CN105772083B - A kind of resin-carried anionic acid ionic-liquid catalyst and its application - Google Patents
A kind of resin-carried anionic acid ionic-liquid catalyst and its application Download PDFInfo
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Abstract
The invention discloses a kind of resin-carried anionic acid ionic-liquid catalyst, which is prepared via a method which：Storng-acid cation exchange resin is scattered in toluene, zwitterionic compound is added, is reacted 12 ~ 24 hours at 80 ~ 100 DEG C；It filters after reaction, then filter cake dichloromethane is extracted at 40 ~ 50 DEG C, be then dried in vacuo 12 ~ 24 hours at 60 ~ 80 DEG C.The present invention is using the storng-acid cation exchange resin with sulfonic acid group as counter-anion, prepare load anionic acidic ion liquid, preparation process is simple and practicable, it is i.e. recyclable through filtering or centrifuging after reaction, reaction cost is reduced, is to realize ionic liquid loaded effective ways.The invention also discloses application of the catalyst in Prins condensation reactions, acetal (ketone) react and prepare polyoxymethylene dialkyl ether reaction, and excellent catalytic effect, dosage is low and recycling is convenient.
Description
Technical field
The present invention relates to a kind of resin-carried anionic acid ionic-liquid catalyst and its application, the especially catalyst
Application in Prins condensation reactions, acetal (ketone) react and prepare polyoxymethylene dialkyl ether reaction.
Background technology
Ionic liquid is made of zwitterion, and designability is strong, can be set by the functionalization to anion or cation
It counts to meet the needs of real work.Strong acid group with catalytic performance is introduced into ionic liquid cation structure and
Obtained acidic functionalized ionic liquid, due to being better than common Bronsted acid with acidity, and corrosivity is low, and stability is good, easily
In detaching the characteristics of recycling, be widely studied, and it is a large amount of experiments have shown that the activity of acidic functionalized ionic liquid catalyst it is good,
Selective higher.But since the price of ionic liquid is relatively expensive, viscosity is usually larger to be brought inconvenient, and is being catalyzed
The problems such as being lost in the process there are still component, is more widely applied to limit it.Therefore more researchs are inclined in recent years
To in the characteristic of ionic liquid to be combined with inorganic or organic solid material, new ionic liquid solid catalysis material is formed.
This is lost in reduce homogeneous system ionic liquid dosage and being avoided, simplifies separation operation process, improves its service efficiency and provide
One new way.
Polymer material (such as polystyrene PS) is used as a kind of novel carriers, have it is cheap, be easy to the spies such as surface modification
Point is commonly used for forming immobilized AlCl_3 catalyst as catalyst carrier or by catalysis unit in-situ polymerization.For example, will
Functionalized ion liquid monomer with it is styrene copolymerized, the condensation that the copolymer of preparation can be catalyzed aldehyde radical under mild conditions is anti-
It answers, product yield 95%（Sugimura R., et al. Cataly. Commun., 2007,8：770）.With polyvinyl pyrrole
Alkanone is dispersant, azodiisobutyronitrile is initiator, ethyl alcohol is decentralized medium, passes through styrene and acidic ion liquid 1-
The dispersin polymerization of (3- sulfonic groups) propyl -3- vinyl imidazole disulfates, the PS supported acidic ionic-liquid catalysts of preparation,
The yield for catalyzing and synthesizing n-butyl acetate has reached 97.8%, reuses 4 yields for remaining to obtain 80%（Xu Zhen a beautiful gems etc., stone
Oiling work, 2010,39：971）.1- (3- sulfonic groups) propyl -3- vinyl imidazoles disulfates and butane are coupled bi-vinyl
Imidazole bisulfate carries out copolymerzation with cross-linking, obtains the high polymerizable acidic ionic liquid of thermal stability, can in a mild condition efficiently
It is catalyzed Bigenilli reactions（Pourjavadi A. et al. J. Mole. Cataly. A:Chem., 2012,365：
55）.
CN 102633929B provide a kind of preparation method of the mesoporous polymeric material of acidic ion liquid, from containing ethylene linkage
Glyoxaline compound and sultone set out, and are copolymerized by ethylene linkage and divinylbenzene, acidic ion liquid Jie has been obtained by 5 steps
Hole polymeric material has thermal stability height, excellent catalytic effect, the advantage of separation process simplicity.
CN 102628008B describe a kind of method of the ionic liquid-catalyzed waste grease biodiesel synthesis of aggretion type,
The preparation of wherein aggretion type ionic-liquid catalyst is also to be prepared through 4 steps from vinyl imidazol and sultone.
From the foregoing, it can be seen that the preparation of Polymer-supported ionic-liquid catalyst at present has special want to the structure of raw material
It asks, that is, contains polymerizable ethylene linkage, and preparation process is cumbersome, it is difficult to ensure that the stabilization of catalyst performance prepared by batch.This
Outside, these methods are usually all that imidazole cation group is fixed in macromolecular chain, are unfavorable for functional groups on cation
It plays a role.
To solve the above problems, the present invention considers to be prone to ion using the storng-acid cation exchange resin of commercialization
The characteristic of exchange is prepared resin-carried anionic acid ionic-liquid catalyst by simple single step reaction, passes through negative and positive
Interionic synergistic effect enhances the activity of acidic hydrogen, on the basis of keeping high catalytic activity, reduces the use of ionic liquid
Amount, the removal process for simplifying catalyst.
Invention content
The purpose of the present invention is to solve raw material mix existing for existing Polymer-supported ionic liquid is special, prepare
The cumbersome problem of process, provides that a kind of preparation process is simple and practicable, active high, the convenient resin-carried anionic acid of separation and recovery
Property ionic-liquid catalyst, and the preparation method of this catalyst is provided.It is anti-in Prins condensations that the present invention also provides the catalyst
Answer, acetal (ketone) reaction and prepare polyoxymethylene dialkyl ether reaction in application.
For achieving the above object, the present invention adopts the following technical scheme that：
A kind of resin-carried anionic acid ionic-liquid catalyst, is prepared via a method which：By highly acidic cation
Exchanger resin is scattered in toluene, and zwitterionic compound is added, is reacted 12 ~ 24 hours at 80 ~ 100 DEG C；After reaction
Filtering, then filter cake dichloromethane is extracted at 40 ~ 50 DEG C, it is then dried in vacuo 12 ~ 24 hours at 60 ~ 80 DEG C, obtains resin
Load anionic acid ionic-liquid catalyst；The storng-acid cation exchange resin be selected from Purolite C100E,
Purolite C150、Purolite CT110、Purolite CT175、Purolite CT175DR、Purolite CT169、
Purolite CT169DR、Purolite CT275、Purolite CT269、Purolite CT276、Purolite CT482、
One kind in Amberlite IR120, Amberlyst15, Nafion-H, Nafion NR50,001 × 7 (732), NKC-9；Institute
It is one kind in following structural formula to state zwitterionic compound：
, wherein R1、R2、R3、R4、R5It is identical or different, and represent H, aliphatic group, cycloaliphatic radical or
Aryl, the integer that n is 0-6.
The mass ratio of the storng-acid cation exchange resin and zwitterionic compound is 1:5~1:10.
Preferred zwitterionic compound is one kind in following structural formula：
The storng-acid cation exchange resin is commercially available commodity, preferably Purolite CT175, Purolite
CT175DR、Purolite CT276、Purolite CT482、Amberlite IR120、Amberlyst15、Nafion
One kind in NR50,001 × 7 (732), NKC-9.
Application of the resin-carried anionic acid ionic-liquid catalyst of the present invention in Prins condensation reactions,
It is characterized in that resin-carried anionic acid ionic-liquid catalyst, metaformaldehyde and olefin；Metaformaldehyde and alkene
Molar ratio be 0.4:1~1.5:1, catalyst charge is the 1 ~ 10% of raw material gross weight；Nitrogen replace 3 times after, in 50 DEG C ~
100 DEG C are stirred to react 2 ~ 12 hours, and organic phase is concentrated after reaction, column chromatography for separation obtains 4- substitution -1,3- dioxanes,
Catalyst separates reuse through centrifugation.
The alkene of the progress Prins condensation reactions is aliphatic or aromatic olefin, and the aliphatic olefin is different
Butylene or octene, the aromatic olefin are styrene, contraposition substituted phenylethylene or naphthalene ethylene.
The present invention provides application of the above-mentioned resin-carried anionic acid ionic-liquid catalyst in acetal (ketone) reaction,
It is characterized in that using the resin-carried anionic acid ionic liquid as catalyst, catalyzing glycerol with 37% formaldehyde it is water-soluble
The acetal (ketone) of liquid or acetone reacts, and prepares corresponding methene glycerine or isopropylidene glycerol-4-methanol compound, wherein glycerine and formaldehyde or
The molar ratio of acetone is 1:1~1:Between 5, catalyst amount is the 1~5% of reactant gross mass, and reaction temperature is 70 DEG C ~ 100
DEG C, 5 ~ 10 hours reaction time centrifuged out catalyst after reaction, and reaction solution obtains methene glycerine through vacuum distillation
Or isopropylidene glycerol-4-methanol.
The reaction solution of the glycerine and formaldehyde is decompressed to 1.33 ~ 2.00 kPa, and the fraction for collecting 95 ~ 110 DEG C is methene
Glycerine；The reaction solution of glycerine and acetone is decompressed to 1.33 kPa, and the fraction for collecting 80 ~ 83 DEG C is isopropylidene glycerol-4-methanol.
The present invention also provides above-mentioned resin-carried anionic acid ionic-liquid catalysts to be used to prepare polyoxymethylene dialkyl
The reaction of ether, wherein the application is specially：By methylal or formaldehyde contract two butanol and paraformaldehyde in molar ratio 0.5 ~
3:1 is placed in the 100mL reaction kettles equipped with mechanical agitator, cooling device and temperature thermocouple, and weight is added and accounts for reaction raw materials
The resin-carried anionic acid ionic-liquid catalyst of 1 ~ 8 wt% of total weight is warming up to 60 DEG C ~ 100 DEG C, reaction 1
h.Reaction mixture is filtered, liquid product is formed by 6820 gas of Agilent 7890N/5970C gas chromatograph-mass spectrometers and Agilent
Chromatography carries out qualitative and quantitative analysis.
Compared with prior art, the beneficial effects are mainly as follows：
（1）The present invention provides a kind of using highly acidic resin as the anti-lotus polyanion of sulfonic functional cation
Method synthesizes resin-carried anionic acid ionic liquid, enriches the type of ionic liquid；
（2）Ionic liquid technology of preparing provided by the invention using be commercialized resin, zwitterionic compound as raw material, warp
One step is prepared, and compared with existing polymer ions fluent material, has and derives from a wealth of sources, of low cost, method is simply excellent
Gesture；
（3）In ionic liquid provided by the invention, zwitterion contains the sulfonic acid group of strong Bronsted acidity, collaboration
The result of effect so that acidic hydrogen is more active, therefore its acid strength is high, and activity is good, it is convenient to as needing the anti-of strong acid catalyst
Catalyst is answered to use.
Specific implementation mode
The present invention is described in further details with reference to embodiment, but the scope of the present invention is not limited in described
Hold；Zwitterionic compound of the present invention can be prepared by means commonly known in the art, such as according to documentJ. Mol. Catal. A:Chem.,2005,234:107；Synthesis, 2003,17: 2626；J. Am. Chem. Soc.,
2002,124: 5962；Journal of Molecular Catalysis, 2008,22 (5):392 and Chinese invention patent ZL 200710305965.1；
Preparation method recorded in CN200910206549.5 etc. is prepared.
The explanation of embodiment 1 ~ 13 is suitable for catalyst of the method for the present invention and preparation method thereof.
Embodiment 1
50g storng-acid cation exchange resin Purolite CT175 are scattered in 250mL toluene, 37g both sexes are added
Ionic compound reacts 24 hours at 80 DEG C；It filters after reaction, then with dichloromethane, the Soxhlet at 40 DEG C carries by filter cake
It takes 24 hours, is then dried in vacuo 12 hours at 70 DEG C, obtain resin-carried anionic acid ionic-liquid catalyst Cat-1.
Embodiment 2 ~ 13
The preparation process of embodiment 2 ~ 13 is identical as method and embodiment 1, only changes storng-acid cation exchange resin
With the type of zwitterionic compound.Specific preparation condition is shown in Table 1.
Table 1
| Embodiment | Catalyst | Storng-acid cation exchange resin | Zwitterionic compound structure used |
| 1 | Cat-1 | Purolite CT175 | |
| 2 | Cat-2 | Purolite CT175 | |
| 3 | Cat-3 | Purolite CT175DR | |
| 4 | Cat-4 | Purolite CT175DR | |
| 5 | Cat-5 | Purolite CT276 | |
| 6 | Cat-6 | Purolite CT276 | |
| 7 | Cat-7 | Purolite CT482 | |
| 8 | Cat-8 | Amberlite IR120 | |
| 9 | Cat-9 | Amberlyst15 | |
| 10 | Cat-10 | Amberlyst15 | |
| 11 | Cat-11 | 001×7(732) | |
| 12 | Cat-12 | Nafion NR50 | |
| 13 | Cat-13 | NKC-9 |
Embodiment 14
The catalyst Cat-1 0.3g that Example 1 synthesizes are put into three-necked bottle, and metaformaldehyde 2.7g is then added
（0.03mol）, styrene 4.7g（0.045mol）, after nitrogen is replaced 3 times, 80 DEG C are stirred to react 10 hours.It will after reaction
Organic phase concentrates, and chromatography obtains 4- phenyl -1,3- dioxanes, yield 86% on a silica gel column.Catalyst is separated through centrifugation,
According to reacting for above-mentioned same steps catalytic trimerization formaldehyde and styrene, it is 86% to repeat first time product yield.It repeats second
Product yield 85%.
Embodiment 15
The catalyst Cat-4 0.3g that Example 4 synthesizes are put into three-necked bottle, and metaformaldehyde 2.7g is then added
（0.03mol）, 1- octenes 6.7g（0.06mol）, after nitrogen is replaced 3 times, 80 DEG C are stirred to react 10 hours.To have after reaction
Machine mutually concentrates, and chromatography obtains 4- hexyl -1,3- dioxanes, yield 63% on a silica gel column.
Embodiment 16
The catalyst Cat-5 0.5g that Example 5 synthesizes are put into three-necked bottle, and glycerine 13.8g is then added
（0.15mol）, formaldehyde（37% formalin）13.4g（0.17mol）, using hexamethylene as water entrainer, in 80 DEG C of back flow reactions 8
Hour, after reaction, catalyst is centrifuged out, reaction solution is decompressed to 1.33 ~ 2.00 kPa, and 95 ~ 110 DEG C of collection evaporates
Point, the yield of product methene glycerine reaches 80%.
Embodiment 17
It is carried out according to the method for embodiment 16, the difference is that the catalyst Cat-6 synthesized using the embodiment 6 of identical weight
Instead of Cat-5, reaction solution is decompressed to 1.33 ~ 2.00 kPa, collects 95 ~ 110 DEG C of fraction, and the yield of product methene glycerine reaches
83%。
Embodiment 18
The catalyst Cat-7 0.5g that Example 7 synthesizes are put into three-necked bottle, are then added, glycerine 10.2g
（0.11mol）, acetone 31.9g（0.55mol）, in 80 DEG C of back flow reactions 5 hours, after reaction, catalyst is centrifuged out,
Reaction solution is decompressed to 1.33 kPa, collects 80 ~ 83 DEG C of fraction, and the yield of product isopropylidene glycerol-4-methanol reaches 96%.
Embodiment 19
It is carried out according to the method for embodiment 18, the difference is that the catalyst Cat-8 synthesized using the embodiment 8 of identical weight
Instead of Cat-7, reaction solution is decompressed to 1.33 kPa, collects 80 ~ 83 DEG C of fraction, and the yield of product isopropylidene glycerol-4-methanol reaches 95%.
Embodiment 20
It is carried out according to the method for embodiment 18, the difference is that the catalyst Cat-9 synthesized using the embodiment 9 of identical weight
Instead of Cat-7, reaction solution is decompressed to 1.33 kPa, collects 80 ~ 83 DEG C of fraction, and the yield of product isopropylidene glycerol-4-methanol reaches 88%.
Embodiment 21
It is carried out according to the method for embodiment 18, the difference is that the catalyst Cat- synthesized using the embodiment 10 of identical weight
10 replace Cat-7, reaction solution to be decompressed to 1.33 kPa, collect 80 ~ 83 DEG C of fraction, the yield of product isopropylidene glycerol-4-methanol reaches
90%。
Embodiment 22
The catalyst Cat-11 1.3g that Example 11 synthesizes are put into equipped with mechanical agitator, cooling device and thermometric heat
In the 100mL autoclaves of galvanic couple, methylal 22.8g is added（0.3mol）, paraformaldehyde 9g（0.3mol）, nitrogen charging
Gas to pressure is 2.0MPa, is heated to 100 DEG C and is stirred to react 1h.Reaction mixture is filtered, liquid product is formed by Agilent
7890N/5970C gas chromatograph-mass spectrometers and 6820 gas chromatographs of Agilent carry out qualitative and quantitative analysis.Paraformaldehyde converts
Rate is 66.7 %, each component relative amount：CH3OCH2OCH3: 32.6 %；CH3O(CH2O)2CH3: 20.3 %；CH3O
(CH2O)3~8CH3: 53.4 %；CH3O(CH2O)≥9CH3:It is not detected.
Embodiment 23
It is carried out according to the method for embodiment 22, the difference is that the catalyst Cat- synthesized using the embodiment 12 of identical weight
12 replace Cat-11.Paraformaldehyde conversion ratio is 67.5 %, each component relative amount：CH3OCH2OCH3: 29.7 %；CH3O
(CH2O)2CH3: 25.6 %；CH3O(CH2O)3~8CH3: 53.8 %；CH3O(CH2O)≥9CH3:It is not detected.
Embodiment 24
It is carried out according to the method for embodiment 22, the difference is that the catalyst Cat- synthesized using the embodiment 13 of identical weight
13 replace Cat-11.Paraformaldehyde conversion ratio is 60.3%, each component relative amount：CH3OCH2OCH3: 35.6 %；CH3O
(CH2O)2CH3: 22.6 %；CH3O(CH2O)3~8CH3: 50.1 %；CH3O(CH2O)≥9CH3:It is not detected.
Embodiment 25
It is carried out according to the method for embodiment 22, the difference is that reaction raw materials are two butanol 48.1g of formaldehyde contracting（0.3mol）, more
Polyformaldehyde 9g（0.3mol）.Paraformaldehyde conversion ratio is 54.4%, each component relative amount：C4H9OCH2OC4H9: 35.6 %；
C4H9O(CH2O)2C4H9: 11.9 %；C4H9O(CH2O)3~8C4H9:15.1 %；C4H9O(CH2O)≥9C4H9:It is not detected.
Claims (10)
1. a kind of resin-carried anionic acid ionic-liquid catalyst, it is characterised in that the catalyst is made by the following method
It is standby：Storng-acid cation exchange resin is scattered in toluene, be added zwitterionic compound, at 80 ~ 100 DEG C react 12 ~
24 hours；It filters after reaction, then filter cake is extracted with dichloromethane at 40 ~ 50 DEG C, be then dried in vacuo at 60 ~ 80 DEG C
12 ~ 24 hours, obtain resin-carried anionic acid ionic-liquid catalyst；The storng-acid cation exchange resin is selected from
Purolite C100E、Purolite C150、Purolite CT110、Purolite CT175、Purolite CT175DR、
Purolite CT169、Purolite CT169DR、Purolite CT275、Purolite CT269、Purolite CT276、
Purolite CT482、Amberlite IR120、Amberlyst15、Nafion-H、Nafion NR50、001×7(732)、
One kind in NKC-9；The zwitterionic compound is one kind in following structural formula：
, wherein R1、R2、R3、R4And R5H, aliphatic group, cycloaliphatic radical or aryl are represented, and identical or different, n
For 0-6 integer.
2. catalyst as described in claim 1, it is characterised in that the storng-acid cation exchange resin and bisexual ion purification
The mass ratio for closing object is 1:5~1:10.
3. catalyst as described in claim 1, it is characterised in that the zwitterionic compound is one in following structural formula
Kind：
。
4. catalyst as described in claim 1, it is characterised in that the storng-acid cation exchange resin is Purolite
CT175、Purolite CT175DR、Purolite CT276、Purolite CT482、Amberlite IR120、
One kind in Amberlyst15, Nafion NR50,001 × 7 (732) and NKC-9.
5. the catalyst as described in claim 1,2,3 or 4 in Prins condensation reactions, acetal or ketal reaction and is being prepared
Application in polyoxymethylene dialkyl ether reaction.
6. application as claimed in claim 5, it is characterised in that the reaction raw materials of the Prins condensation reactions be metaformaldehyde with
Alkene.
7. application as claimed in claim 6, it is characterised in that the alkene is aliphatic olefin or aromatic olefin.
8. the use as claimed in claim 7, it is characterised in that the aliphatic olefin is isobutene or octene, the aromatic series
Alkene is styrene, contraposition substituted phenylethylene or naphthalene ethylene.
9. application as claimed in claim 5, it is characterised in that the raw material of the acetal or ketal reaction is glycerine and 37% first
Aldehyde aqueous solution or glycerine and acetone.
10. application as claimed in claim 5, it is characterised in that the raw material for preparing polyoxymethylene dialkyl ether reaction is formaldehyde
Dimethyl acetal and paraformaldehyde or formaldehyde two butanol of contracting and paraformaldehyde.
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| CN109776264A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | The method of olefine aldehyde condensation reaction |
| CN109776458A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | The method that alkene epoxidation prepares epoxide |
| CN109776263A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | Method for olefine aldehyde condensation reaction |
| CN109776262A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | Olefine aldehyde condensation reaction method |
| CN109776454A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | The method that epoxidation reaction of olefines prepares epoxide |
| CN109776455A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | Epoxidation reaction of olefines method |
| CN109772451A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | Olefin epoxidation process |
| CN109772456A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | For olefine aldehyde condensation reaction method |
| CN112441880B (en) * | 2019-09-02 | 2023-04-07 | 中国石油化工股份有限公司 | Aldehyde removing agent for glycol aldehyde removing and refining and method for glycol aldehyde removing and refining |
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