3 grams of divinylbenzenes, 40 grams of polystyrene and 1.6 are added in 500 milliliters of three-necked flasks
Gram benzoyl peroxide initiator, is stirred to react 2.0 hours at 60 DEG C；Then 0.6 gram of single-layer graphene is added, continues to stir
Progress prepolymerization in 1 hour.The 260 ml deionized water solution for being dissolved with 2.0 grams of gelatin are added.Mixing speed is adjusted, simultaneously
80 DEG C are gradually warming up to, is reacted 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 6 hours.Reaction
After, supernatant liquid is poured out, is washed with 85 DEG C of hot water, then washed with cold water, is then filtered, is put into 80 DEG C of bakings in baking oven
It is dry, sieving, compound macroporous microsphere A2 of the collection cut size within the scope of 0.35~0.60mm.
Compound macroporous microsphere chloromethylation: in the three-necked flask of 500ml, be added 40 grams of compound macroporous microsphere A2 and
200ml chloromethyl ether is stored at room temperature 3 hours, starts to stir, and it is catalyst that 20 grams of zinc chloride, which are added, and it is small to be warming up to 60 DEG C of reactions 10
When, it is cooled to room temperature after chloromethylation, filters out chlorination mother solution, washed repeatedly with methanol, dry 8 hours, obtain at 100 DEG C
To compound macropore chlorine ball A2.
30 grams of compound macropore chlorine ball A2 (chlorinity 3.4mmolCl/g), imidazoles are added in 500ml there-necked flask
(102.0mmol) and 200ml acetonitrile, reacts 24 hours at 70 DEG C, are cooled to room temperature, and filter, successively use ethyl acetate,
The HCl of 0.1mol/L, deionized water, methanol washing, then 60 DEG C of vacuum bakings obtain compound imidazoles microballoon A2 in 12 hours.
In 500ml three-necked flask, the compound imidazoles microballoon A2 of 30 grams of addition (imidazole group content is 3.1mmol/g), 9.4
Gram eight chloromethyl silsesquioxanes and 300ml tetrahydrofuran filter after reaction 24 hours at 100 DEG C, with tetrahydro furan
Mutter, deionized water is successively washed, obtain compound imidazoles/POSS microballoon A2.
In 1000ml three-necked flask, it is 0.1mol/L's that 30 grams of compound imidazoles/POSS microballoon A2,500ml concentration, which is added,
Progress ion-exchange reactions 24 hours is stirred at room temperature in the deionized water solution of sodium phosphotungstate；It is then washed with deionized straight
To washing lotion pH=7, the ion-exchange resin catalyst of the different nano materials of of the invention two kinds is obtained after vacuum drying, is denoted as
Cat-A2, wherein POSS unit content is 4.1%, and structural formula is as follows:
The preparation of [embodiment 5] ion-exchange resin catalyst
In 500 milliliters of three-necked flasks be added containing initiator monomer mixture solution (60.0 grams of styrene, 1.0 grams
Divinylbenzene, 60 grams of polystyrene, 1.6 grams of single-layer graphenes and 1.0 grams of benzoyl peroxides, the solution are stirred prior to 70 DEG C
Reaction 0.5 hour), blender is started, the mixed solution of 200 ml deionized waters and 4 grams of polyvinyl alcohol is added, is warming up to 85
DEG C, it reacts 3 hours, then be warming up to 90 DEG C, reacts 9 hours, be finally warming up to 100 DEG C, react 10 hours.After reaction, incline
Supernatant liquid is poured out, is washed with 85 DEG C of hot water, then washed with cold water, is then filtered, 80 DEG C of drying in baking oven is put into, is sieved, receive
Collect compound macroporous microsphere B2 of the partial size within the scope of 0.35~0.60 millimeter.
The chloromethylation of complex microsphere: in 500 milliliters of three-necked flask, 50 grams of complex microsphere B2 and 200 milliliters are added
Dichloroethyl ether is stored at room temperature 6 hours, and it is catalyst that 30 grams of zinc chloride, which are added, starts to stir, and is warming up to 50 DEG C and is reacted 30 hours, chlorine
It is cooled to room temperature after methylation, filters out chlorination mother solution, washed repeatedly with methanol, dried 8 hours, answered at 100 DEG C
Close macropore chlorine ball B2.
50 grams of compound macropore chlorine ball B2 (chlorinity 4.5mmolCl/g), imidazoles are added in 500ml there-necked flask
(225.0mmol) and 300ml acetonitrile, reacts 16 hours at 80 DEG C, are cooled to room temperature, and filter, successively use ethyl acetate,
The HCl of 0.1mol/L, deionized water, methanol washing, then 60 DEG C of vacuum bakings obtain compound imidazoles microballoon B2 in 12 hours.
In 1000ml three-necked flask, 50 grams of compound imidazoles microballoon B2 (imidazole group content is 3.9mmol/g) are added,
19.8 gram of eight chloromethyl silsesquioxane and 500ml tetrahydrofuran filter after reaction 72 hours at 100 DEG C, with four
Hydrogen furans, deionized water are successively washed, and compound imidazoles/POSS microballoon B2 is obtained.
In 1000ml three-necked flask, it is 1.0mol/L's that 40 grams of compound imidazoles/POSS microballoon B2,400ml concentration, which is added,
Progress ion-exchange reactions 12 hours is stirred at room temperature in the deionized water solution of sodium phosphotungstate；It is then washed with deionized straight
To washing lotion pH=7, the ion-exchange resin catalyst of the different nano materials of of the invention two kinds is obtained after vacuum drying, is denoted as
Cat-B2, wherein POSS unit content is 4.3%, and structural formula is as follows:
The preparation of [embodiment 6] ion-exchange resin catalyst
In 500 milliliters of three-necked flasks be added containing initiator monomer mixture solution (42.5 grams of styrene, 2.5 grams
Divinylbenzene, 10 grams of polystyrene, 0.1 gram of single-layer graphene and 2.0 grams of benzoyl peroxides, the solution are stirred prior to 70 DEG C
Reaction 1.5 hours), the mixed solution of 200 ml deionized waters and 4 grams of polyvinyl alcohol is added, is warming up to 85 DEG C, reacts 3 hours,
It is warming up to 90 DEG C again, reacts 9 hours, is finally warming up to 100 DEG C, reacts 10 hours.After reaction, supernatant liquid is poured out,
Washed with 85 DEG C of hot water, then washed with cold water, then filtered, be put into baking oven 80 DEG C of drying, sieving, collection cut size 0.35~
Compound macroporous microsphere C2 within the scope of 0.60 millimeter.
The chloromethylation of complex microsphere: in 250 milliliters of three-necked flask, 20 grams of complex microsphere C2 and 100 milliliters are added
Isosorbide-5-Nitrae-dichloro methyl butyl ether is stored at room temperature 6 hours, and it is catalyst that 8 grams of zinc chloride, which are added, starts to stir, and is warming up to 30 DEG C instead
It answers 12 hours, is cooled to room temperature after chloromethylation, filters out chlorination mother solution, washed repeatedly with methanol, dry 8 at 100 DEG C
Hour, obtain compound macropore chlorine ball C2.
20 grams of compound macropore chlorine ball C2 (chlorinity 1.6mmolCl/g), imidazoles are added in 250ml there-necked flask
(32.0mmol) and 150ml acetonitrile, reacts 16 hours at 90 DEG C, are cooled to room temperature, and filter, successively use ethyl acetate,
The HCl of 0.1mol/L, deionized water, methanol washing, then 60 DEG C of vacuum bakings obtain compound imidazoles microballoon C2 in 12 hours.
In 250ml three-necked flask, the compound imidazoles microballoon C2 of 20 grams of addition (imidazole group content is 1.5mmol/g), 3.6
Gram eight chloroethyl silsesquioxanes and 150ml tetrahydrofuran filter after reaction 72 hours at 100 DEG C, with tetrahydro furan
Mutter, deionized water is successively washed, obtain compound imidazoles/POSS microballoon C2.
In 500ml three-necked flask, the phosphorus that 20 grams of compound imidazoles/POSS microballoon C2,300ml concentration is 0.5mol/L is added
Progress ion-exchange reactions 12 hours is stirred at room temperature in the deionized water solution of sodium tungstate；Then be washed with deionized until
Washing lotion pH=7 obtains the ion-exchange resin catalyst of the different nano materials of of the invention two kinds, is denoted as Cat- after vacuum drying
C2, wherein POSS unit content is 3.2%, and structural formula is as follows:
The preparation of [comparative example 1] comparative catalyst
Nano material is not added prepares macroporous microsphere: 47.0 grams of styrene of addition in 500 milliliters of three-necked flasks, 2.3 grams
260 millis for being dissolved with 2.0 grams of gelatin are added in divinylbenzene, 30 grams of polystyrene and 1.6 grams of benzoyl peroxide initiators
Rise deionized water solution.Mixing speed is adjusted, is stirred 2 hours.It is stirred to react at 60 DEG C 2.0 hours, is then gradually warming up to
It 80 DEG C, reacts 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 8 hours.After reaction, incline
Supernatant liquid is poured out, is washed with 85 DEG C of hot water, then washed with cold water, is then filtered, 80 DEG C of drying in baking oven is put into, is sieved, receive
Collect macroporous microsphere DZ-1 of the partial size within the scope of 0.35~0.60mm.
Macroporous microsphere chloromethylation: in the three-necked flask of 500ml, 40 grams of macroporous microsphere DZ-1 and 200ml chloromethanes are added
Ether is stored at room temperature 3 hours, starts to stir, and it is catalyst that 15 grams of zinc chloride, which are added, is warming up to 50 DEG C and reacts 12 hours, chloromethyl
It is cooled to room temperature after change, filters out chlorination mother solution, washed repeatedly with methanol, dried 8 hours at 100 DEG C, obtain macropore chlorine
Ball DZ-1.
Halogenated alkyl POSS compound is not used: 30 grams of macropore chlorine ball DZ-1 (chlorinities being added in 500ml there-necked flask
For 3.4mmol Cl/g), N- methylimidazole (102.0mmol) and 200ml acetonitrile, is reacted 24 hours at 80 DEG C, be cooled to room
Temperature, filtering, is successively washed with ethyl acetate, the HCl of 0.1mol/L, deionized water, methanol, is then dried 12 hours for 60 DEG C of vacuum
To imidazoles microballoon DZ-1.
In 1000ml three-necked flask, the sodium phosphotungstate that 30 grams of imidazoles microballoon DZ-1,500ml concentration are 0.1mol/L is added
Deionized water solution be stirred at room temperature progress ion-exchange reactions 24 hours；It is then washed with deionized until washing lotion pH
=7, ion-exchange resin catalyst is obtained after vacuum drying, is denoted as Cat-DZ-1, structural formula is as follows:
The preparation of [comparative example 2] comparative catalyst
47.0 grams of styrene, 2.3 grams of divinylbenzenes, 30 grams of polystyrene and 1.6 are added in 500 milliliters of three-necked flasks
Gram benzoyl peroxide initiator, is stirred to react 1.5 hours at 60 DEG C；Then 0.6 gram of multi-layer graphene is added, continues to stir
Progress prepolymerization in 1 hour.The 260 ml deionized water solution for being dissolved with 2.0 grams of gelatin are added.Mixing speed is adjusted, simultaneously
80 DEG C are gradually warming up to, is reacted 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 8 hours.Reaction
After, supernatant liquid is poured out, is washed with 85 DEG C of hot water, then washed with cold water, is then filtered, is put into 80 DEG C of bakings in baking oven
It is dry, sieving, compound macroporous microsphere DZ-2 of the collection cut size within the scope of 0.35~0.60mm.
Compound macroporous microsphere chloromethylation: in the three-necked flask of 500ml, be added 40 grams of compound macroporous microsphere DZ-2 and
200ml chloromethyl ether is stored at room temperature 3 hours, starts to stir, and it is catalyst that 15 grams of zinc chloride, which are added, and it is small to be warming up to 50 DEG C of reactions 12
When, it is cooled to room temperature after chloromethylation, filters out chlorination mother solution, washed repeatedly with methanol, dry 8 hours, obtain at 100 DEG C
To compound macropore chlorine ball DZ-2.
Halogenated alkyl POSS compound is not used: 30 grams of compound macropore chlorine ball DZ-2 (chlorine being added in 500ml there-necked flask
Content is 3.3mmol Cl/g), N- methylimidazole (99.0mmol) and 200ml acetonitrile, reacts 24 hours, is cooled at 80 DEG C
Room temperature, filtering, is successively washed with ethyl acetate, the HCl of 0.1mol/L, deionized water, methanol, is then dried 12 hours for 60 DEG C of vacuum
Obtain compound imidazoles microballoon DZ-2.
In 1000ml three-necked flask, the phosphorus tungsten that 30 grams of compound imidazoles microballoon DZ-2,500ml concentration are 0.1mol/L is added
Progress ion-exchange reactions 24 hours is stirred at room temperature in the deionized water solution of sour sodium；It is then washed with deionized until washing
Liquid pH=7 obtains ion-exchange resin catalyst after vacuum drying, is denoted as Cat-DZ-2, and structural formula is as follows:
The preparation of [comparative example 3] comparative catalyst
Nano material is not added prepares macroporous microsphere: 47.0 grams of styrene of addition in 500 milliliters of three-necked flasks, 2.3 grams
260 millis for being dissolved with 2.0 grams of gelatin are added in divinylbenzene, 30 grams of polystyrene and 1.6 grams of benzoyl peroxide initiators
Rise deionized water solution.Mixing speed is adjusted, is stirred 2 hours.It is stirred to react at 60 DEG C 2.0 hours, is then gradually warming up to
It 80 DEG C, reacts 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 8 hours.After reaction, incline
Supernatant liquid is poured out, is washed with 85 DEG C of hot water, then washed with cold water, is then filtered, 80 DEG C of drying in baking oven is put into, is sieved, receive
Collect macroporous microsphere DZ-3 of the partial size within the scope of 0.35~0.60mm.
Macroporous microsphere chloromethylation: in the three-necked flask of 500ml, 40 grams of macroporous microsphere DZ-3 and 200ml chloromethanes are added
Ether is stored at room temperature 3 hours, starts to stir, and it is catalyst that 15 grams of zinc chloride, which are added, is warming up to 50 DEG C and reacts 12 hours, chloromethyl
It is cooled to room temperature after change, filters out chlorination mother solution, washed repeatedly with methanol, dried 8 hours at 100 DEG C, obtain macropore chlorine
Ball DZ-3.
30 grams of macropore chlorine ball DZ-3 (chlorinity 3.4mmolCl/g), imidazoles are added in 500ml there-necked flask
(102.0mmol) and 200ml acetonitrile, reacts 24 hours at 80 DEG C, are cooled to room temperature, and filter, successively use ethyl acetate,
The HCl of 0.1mol/L, deionized water, methanol washing, then 60 DEG C of vacuum bakings obtain imidazoles microballoon DZ-3 in 12 hours.
In 500ml three-necked flask, it is added 30 grams of imidazoles microballoon DZ-3 (imidazole group content is 3.0mmol/g), 9.4 grams
Eight chloromethyl silsesquioxanes and 300ml tetrahydrofuran filter after reaction 24 hours at 100 DEG C, with tetrahydro furan
Mutter, deionized water is successively washed, obtain imidazoles/POSS microballoon DZ-3.
In 1000ml three-necked flask, the phosphorus that 30 grams of imidazoles/POSS microballoon DZ-3,500ml concentration is 0.1mol/L is added
Progress ion-exchange reactions 24 hours is stirred at room temperature in the deionized water solution of sodium tungstate；Then be washed with deionized until
Washing lotion pH=7 obtains ion-exchange resin catalyst after vacuum drying, is denoted as Cat-DZ-3, and structural formula is as follows:
[embodiment 7] catalytic applications
The ion-exchange resin catalyst of [embodiment 1] preparation is used for the epoxidation reaction of alkene and oxidant, reaction
Condition is as follows: under inert gas protection, reaction under high pressure is added according to the molar ratio of 1:1.5 in cyclohexene, hydrogen peroxide (30%)
In kettle, the catalyst Cat-A1 and acetonitrile solvent that quality is cyclohexene 10% is then added, 70 DEG C of reaction temperature are reacted 4 hours.
Sampling carries out analysis measurement after reaction, and the conversion ratio for measuring cyclohexene is 98.9%, and the selectivity of epoxy hexane is
95.8%.
[embodiment 8~14] catalytic applications
Change used in resin catalyst, and reaction temperature and time, remaining reaction condition all with [embodiment 7]
It is identical, the epoxidation reaction of cyclohexene and hydrogen peroxide is carried out, obtained reaction result is shown in Table 1.
Table 1
[embodiment 15] catalytic applications
Catalyst Cat-A1 used in [embodiment 7] is filtered, is washed, it is dry, then according to the anti-of [embodiment 7]
Answer step and reaction condition, be catalyzed the epoxidation reaction of cyclohexene and hydrogen peroxide, obtain catalyst circulation using 2 times as a result,
It is shown in Table 2.The rest may be inferred, carries out the catalysis that cycle-index is 3~5 times respectively and reacts, the results are shown in Table 2.
Table 2
| Cycle-index | 2 | 3 | 4 | 5 |
| Cyclohexene conversion rate/% | 98.9 | 99.0 | 98.9 | 98.9 |
[comparative example 4-6] catalytic applications
The ion-exchange resin catalyst of [comparative example 1-3] preparation is used for the epoxidation reaction of alkene and oxidant.Instead
Answer condition as follows: under inert gas protection, cyclohexene, hydrogen peroxide (30%) is anti-according to the molar ratio addition high pressure of 1:1.5
It answers in kettle, the catalyst and acetonitrile solvent that quality is cyclohexene 10% is then added, 70 DEG C of reaction temperature are reacted 4 hours.Reaction
After sampling carry out analysis measurement, test result is as shown in table 3.
Table 3
[comparative example 7] catalytic applications
By catalyst filtration used in [comparative example 4-6], wash, it is dry, then according to the reaction of [comparative example 4-6]
Step and reaction condition are catalyzed the epoxidation reaction of cyclohexene and hydrogen peroxide, obtain catalyst circulation using 2 times as a result, seeing
Table 4.The rest may be inferred, carries out the catalysis that cycle-index is 3~5 times respectively and reacts, the results are shown in Table 4.
Table 4
Claims (10)
1. a kind of olefin epoxidation process, is included under epoxidation reaction condition, alkene and oxidant are urged with ion exchange resin
The step of agent contacts；The ion-exchange resin catalyst has following structure general formula:
Wherein,For macroporous type nanocomposite resin matrix；
M- is anion, is selected from phosphotungstic acid root, phosphomolybdic acid root, silico-tungstic acid root, silicomolybdic acid root, arsenowolframic acid root, arsenic molybdate, germanium tungsten
Acid group, germanium molybdate, tungstovanadophosphoric acid root or molybdovanaphosphoric acid root；
POSS is cage-type silsesquioxane unit, and general formula is (- SiO1.5)m；M is 6,8,10 or 12；
For glyoxaline cation unit；
Linking group of the R between POSS unit and glyoxaline cation unit, R are alkylidene or arylene；
The macroporous type nanocomposite resin matrix is styrene monomer, comonomer, nano material and pore-foaming agent through original position
It is copolymerized obtained nanometer macroporous type copolymer；The nano material be selected from single-layer graphene, multi-layer graphene, graphene oxide,
At least one of graphite alkene.
2. olefin epoxidation process according to claim 1, which is characterized in that POSS unit is urged in the ion exchange resin
Content in agent is 2~8 weight %.
3. olefin epoxidation process according to claim 1, which is characterized in that M- is phosphotungstic acid radical ion.
4. olefin epoxidation process according to claim 1, which is characterized in that alkylidene is selected from methylene, ethylidene or Asia
Propyl；Arylene is selected from phenylene, naphthylene or sub- benzyl.
5. olefin epoxidation process according to claim 1, which is characterized in that the styrene monomer be selected from styrene,
At least one of α-methylstyrene or 4- butylstyrene；
The comonomer is selected from ethyleneglycol dimethyacrylate, diallyl benzene, divinyl phenylmethane or divinyl
At least one of base benzene；
The pore-foaming agent be selected from aliphatic hydrocarbon, polystyrene, gasoline, poly- (propylene glycol), poly(ethylene glycol), dimethyl silicone polymer,
At least one of fatty acid or paraffin.
6. olefin epoxidation process according to claim 5, which is characterized in that the styrene monomer is selected from styrene；
The comonomer is selected from divinylbenzene；The pore-foaming agent is selected from polystyrene.
7. olefin epoxidation process according to claim 1, which is characterized in that the nano material is selected from multi-layer graphene.
8. olefin epoxidation process according to claim 1, which is characterized in that the dosage of styrene monomer is 85~95
Part, the dosage of comonomer is 2~5 parts, and the dosage of nano material is 0.1~3 part, and the dosage of pore-foaming agent is 10~100 parts.
9. olefin epoxidation process according to claim 1, which is characterized in that the alkene is selected from styrene, 1- butylene, ring
Any one of amylene, cyclohexene, cyclo-octene, n-hexylene, positive octene, dipentene, australene；The oxidant is selected from peroxide
Change any one of hydrogen, alkyl hydroperoxide compounds.
10. olefin epoxidation process according to claim 1, which is characterized in that the epoxidation reaction condition includes: alkene
Molar ratio with oxidant is 1:10~10:1, and catalyst amount is the 0.1~15% of alkene quality, reaction temperature 40~100
DEG C, the reaction time 1~24 hour.
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