CN109772456A - For olefine aldehyde condensation reaction method - Google Patents
For olefine aldehyde condensation reaction method Download PDFInfo
- Publication number
- CN109772456A CN109772456A CN201711111544.5A CN201711111544A CN109772456A CN 109772456 A CN109772456 A CN 109772456A CN 201711111544 A CN201711111544 A CN 201711111544A CN 109772456 A CN109772456 A CN 109772456A
- Authority
- CN
- China
- Prior art keywords
- ion
- condensation reaction
- aldehyde condensation
- hours
- grams
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to one kind to be used for olefine aldehyde condensation reaction method.The method includes the step of under olefine aldehyde condensation reaction condition, alkene and formaldehyde and ion-exchange resin catalyst are contacted；The ion-exchange resin catalyst has following structure general formula:Wherein,For macroporous type nanocomposite resin matrix；M‑For anion, it is selected from trifluoromethanesulfonic acid radical ion, hydrogen sulfate ion, phosphoric acid hydrogen radical ion, tetrafluoroborate ion or hexafluorophosphoricacid acid ions；POSS is cage-type silsesquioxane unit；
Description
Technical field
The present invention relates to one kind to be used for olefine aldehyde condensation reaction method, more particularly to a kind of olefine aldehyde condensation reaction preparation 1,3-
The method of dihydric alcohol and/or 1,3- 3-dioxane derivatives.
Background technique
1,3- dihydric alcohol has the characteristics that odorless, less toxic, good water solubility, fine chemistry industry, medicine, in terms of have
Extensive purposes.1,3- dihydric alcohol is mainly as polyester, the synthon of polyurethane and solvent, antifreeze etc. and important
Medicine intermediate and organic synthesis intermediate.Especially 1,3-PD is widely used, its most important application be prepare it is poly-
Propylene glycol ester terephthalate.Polypropylene terephthalate is a kind of polyester material haveing excellent performance, and is had both poly- to benzene two
The high-performance of formic acid glycol ester and the workability of polybutylene terephthalate (PBT), but have the good resilience of nylon and
Antifouling property, and easily contaminate, is wear-resisting, fully develop talents in fields such as carpet, engineering plastics, garment materials, there is wide application
Prospect is the hot spot that synthetic fibers are developed in the world at present, is one of 21 century most important Fresh fats kind by scholarly forecast.
The preparation of 1,3- dihydric alcohol or 1,3- 3-dioxane derivatives can be by the aldehyde materials such as alkene and formaldehyde in acidity
It reacts to obtain through Prins under catalyst, 1,3- 3-dioxane derivatives can further obtain 1,3- dihydric alcohol by hydrolysis.
In the 1970s, Di Ren company, Japan, which has inquired into be set out by ethylene, synthesizes the technology path of 1,3-PD.Hair
Existing BF3(JP 76146405)、CuSO4-H2SO4(JP 76143605), p-methyl benzenesulfonic acid (JP 76143606), phosphotungstic acid (JP
113809)、HI-BiI3(US 4338290) can be used as catalyst ethylene and react with the Prins of formaldehyde.The route is first
To be ethylene, which occur Prins with formaldehyde, react, forms dioxane, the latter hydrolyzed again through acetic acid acidolysis generation monoesters, monoesters or after
Generation 1,3-PD, and recovery of acetic acid are hydrolyzed again after continuous esterification.But catalytic erosion is strong in the route, side reaction is more,
Aftertreatment technology is complicated, be easy to cause problem of environmental pollution.2000, DuPont disclosed one kind in US 6111135
It is catalyst with trifluoroacetic acid ytterbium (or bismuth), prins reaction occurs with formaldehyde and ethylene, it is anti-under the conditions of 130 DEG C, 6.9MPa
It answers 16 hours, 62~66% 1,3-PD dicarboxylic acid esters can be obtained, 1,3-PD can be obtained after hydrolysis.The caltalyst
It is that severe reaction conditions, selectivity of product are low.
Document CN201110355402.X discloses a kind of using solid acid metal oxide as catalyst, 1,3- dioxy six
Ring or derivatives thereof is used as reactant, the method through hydrolysis preparation 1,3- dihydric alcohol under catalytic action.
Document CN201110355127.1 discloses a kind of method that 1,3- dihydric alcohol is directly prepared by alkene.This method is adopted
Use formaldehyde, alkene and water as reaction substrate, in the work of acidic catalyst (including molecular sieve, heteropoly acid, solid super-strong acid etc.)
Under, 1,3- dihydric alcohol is directly prepared.2 are at least reacted under the conditions of formaldehyde, alkene and water are blended in catalyst higher than 80 DEG C
Hour, post catalyst reaction is easily separated with reaction system and can be recycled for multiple times, the separation yield highest of 1,3- dihydric alcohol
Reach 95%.
Document CN201110379819.X discloses one kind using carried heteropoly acid salt as catalyst ethylene and formaldehyde
The method that condensation reaction prepares 1,3- dioxanes.Under relatively mild reaction condition, using ethylene and formalin as reactant
Catalyze and synthesize 1,3- dioxanes.This method raw material is cheap and easy to get, and catalytic erosion is low, catalytic activity is high, is easy to and reactant
And product separation, reaction process, aftertreatment technology are simple, and operating condition is mild.
Acidic ion liquid is provided simultaneously with traditional liquid as a kind of novel environmentally friendly solvent and effective catalyst
The high density reaction active site of acid catalyst and the fixedness of solid acid, and because its molecular structure and acidity have and can design
Property, it is considered to be one of most promising green catalyst.
Yadav et al. reports [Bmim] ClAlClxApplication in olefine aldehyde condensation reaction
(Eur.J.Org.Chem.2003,1779-1783), the conversion ratio of aldehyde is up to 95% in reaction, but AlCl3Type ionic liquid pair
Water sensitive limits its application in organic reaction.
Wang wenjuan et al. is reported using imidazole type, pyrrolidones type ionic liquid as catalyst, is catalyzed benzene second
The condensation reaction of alkene and formaldehyde.With ionic liquid [BMIM] [HSO4] be used as catalyst when, formaldehyde conversion reaches as high as 95%,
But repeatedly experiments have shown that, the repeat performance of the ionic-liquid catalyst is bad, and after 5 uses, formaldehyde conversion has been reduced
To 90%.
Document CN201410774243.0 discloses a kind of preparation of resin-carried anionic acid ionic-liquid catalyst
Method.Using the storng-acid cation exchange resin with sulfonic acid group as counter-anion, ionic compound is added and carries out instead
Load anionic acidic ion liquid should be prepared, which can the effectively styrene catalyzed Prins contracting with metaformaldehyde
Reaction is closed, is reacted 10 hours at 80 DEG C, the yield of 4- phenyl -1,3- dioxane is up to 86%.
It can be seen that the catalytic activity of solid-carrying type ionic-liquid catalyst depends not only on the performance of ionic liquid itself,
Additionally depend on the various performances of carrier, such as heat resistance, solvent resistance, porosity etc..It can be seen that designing a kind of with height
The excellent catalyst of activity, recycling performance is of crucial importance.
Summary of the invention
The present invention provides a kind of for olefine aldehyde condensation reaction method.The method includes under olefine aldehyde condensation reaction condition,
The step of alkene and formaldehyde and ion-exchange resin catalyst contact；The ion-exchange resin catalyst has following structure logical
Formula:
Wherein,For macroporous type nanocomposite resin matrix；
M-For anion, it is selected from trifluoromethanesulfonic acid radical ion, hydrogen sulfate ion, phosphoric acid hydrogen radical ion, tetrafluoroborate
Ion or hexafluorophosphoricacid acid ions；
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 multi-walled carbon nanotube, single-walled carbon nanotube, C60
Or at least one of C70 fullerene.
According to an aspect of the present invention, content of the POSS unit in the ion exchange resin is 5~15 weight %.
According to an aspect of the present invention, M-For trifluoromethanesulfonic 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-walled carbon nanotube of the nano material.
According to an aspect of the present invention, the alkene be selected from ethylene, trimethyl-ethylene, propylene, 1- butylene, 2- butylene,
Isobutene, 1- amylene, 2- amylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 2- methyl-2-butene, isoprene, 1- oneself
Alkene, 1- octene, styrene, α-methylstyrene or cyclohexene.
According to an aspect of the present invention, the olefine aldehyde condensation reaction condition includes: that the molar ratio of alkene and formaldehyde is
(0.1~10): 1, catalyst amount is 1~15 weight % of raw material total amount, and reaction temperature is 50~150 DEG C, the reaction time 1
~24 hours, reaction pressure was 2.0~6.0MPa.
In the method for the present invention, formaldehyde can use the aqueous solution of formaldehyde, and the mass fraction of formalin is 35~60%.
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 multi-walled carbon nanotube, single wall
At least one of carbon nanotube, C60 or C70 fullerene；The initiator be selected from benzoyl peroxide, azodiisobutyronitrile,
At least one of lauroyl peroxide or isopropyl benzene hydroperoxide；The pore-foaming agent be selected from aliphatic hydrocarbon, polystyrene, gasoline,
At least one of poly- (propylene glycol), poly(ethylene glycol), dimethyl silicone polymer, fatty acid or paraffin；The auxiliary agent is selected from poly-
At least one of vinyl alcohol, gelatin, starch, methylcellulose, bentonite or calcium carbonate；Based on parts by weight, styrene list
The dosage of body is 85~95 parts, and the dosage of comonomer is 2~5 parts, and the dosage of nano material is 0.1~3 part, the use of initiator
Amount 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 trifluoromethanesulfonic acid (salt), disulfate, hydrophosphate, tetrafluoro boron
Hydrochlorate, at least one of hexafluorophosphoric 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 in situ copolymerization of the styrene, divinylbenzene and multi-walled carbon nanotube of chloromethylation
Resin matrix is reacted with imidazoles, obtains compound imidazoles microballoon, then passes through the POSS compound of imidazole group and halogenated alkyl
Reaction finally carries out ion-exchange reactions with salting liquid again, and the macroporous type ion containing two kinds of different nano materials is prepared and hands over
Change resin.It is reacted by the in-situ copolymerization between carbon nanotube and monomer, comonomer and realizes carbon nanotube and polymeric matrix
Covalent bond, and by the chemical reaction of halogenated alkyl POSS compound and imidazole group realize POSS and resin matrix it
Between combination.
The macroreticular ion exchange resin catalyst containing two kinds of different nano materials in the present invention is used for alkene and formaldehyde
Olefine aldehyde condensation reaction, have the advantage that
(1) catalytic erosion is low, and activity is high；
(2) catalyst easily recycles, and 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-walled carbon nanotube is added, continues to stir
Mix 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, together
When be gradually warming up to 80 DEG C, react 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.Instead
After answering, 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 is 2.84mmol Cl/g), imidazoles are added in 500ml there-necked flask
(84.0mmol) 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 2.6mmol/g), 7.9
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 trifluoromethanesulfonic acid lithium；Then it is washed with deionized water
It washs until washing lotion pH=7, obtains the ion-exchange resin catalyst of the different nano materials of of the invention two kinds, note after vacuum drying
For Cat-A1, wherein POSS unit content is 8.6%, 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-walled carbon nanotubes and 1.0 grams of benzoyl peroxides, the solution are stirred prior to 70 DEG C
Mix 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 is 4.1mmol Cl/g), imidazoles are added in 500ml there-necked flask
(205.0mmol) 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 3.6mmol/g) are added,
18.3 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 trifluoromethanesulfonic acid lithium；Then it is washed with deionized water
It washs until washing lotion pH=7, obtains the ion-exchange resin catalyst of the different nano materials of of the invention two kinds, note after vacuum drying
For Cat-B1, wherein POSS unit content is 10.6%, 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-walled carbon nanotube and 2.0 grams of benzoyl peroxides, the solution are stirred prior to 70 DEG C
Mix 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, reaction 3 is small
When, then 90 DEG C are warming up to, it reacts 9 hours, is finally warming up to 100 DEG C, react 10 hours.After reaction, upper liquid is poured out
Body is washed with 85 DEG C of hot water, then is washed with cold water, is then filtered, and 80 DEG C of drying in baking oven, sieving are put into, and collection cut size exists
Compound macroporous microsphere C1 within the scope of 0.35~0.60 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 is 1.4mmol Cl/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, three that 20 grams of compound imidazoles/POSS microballoon C1,300ml concentration is 0.5mol/L are added
Progress ion-exchange reactions 12 hours is stirred at room temperature in the deionized water solution of fluorine methanesulfonic acid lithium；Then it is 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 after vacuum drying
Cat-C1, wherein POSS unit content is 5.3%, 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 is 3.34mmol Cl/g), imidazoles are added in 500ml there-necked flask
(992.0mmol) 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 3.0mmol/g), 9.1
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 trifluoromethanesulfonic acid lithium；Then it is washed with deionized water
It washs until washing lotion pH=7, obtains the ion-exchange resin catalyst of the different nano materials of of the invention two kinds, note after vacuum drying
For Cat-A2, wherein POSS unit content is 9.4%, 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 is 4.2mmol Cl/g), imidazoles are added in 500ml there-necked flask
(210.0mmol) 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 3.7mmol/g) are added,
18.8 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 trifluoromethanesulfonic acid lithium；Then it is washed with deionized water
It washs until washing lotion pH=7, obtains the ion-exchange resin catalyst of the different nano materials of of the invention two kinds, note after vacuum drying
For Cat-B2, wherein POSS unit content is 10.7%, 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 is 1.6mmol Cl/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, three that 20 grams of compound imidazoles/POSS microballoon C2,300ml concentration is 0.5mol/L are added
Progress ion-exchange reactions 12 hours is stirred at room temperature in the deionized water solution of fluorine methanesulfonic acid lithium；Then it is 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 after vacuum drying
Cat-C2, wherein POSS unit content is 5.9%, 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 2.9mmol Cl/g), N- methylimidazole (87.0mmol) 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 trifluoro methylsulphur that 30 grams of imidazoles microballoon DZ-1,500ml 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 lithium；It is then washed with deionized until washing
Liquid pH=7 obtains ion-exchange resin catalyst after vacuum drying, is denoted as Cat-DZ-1, and 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-walled carbon nanotube is added, continues to stir
Mix 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, together
When be gradually warming up to 80 DEG C, react 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.Instead
After answering, 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 2.8mmol Cl/g), N- methylimidazole (84.0mmol) 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 trifluoro 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 methanesulfonic acid lithium；It is then washed with deionized straight
To washing lotion pH=7, ion-exchange resin catalyst is obtained after vacuum drying, is denoted as Cat-DZ-2, 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 is 2.9mmol Cl/g), imidazoles are added in 500ml there-necked flask
(87.0mmol) 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 2.6mmol/g), 7.9 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, three that 30 grams of imidazoles/POSS microballoon DZ-3,500ml concentration is 0.1mol/L are added
Progress ion-exchange reactions 24 hours is stirred at room temperature in the deionized water solution of fluorine methanesulfonic acid lithium；Then it is washed with deionized
Until washing lotion pH=7, obtains ion-exchange resin catalyst after vacuum drying, is denoted as Cat-DZ-3, structural formula is as follows:
[embodiment 7] catalytic applications
The ion-exchange resin catalyst of [embodiment 1] preparation is reacted for alkene with the olefine aldehyde condensation of formaldehyde, is reacted
Condition is as follows: the formalin and catalyst Cat-A1 that concentration is 37% being added in a high pressure reaction kettle, then confined reaction
Device, with the air in inert gas replacement reactor.Then, propylene is filled with high pressure according to the proportion that olefine aldehydr molar ratio is 1:1
In reaction kettle, the addition quality of catalyst Cat-A1 is alkene/formalin gross mass 10%.Start to stir,
Under the pressure condition of 5.0MPa, reacted 10 hours under 80 DEG C of reaction temperatures.It is cooled to room temperature after reaction, release sampling point
Analysis measurement, measures formaldehyde conversion 94.6%, product 1,3-BDO and 4- methyl-1, the overall selectivity of 3- dioxane is
90.8%.
[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, it carries out propylene and is reacted with the olefine aldehyde condensation of formaldehyde, 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]
Step and reaction condition are answered, catalysis propylene is reacted with the olefine aldehyde condensation of formaldehyde, obtains catalyst circulation using 2 times as a result, seeing
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 |
| Formaldehyde conversion/% | 94.5 | 94.4 | 94.5 | 94.4 |
[comparative example 4-6] catalytic applications
The ion-exchange resin catalyst of [comparative example 1-3] preparation is reacted for alkene with the olefine aldehyde condensation of formaldehyde.Instead
It answers condition as follows: the formalin and catalyst that concentration is 37% being added in a high pressure reaction kettle, then closed reactor, use
Air in inert gas replacement reactor.Then, propylene is filled with autoclave according to the proportion that olefine aldehydr molar ratio is 1:1
In, the addition quality of catalyst is alkene/formalin gross mass 10%.Start to stir, in the pressure condition of 5.0MPa
Under, it is reacted 10 hours under 80 DEG C of reaction temperatures.It is cooled to room temperature after reaction, release sampling analysis measuring.
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, catalysis propylene are reacted with the olefine aldehyde condensation of formaldehyde, obtain catalyst circulation using 2 times as a result, being shown in 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. one kind is used for olefine aldehyde condensation reaction method, it is included under olefine aldehyde condensation reaction condition, alkene and formaldehyde and ion exchange
The step of resin catalyst contacts；The ion-exchange resin catalyst has following structure general formula:
Wherein,For macroporous type nanocomposite resin matrix；
M-For anion, selected from trifluoromethanesulfonic acid radical ion, hydrogen sulfate ion, phosphoric acid hydrogen radical ion, tetrafluoroborate ion or
Hexafluorophosphoricacid acid ions；
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 is selected from multi-walled carbon nanotube, single-walled carbon nanotube, C60 or C70
At least one of fullerene.
2. being used for olefine aldehyde condensation reaction method according to claim 1, which is characterized in that POSS unit is in the ion exchange
Content in resin catalyst is 5~15 weight %.
3. being used for olefine aldehyde condensation reaction method according to claim 1, which is characterized in that M-For phosphotungstic acid radical ion.
4. being used for olefine aldehyde condensation reaction method according to claim 1, which is characterized in that alkylidene is selected from methylene, sub- second
Base or propylidene；Arylene is selected from phenylene, naphthylene or sub- benzyl.
5. being used for olefine aldehyde condensation reaction method according to claim 1, which is characterized in that the styrene monomer is selected from benzene
At least one of ethylene, 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. being used for olefine aldehyde condensation reaction method according to claim 5, which is characterized in that the styrene monomer is selected from benzene
Ethylene；The comonomer is selected from divinylbenzene；The pore-foaming agent is selected from polystyrene.
7. being used for olefine aldehyde condensation reaction method according to claim 1, which is characterized in that the nano material is selected from multi wall carbon
Nanotube.
8. being used for olefine aldehyde condensation reaction method according to claim 1, which is characterized in that the dosage of styrene monomer is 85
~95 parts, 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
Part.
9. being used for olefine aldehyde condensation reaction method according to claim 1, which is characterized in that the alkene is selected from ethylene, front three
Base ethylene, propylene, 1- butylene, 2- butylene, isobutene, 1- amylene, 2- amylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-
Methyl-2-butene, isoprene, 1- hexene, 1- octene, styrene, α-methylstyrene or cyclohexene.
10. being used for olefine aldehyde condensation reaction method according to claim 1, which is characterized in that the olefine aldehyde condensation reaction condition
The molar ratio for including: alkene and formaldehyde is (0.1~10): 1, catalyst amount is 1~15 weight % of raw material total amount, reaction temperature
Degree is 50~150 DEG C, and the reaction time is 1~24 hour, and reaction pressure is 2.0~6.0MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711111544.5A CN109772456A (en) | 2017-11-13 | 2017-11-13 | For olefine aldehyde condensation reaction method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711111544.5A CN109772456A (en) | 2017-11-13 | 2017-11-13 | For olefine aldehyde condensation reaction method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109772456A true CN109772456A (en) | 2019-05-21 |
Family
ID=66485507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711111544.5A Pending CN109772456A (en) | 2017-11-13 | 2017-11-13 | For olefine aldehyde condensation reaction method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109772456A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115477568A (en) * | 2022-09-20 | 2022-12-16 | 润泰化学（泰兴）有限公司 | Method for synthesizing 2, 5-dimethyl-2, 4-hexadiene based on Prins condensation reaction catalyzed by heteropoly acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665409A (en) * | 2008-09-04 | 2010-03-10 | 中国科学院兰州化学物理研究所 | Method for catalytic synthesis of 1,3-dibasic alcohol or cyclic acetal of 1,3-dibasic alcohol by using ionic liquid |
| CN105772083A (en) * | 2014-12-16 | 2016-07-20 | 中国科学院兰州化学物理研究所 | Resin-supported anionic acidic ionic liquid catalyst and application thereof |
| CN106008586A (en) * | 2016-05-23 | 2016-10-12 | 上海大学 | POSS-containing high temperature-resistant solid ionic liquid and preparation method thereof |
-
2017
- 2017-11-13 CN CN201711111544.5A patent/CN109772456A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665409A (en) * | 2008-09-04 | 2010-03-10 | 中国科学院兰州化学物理研究所 | Method for catalytic synthesis of 1,3-dibasic alcohol or cyclic acetal of 1,3-dibasic alcohol by using ionic liquid |
| CN105772083A (en) * | 2014-12-16 | 2016-07-20 | 中国科学院兰州化学物理研究所 | Resin-supported anionic acidic ionic liquid catalyst and application thereof |
| CN106008586A (en) * | 2016-05-23 | 2016-10-12 | 上海大学 | POSS-containing high temperature-resistant solid ionic liquid and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| 上海市经济团体联合会: "《节能减排新途径与新技术》", 31 May 2010, 华东理工大学出版社 * |
| 何领好 等: "《功能高分子材料》", 31 August 2016, 华中科技大学出版社 * |
| 罗文君 等: "《稀土生产废水处理技术》", 31 December 2016, 武汉中国地质大学出版社 * |
| 赵丽萍: "纳米微粒阻燃聚合物的研究进展", 《上海塑料》 * |
| 金万勤 等: "《材料化学工程进展》", 30 September 2007, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115477568A (en) * | 2022-09-20 | 2022-12-16 | 润泰化学（泰兴）有限公司 | Method for synthesizing 2, 5-dimethyl-2, 4-hexadiene based on Prins condensation reaction catalyzed by heteropoly acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109574807A (en) | The method of epoxyalkane catalysis hydration preparing ethylene glycol | |
| CN109569717A (en) | Ion exchange resin and purposes | |
| CN104492495A (en) | Ionic liquid immobilized magnetic solid acid material catalyst and preparation method thereof | |
| CN102633929A (en) | Preparation method of acid ionic liquid mesoporous polymeric material | |
| CN109776264A (en) | The method of olefine aldehyde condensation reaction | |
| CN109453814B (en) | Multi-level pore polymer supported rhodium catalyst containing sulfonic group and phosphine ligand, preparation and application thereof | |
| CN109772456A (en) | For olefine aldehyde condensation reaction method | |
| CN109776262A (en) | Olefine aldehyde condensation reaction method | |
| CN109776263A (en) | Method for olefine aldehyde condensation reaction | |
| CN109574793B (en) | Method for preparing glycol by hydrating alkylene oxide | |
| CN109575295B (en) | Method for catalytic hydration of alkylene oxides | |
| CN109574794A (en) | The method of epoxyalkane catalysis hydration production ethylene glycol | |
| CN105439866A (en) | A dimethyl carbonate preparing method by transesterification | |
| CN104492485B (en) | Acidic ionic liquid-coated polymeric core solid acid material catalyst and preparation method thereof | |
| CN109575162B (en) | Ion exchange resin and use | |
| CN110283285A (en) | A kind of preparation method of sulfonic acid type fragrance block cationoid exchanger resin | |
| CN109590029A (en) | Ion exchange resin and its purposes | |
| CN109776454A (en) | The method that epoxidation reaction of olefines prepares epoxide | |
| CN109575292B (en) | Ion exchange resin and use thereof | |
| CN109772451A (en) | Olefin epoxidation process | |
| CN105272858A (en) | Dimethyl carbonate production method | |
| CN109777629A (en) | The preparation method of biodiesel | |
| CN109777625A (en) | The synthetic method of biodiesel | |
| CN111944083A (en) | Preparation method of modified macroporous acidic cation exchange resin | |
| CN109777628B (en) | Method for preparing biodiesel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190521 |
|
| RJ01 | Rejection of invention patent application after publication |