CN105772083A - Resin-supported anionic acidic ionic liquid catalyst and application thereof - Google Patents
Resin-supported anionic acidic ionic liquid catalyst and application thereof Download PDFInfo
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Abstract
The invention discloses a resin-supported anionic acidic ionic liquid catalyst which is prepared through the following steps: strongly acidic cation exchange resin is dispersed in toluene; a zwitterionic compound is added, and a reaction is conducted at a temperature of 80-100 DEG C for 12-24h; filtering is carried out after the reaction is completed; a filter cake is extracted with dichloromethane under a temperature of 40-50 DEG C; and vacuum drying is carried out for 12-24h under a temperature of 60-80 DEG C. According to the invention, the strongly acidic cation exchange resin with sulfonic acid group is adopted as counter anion for preparing the supported anionic acidic ionic liquid. The preparation process is simple and feasible. After a reaction, the ionic liquid can be recycled after filtration or centrifugation, such that reaction cost is reduced. The method is an effective method for realizing ionic liquid supporting. The invention also discloses applications of the catalyst in Prins condensation reactions, acetal (ketal) reactions and reactions for preparing polyoxymethylene dialkyl ether. With the catalyst, a catalytic effect is good, catalyst dose is low, and catalyst recovery is convenient.
Description
Technical field
The present invention relates to a kind of resin-carried anionic acid ionic-liquid catalyst and application, particularly this catalyst react at Prins condensation reaction, acetal (ketone) and prepare the application in polyoxymethylene dialkyl ether reaction.
Background technology
Ionic liquid is made up of zwitterion, and designability is strong, it is possible to by anion or cationic functionalized design meet the needs of real work.The strong acid group with catalytic performance is incorporated in ionic liquid cation structure the acidic functionalized ionic liquid obtained, it is better than common Bronsted acid owing to having acidity, and corrosivity is low, good stability, it is easily isolated the feature of circulation, it is widely studied, and the activity that substantial amounts of experiment proves acidic functionalized ionic liquid catalyst is good, selectivity is higher.But owing to the price of ionic liquid is relatively costly, viscosity brings generally more greatly operation inconvenience, and still suffers from the problems such as component loss in catalytic process, is more widely applied thus limiting it.Therefore more research trend, in the characteristic of ionic liquid being combined with inorganic or organic solid material, forms new ionic liquid solid catalysis material in recent years.This is for reducing homogeneous system ionic liquid consumption being avoided and run off, simplify separation operation process, improving its service efficiency and provide a new way.
Polymeric material (such as polystyrene PS etc.), as a kind of novel carriers, has inexpensively, is prone to the features such as finishing, is commonly used for forming immobilized AlCl_3 catalyst as catalyst carrier or by catalysis unit in-situ polymerization.Such as, by functionalized ion liquid monomer with styrene copolymerized, the copolymer of preparation can the condensation reaction of catalysis aldehyde radical under mild conditions, product yield is 95%(SugimuraR., etal.Cataly.Commun., 2007,8:770).With polyvinylpyrrolidone be dispersant, azodiisobutyronitrile be initiator, ethanol is for disperse medium, dispersin polymerization by styrene Yu acidic ion liquid 1-(3-sulfonic group) propyl group-3-vinyl imidazole disulfate, the PS supported acidic ionic-liquid catalyst of preparation, the yield catalyzing and synthesizing n-butyl acetate has reached 97.8%, reuse yield (the Xu Zhen a beautiful gem etc. remaining to obtain 80% 4 times, petrochemical industry, 2010,39:971).1-(3-sulfonic group) propyl group-3-vinyl imidazole disulfate and butane coupling bi-vinyl imidazole bisulfate are carried out copolymerzation with cross-linking, obtain the polymerizable acidic ionic liquid that heat stability is high, (PourjavadiA.etal.J.Mole.Cataly.A:Chem. can be reacted by efficient catalytic Bigenilli in a mild condition, 2012,365:55).
The preparation method that CN102633929B provides the mesoporous polymeric material of a kind of acidic ion liquid, from the glyoxaline compound containing ethylene linkage and sultone, by ethylene linkage and divinylbenzene copolymerization, the mesoporous polymeric material of acidic ion liquid is obtained through 5 steps, there is heat stability height, excellent catalytic effect, the advantage that separation process is easy.
CN102628008B describes the method for the ionic liquid-catalyzed waste grease biodiesel synthesis of a kind of aggretion type, and wherein the preparation of aggretion type ionic-liquid catalyst is also from vinyl imidazol and sultone, prepares through 4 steps.
From above-mentioned, the structure of raw material is all had particular/special requirement by the preparation of current Polymer-supported ionic-liquid catalyst, namely contain polymerisable ethylene linkage, and preparation process is loaded down with trivial details, it is difficult to ensure that the stablizing of batch catalyst performance prepared.Additionally, these methods are generally all be fixed in macromolecular chain by imidazole cation group, being unfavorable in cation, functional groups plays a role.
For solving the problems referred to above, the present invention considers the characteristic utilizing commercial storng-acid cation exchange resin to be prone to occur ion exchange, resin-carried anionic acid ionic-liquid catalyst is prepared by simple single step reaction, by the synergism between zwitterion, strengthen the activity of acidic hydrogen, keeping on the basis of high catalytic activity, reducing the consumption of ionic liquid, simplify the removal process of catalyst.
Summary of the invention
The raw material mix that the invention aims to solve the existence of existing Polymer-supported ionic liquid is special, the problem that preparation process is loaded down with trivial details, a kind of preparation process height simple, active is provided, separates and recovers convenient resin-carried anionic acid ionic-liquid catalyst the preparation method that this catalyst is provided.The present invention also provides for this catalyst and reacts at Prins condensation reaction, acetal (ketone) and prepare the application in polyoxymethylene dialkyl ether reaction.
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: be scattered in toluene by storng-acid cation exchange resin, adds zwitterionic compound, reacts 12 ~ 24 hours at 80 ~ 100 DEG C；Reaction is filtered after terminating, then by filter cake dichloromethane 40 ~ 50 DEG C of extractions, then 60 ~ 80 DEG C of vacuum dryings 12 ~ 24 hours, obtains resin-carried anionic acid ionic-liquid catalyst；Described storng-acid cation exchange resin selected from PuroliteC100E, PuroliteC150, PuroliteCT110, PuroliteCT175, PuroliteCT175DR, PuroliteCT169, PuroliteCT169DR, PuroliteCT275, PuroliteCT269, PuroliteCT276, PuroliteCT482, AmberliteIR120, Amberlyst15, Nafion-H, NafionNR50,001 × 7 (732), one in NKC-9；Described zwitterionic compound is the one in following structural formula:
, wherein, R1、R2、R3、R4、R5Identical or different, and represent H, aliphatic group, cycloaliphatic radical or aryl, n is the integer of 0-6.
The mass ratio of described storng-acid cation exchange resin and zwitterionic compound is 1:5 ~ 1:10.
Preferred zwitterionic compound is the one in following structural formula:
Described storng-acid cation exchange resin is commercially available commodity, it is preferable that PuroliteCT175, PuroliteCT175DR, PuroliteCT276, PuroliteCT482, AmberliteIR120, Amberlyst15, NafionNR50,001 × 7 (732), one in NKC-9.
The resin-carried anionic acid ionic-liquid catalyst of the present invention application in Prins condensation reaction, it is characterised in that by resin-carried anionic acid ionic-liquid catalyst, metaformaldehyde and olefin；The mol ratio of metaformaldehyde and alkene is 0.4:1 ~ 1.5:1, and catalyst charge is the 1 ~ 10% of raw material gross weight；Nitrogen is replaced after 3 times, and in 50 DEG C ~ 100 DEG C stirring reactions 2 ~ 12 hours, reaction terminated that rear organic facies is concentrated, column chromatography for separation obtains 4-and replaces-1, and 3-dioxanes, catalyst separates by centrifugation and reuses.
The described alkene carrying out Prins condensation reaction is aliphatic or aromatic olefin, and described aliphatic alkene is isobutene. or octene, and described aromatic olefin is styrene, para-orientation styrene or naphthalene ethylene.
The present invention provides the application in acetal (ketone) reacts of the above-mentioned resin-carried anionic acid ionic-liquid catalyst, it is characterized in that using this resin-carried anionic acid ionic liquid as catalyst, catalyzing glycerol reacts with the formalin of 37% or the acetal (ketone) of acetone, prepare corresponding methene glycerol or isopropylidene glycerol-4-methanol compound, wherein the mol ratio of glycerol and formaldehyde or acetone is between 1:1 ~ 1:5, catalyst amount is the 1～5% of reactant gross mass, reaction temperature is 70 DEG C ~ 100 DEG C, 5 ~ 10 hours response time, after reaction terminates, centrifugation goes out catalyst, reactant liquor is through decompression distillation, obtain methene glycerol or isopropylidene glycerol-4-methanol.
The reactant liquor of described glycerol and formaldehyde is decompressed to 1.33 ~ 2.00kPa, and the fraction collecting 95 ~ 110 DEG C is methene glycerol；The reactant liquor of glycerol and acetone is decompressed to 1.33kPa, and the fraction collecting 80 ~ 83 DEG C is isopropylidene glycerol-4-methanol.
The present invention also provides for above-mentioned resin-carried anionic acid ionic-liquid catalyst for preparing the reaction of polyoxymethylene dialkyl ether, wherein, this application particularly as follows: contract two butanol and paraformaldehyde 0.5 ~ 3:1 in molar ratio is placed in equipped with in the 100mL reactor of mechanical agitator, chiller and temperature thermocouple by methylal or formaldehyde, add the resin-carried anionic acid ionic-liquid catalyst that weight accounts for 1 ~ 8wt% of reaction raw materials gross weight, it is warmed up to 60 DEG C ~ 100 DEG C, reacts 1h.Filtering reactant mixture, liquid product composition is carried out qualitative and quantitative analysis by Agilent7890N/5970C gas chromatograph-mass spectrometer and Agilent6820 gas chromatograph.
Compared with prior art, the beneficial effects are mainly as follows:
(1) the invention provides a kind of method using highly acidic resin as the cationic anti-lotus polyanion of sulfonic functional, synthesize resin-carried anionic acid ionic liquid, enrich the kind of ionic liquid；
(2) ionic liquid technology of preparing provided by the invention is with commercial resin, zwitterionic compound for raw material, prepares through a step, compared with existing polymer ions fluent material, has wide material sources, with low cost, the simple advantage of method；
(3) in ionic liquid provided by the invention, zwitterion all contains the sulfonic acid group that strong Bronsted is acid, and synergistic result makes acidic hydrogen more active, and therefore its acid strength is high, activity is good, it is convenient to use as the catalysts needing strong acid catalyst.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further details, but scope is not limited to described content；Zwitterionic compound of the present invention can prepare by means commonly known in the art, for instance 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 ZL200710305965.1；Preparation method described for CN200910206549.5 etc. prepares.
Embodiment 1 ~ 13 illustrates to be suitable for the Catalysts and its preparation method of the inventive method.
Embodiment 1
50g storng-acid cation exchange resin PuroliteCT175 is scattered in 250mL toluene, adds 37g zwitterionic compound, react 24 hours at 80 DEG C；Reaction is filtered after terminating, then by filter cake dichloromethane surname extraction 24 hours at 40 DEG C, then 70 DEG C of vacuum dryings 12 hours, obtains resin-carried anionic acid ionic-liquid catalyst Cat-1.
Embodiment 2 ~ 13
The preparation process of embodiment 2 ~ 13 is identical with method and embodiment 1, simply changes the kind of storng-acid cation exchange resin and zwitterionic compound.Concrete preparation condition is 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-10.3g of Example 1 synthesis puts in three-necked bottle, is subsequently added metaformaldehyde 2.7g(0.03mol), styrene 4.7g(0.045mol), nitrogen is replaced after 3 times, 80 DEG C of stirring reactions 10 hours.Reaction terminates the concentration of rear organic facies, and chromatography obtains 4-phenyl-1,3-dioxanes, yield 86% on a silica gel column.Catalyst separates by centrifugation, and according to above-mentioned same steps catalytic trimerization formaldehyde and cinnamic reaction, repeating first time product yield is 86%.Repeat second time product yield 85%.
Embodiment 15
The catalyst Cat-40.3g of Example 4 synthesis puts in three-necked bottle, is subsequently added metaformaldehyde 2.7g(0.03mol), 1-octene 6.7g(0.06mol), nitrogen is replaced after 3 times, 80 DEG C of stirring reactions 10 hours.Reaction terminates the concentration of rear organic facies, and chromatography obtains 4-hexyl-1,3-dioxanes, yield 63% on a silica gel column.
Embodiment 16
The catalyst Cat-50.5g of Example 5 synthesis puts in three-necked bottle, it is subsequently added glycerol 13.8g(0.15mol), formaldehyde (37% formalin) 13.4g(0.17mol), with hexamethylene for water entrainer, in 80 DEG C of back flow reaction 8 hours, after reaction terminates, centrifugation goes out catalyst, reactant liquor is decompressed to 1.33 ~ 2.00kPa, collects the fraction of 95 ~ 110 DEG C, and the yield of product methene glycerol reaches 80%.
Embodiment 17
Carrying out according to the method for embodiment 16, the catalyst Cat-6 synthesized except that the embodiment 6 of identical weight replaces Cat-5, and reactant liquor is decompressed to 1.33 ~ 2.00kPa, collects the fraction of 95 ~ 110 DEG C, and the yield of product methene glycerol reaches 83%.
Embodiment 18
The catalyst Cat-70.5g of Example 7 synthesis puts in three-necked bottle, it is subsequently added, glycerol 10.2g(0.11mol), acetone 31.9g(0.55mol), in 80 DEG C of back flow reaction 5 hours, after reaction terminates, centrifugation goes out catalyst, reactant liquor is decompressed to 1.33kPa, collects the fraction of 80 ~ 83 DEG C, and the yield of product isopropylidene glycerol-4-methanol reaches 96%.
Embodiment 19
Carrying out according to the method for embodiment 18, the catalyst Cat-8 synthesized except that the embodiment 8 of identical weight replaces Cat-7, and reactant liquor is decompressed to 1.33kPa, collects the fraction of 80 ~ 83 DEG C, and the yield of product isopropylidene glycerol-4-methanol reaches 95%.
Embodiment 20
Carrying out according to the method for embodiment 18, the catalyst Cat-9 synthesized except that the embodiment 9 of identical weight replaces Cat-7, and reactant liquor is decompressed to 1.33kPa, collects the fraction of 80 ~ 83 DEG C, and the yield of product isopropylidene glycerol-4-methanol reaches 88%.
Embodiment 21
Carrying out according to the method for embodiment 18, the catalyst Cat-10 synthesized except that the embodiment 10 of identical weight replaces Cat-7, and reactant liquor is decompressed to 1.33kPa, collects the fraction of 80 ~ 83 DEG C, and the yield of product isopropylidene glycerol-4-methanol reaches 90%.
Embodiment 22
The catalyst Cat-111.3g of Example 11 synthesis puts into equipped with in the 100mL autoclave of mechanical agitator, chiller and temperature thermocouple, add methylal 22.8g(0.3mol), paraformaldehyde 9g(0.3mol), inflated with nitrogen to pressure is 2.0MPa, heats to 100 DEG C of stirring reaction 1h.Filtering reactant mixture, liquid product composition is carried out qualitative and quantitative analysis by Agilent7890N/5970C gas chromatograph-mass spectrometer and Agilent6820 gas chromatograph.Paraformaldehyde conversion ratio is 66.7%, each component relative amount: CH3OCH2OCH3:32.6%；CH3O(CH2O)2CH3:20.3%；CH3O(CH2O)3~8CH3:53.4%；CH3O(CH2O)≥9CH3: do not detect.
Embodiment 23
Carrying out according to the method for embodiment 22, the catalyst Cat-12 synthesized except that the embodiment 12 of identical weight replaces 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: do not detect.
Embodiment 24
Carrying out according to the method for embodiment 22, the catalyst Cat-13 synthesized except that the embodiment 13 of identical weight replaces 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: do not detect.
Embodiment 25
Carry out according to the method for embodiment 22, the difference is that reaction raw materials is that formaldehyde contracts two butanol 48.1g(0.3mol), paraformaldehyde 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: do not detect.
Claims (9)
1. a resin-carried anionic acid ionic-liquid catalyst, it is characterised in that this catalyst is prepared via a method which: be scattered in toluene by storng-acid cation exchange resin, adds zwitterionic compound, reacts 12 ~ 24 hours at 80 ~ 100 DEG C；Reaction is filtered after terminating, then is extracted at 40 ~ 50 DEG C by filter cake dichloromethane, then 60 ~ 80 DEG C of vacuum dryings 12 ~ 24 hours, obtains resin-carried anionic acid ionic-liquid catalyst；Described storng-acid cation exchange resin selected from PuroliteC100E, PuroliteC150, PuroliteCT110, PuroliteCT175, PuroliteCT175DR, PuroliteCT169, PuroliteCT169DR, PuroliteCT275, PuroliteCT269, PuroliteCT276, PuroliteCT482, AmberliteIR120, Amberlyst15, Nafion-H, NafionNR50,001 × 7 (732), one in NKC-9；Described zwitterionic compound is the one in following structural formula:
, wherein, R1、R2、R3、R4And R5Represent H, aliphatic group, cycloaliphatic radical or aryl, and identical or different, n is the integer of 0-6.
2. catalyst as claimed in claim 1, it is characterised in that the mass ratio of described storng-acid cation exchange resin and zwitterionic compound is 1:5 ~ 1:10.
3. catalyst as claimed in claim 1, it is characterised in that described zwitterionic compound is the one in following structural formula:
Catalyst as claimed in claim 1, it is characterised in that described storng-acid cation exchange resin is the one in PuroliteCT175, PuroliteCT175DR, PuroliteCT276, PuroliteCT482, AmberliteIR120, Amberlyst15, NafionNR50,001 × 7 (732) and NKC-9.
4. the catalyst as described in claim 1,2,3 or 4 is in Prins condensation reaction, acetal or ketal reaction and the application in preparing polyoxymethylene dialkyl ether reaction.
5. apply as claimed in claim 5, it is characterised in that the reaction raw materials of described Prins condensation reaction is metaformaldehyde and alkene.
6. apply as claimed in claim 6, it is characterised in that described alkene is aliphatic alkene or aromatic olefin.
7. applying as claimed in claim 7, it is characterised in that described aliphatic alkene is isobutene. or octene, described aromatic olefin is styrene, para-orientation styrene or naphthalene ethylene.
8. apply as claimed in claim 5, it is characterised in that the raw material of described acetal or ketal reaction be glycerol and 37% formalin or glycerol and acetone.
9. apply as claimed in claim 5, it is characterised in that the described raw material preparing polyoxymethylene dialkyl ether reaction is methylal and paraformaldehyde or formaldehyde contract two butanol 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 |
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| CN106928036A (en) * | 2017-04-19 | 2017-07-07 | 四川达兴能源股份有限公司 | The method that polymethoxy butyl ether is prepared using butyral |
| 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 |
| 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 |
| CN109772451A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | Olefin epoxidation process |
| 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 |
| 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 |
| 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 |
| 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 |
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