CN108558891A - A kind of supported on silica-gel multinuclear sulfonic group acidic ion liquid and application - Google Patents
A kind of supported on silica-gel multinuclear sulfonic group acidic ion liquid and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
- C07D487/18—Bridged systems
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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Abstract
The present invention relates to a kind of supported on silica-gel multinuclear sulfonic group acidic ion liquids, and the method for preparing repefral using the supported on silica-gel multinuclear sulfonic group acidic ion liquid.Supported on silica-gel multinuclear sulfonic group acidic ion liquid multinuclear sulfonic group acidic ion liquid shown in formula (I) is obtained through supported on silica-gel.Catalyst of the present invention avoids conventional acid-catalyzed dose there are subsequent processings the problems such as complicated, equipment seriously corroded and a large amount of industrial wastewater discharges, and the catalyst shows good heat-resistant stability and efficient catalytic activity (esterification yield can reach 96% 99%) in preparing repefral reaction, catalyst and product are easily separated simultaneously, it may be reused, and reclaimer operation is simple, long lifespan, reaction condition is mild, overcome pollution of the acid catalyst to environment and the corrosion to equipment, production technology is simplified, production cost is saved.
Description
(1) technical field
The present invention relates to a kind of supported on silica-gel multinuclear sulfonic group acidic ion liquids, and utilize the supported on silica-gel multinuclear
The method that sulfonic group acidic ion liquid prepares repefral.
(2) background technology
Referred to as (DMP), colourless to yellowish oily liquids is not volatile, flammable, there is fragrance for repefral
Taste.The common organic solvents such as ethyl alcohol, ether can be dissolved in, there is very strong solvability.Water and petroleum ether cannot be dissolved in.Extensively
, especially can be compatible with multi cellulose resin, rubber, Vinylester for plastic plasticizer, culicifuge, there is compatible energy
The features such as power is strong, good film-forming property, adherence are good and good waterproof performance.With the increasing of the development and articles for daily use demand of related industries
Add, the demand of repefral increasingly increases.
Repefral (DMP) is extracted from natural oil earliest, yield is extremely limited.In order to adapt to constantly increase
Long industry and civilian demand, various chemical synthesising technologies come into being, and have developed a variety of production methods and synthesis work so far
Skill route.A series of catalyst of environmental type esterifications has been developed both at home and abroad recent years.For example, solid acid, solid
Body heteropoly acid, zeolite molecular sieve, storng-acid cation exchange resin, rare-earth compounds etc..Currently, domestic phthalic acid two
The industrial production process of methyl esters is mainly using phthalic anhydride and methanol as raw material, using the concentrated sulfuric acid as catalyst for making direct esterification
Carry out synthesis DMP.The above method is very strict due to using sulphuric acid catalysis, anti-leak and the anti-corrosive properties requirement of whole system.
The shortcomings that this method is：1. sulfuric acid severe corrosion to equipment；2. there is side reaction, the quality of product is influenced；3. after reactant
Processing, which will be passed through, to be neutralized, washes to remove sulfuric acid, and a large amount of waste water is generated.Not only make process complications, and pollute environment, no
Conducive to clean manufacturing.
Functionalized ion liquid is swift and violent as development in recent years, by the group for changing ionic liquid cation or anion
At and structure design with certain unique properties and prepare the ionic liquid with unique function.This makes ionic liquid
Body is studied worker and is known as " designer " solution again, while being used as sound response solvent in some reactions, has had both and has urged
Change acts on, and also can individually make catalyst use, be widely used in organic synthesis.Based on the above analysis, due to phthalic acid
The dissolubility of dimethyl ester is preferable, so wanting to design a kind of acid preferable ionic liquid as the catalyst to synthesis phthalic acid
The method of dimethyl ester is significantly.
(3) invention content
The object of the present invention is to provide a kind of Bronsted functionalized acidic ionic liquids with strong acidity, then use
Supported on silica-gel substitutes the sulfuric acid needed for conventional method, then again using this catalyst as catalyst direct catalytic reaction system with this
Standby repefral.
The technical solution adopted by the present invention is：
A kind of supported on silica-gel multinuclear sulfonic group acidic ion liquid, the multinuclear sulfonic group acidic ion liquid structure such as formula
(I) shown in：
Wherein R is-CH2CH2Or-CH2CH2CH2, X=CF3SO3 -Or HSO4 -；
The supported on silica-gel multinuclear sulfonic group acidic ion liquid prepares by the following method：
(1) using methenamine and halogenated hydrocarbons 1.3- propane sultones or 1.4- butyl sultones in the case where ethyl alcohol is as solvent
It reacts, the molar ratio of methenamine and halogenated hydrocarbons is 1:4-6, obtain intermediate again with strong sulfuric acid response, intermediate with it is dense
The molar ratio of sulfuric acid is 1:4-6 obtains four core azochlorosulfonate acid ion liquid；
(2) by tetraethyl orthosilicate, ethyl alcohol and step (1) synthesis four core azochlorosulfonate acid ion liquid mix, tetraethyl orthosilicate with
The volume ratio of ethyl alcohol is 1:0.2~1:10, the mass ratio of four core azochlorosulfonate acid ion liquid and tetraethyl orthosilicate is 5%~25%；
(3) after step (2) mixture stirs evenly, it is 1 to be added with tetraethyl orthosilicate volume ratio:0.1~1:2 molal volumes
It for the hydrochloric acid of 6mol/L, is vigorously stirred to form gel, the gel of formation is put into aging certain time in constant temperature pot, then vacuumizes dry
It is dry to get the supported on silica-gel multinuclear sulfonic group acidic ion liquid.
The invention further relates to the supported on silica-gel multinuclear sulfonic group acidic ion liquids to prepare repefral
In application.It, can be direct using phthalic anhydride and methanol as raw material using the immobilized acidic ion liquid of the present invention as catalyst
Esterification process is prepared without (low) color and luster, high-quality repefral.
The invention further relates to a kind of phthalic acid is prepared using the supported on silica-gel multinuclear sulfonic group acidic ion liquid
The method of dimethyl ester, the method includes：Phthalic anhydride and methanol are put into reactor, suitable supported on silica-gel is added
Multinuclear sulfonic group acidic ion liquid carries out 5~20h of esterification, reaction knot as catalyst, 70~120 DEG C of reaction temperature
Shu Hou, reaction solution obtain repefral through isolating and purifying.
The catalyst quality dosage is the 1%~20% of the quality of phthalic anhydride.
The methanol is 2~10 with the ratio between the amount of substance of phthalic anhydride:1.
The isolation and purification method is as follows：After reaction, filtration catalytic agent while hot, filtrate remove methanol and water, obtain
Repefral.
The beneficial effects are mainly as follows：Catalyst of the present invention avoids conventional acid-catalyzed dose, and there are subsequent processings
The problems such as complicated, equipment seriously corroded and a large amount of industrial wastewater discharges, and the catalyst is preparing repefral
Good heat-resistant stability and efficient catalytic activity (esterification yield can reach 96%-99%) are shown in reaction, are catalyzed simultaneously
Agent is easily separated with product, may be reused, and reclaimer operation is simple, and long lifespan, reaction condition is mild, overcomes acid catalyst
Pollution to environment and the corrosion to equipment simplify production technology, save production cost.
(4) specific implementation mode
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
Embodiment 1：The preparation of ionic liquid (a)
It is added methenamine (0.1mol, 14.0g), halogenated hydrocarbons 1.3- propane sultones in 250mL single-necked flasks
(0.44mol, 53.7g) and 100ml absolute ethyl alcohols react 6 hours at 70 DEG C, wash and be dried to obtain intermediate, are added
(0.4mol, 39.2g) concentrated sulfuric acid, the concentrated sulfuric acid react 10h under certain temperature, flask are rotated at 50 DEG C using being slowly added dropwise,
Yellow viscous liquid is obtained, is washed twice to obtain four ribozyme ionic liquid of final product with ethyl acetate, structural formula is as follows：
Embodiment 2：Collosol and gel solid-loaded ionic-liquid (b)
Three-necked flask is added in 100ml tetraethyl orthosilicates and 100ml ethyl alcohol, 50 DEG C of heat preservation 3h is heated to, is then added real
It applies and synthesizes four core azochlorosulfonate acid ion liquid 20g in example 1, be stirred 2h, until forming uniform mixed phase.40ml moles of body is added
Product is the hydrochloric acid of 6mol/L, is vigorously stirred to form gel.The gel of formation is put into constant temperature pot aging for 24 hours, the head product of generation
Vacuum drying is to get four ribozyme ionic-liquid catalyst of supported on silica-gel sulfonic acid.
Embodiment 3：The preparation of ionic liquid (c)
It is added methenamine (0.1mol, 14.0g), halogenated hydrocarbons 1.4- butyl sultones in 250mL single-necked flasks
(0.44mol, 59.9g) and 100ml absolute ethyl alcohols react 6 hours at 70 DEG C, wash and be dried to obtain intermediate, are added
(0.4mol, 39.2g) concentrated sulfuric acid, the concentrated sulfuric acid react 10h under certain temperature, flask are rotated at 50 DEG C using being slowly added dropwise,
Yellow viscous liquid is obtained, is washed twice to obtain four ribozyme ionic liquid of final product with ethyl acetate, structural formula is as follows：
Embodiment 4：Collosol and gel solid-loaded ionic-liquid (d)
Three-necked flask is added in 100ml tetraethyl orthosilicates and 100ml ethyl alcohol, 50 DEG C of heat preservation 3h is heated to, is then added real
The four core azochlorosulfonate acid ion liquid 20g synthesized in example 3 are applied, 2h is stirred, until forming uniform mixed phase.It is added 40ml moles
Volume is the hydrochloric acid of 6mol/L, is vigorously stirred to form gel.The gel of formation is put into constant temperature pot aging for 24 hours, the primiparity of generation
Product vacuum drying is to get four ribozyme ionic-liquid catalyst of supported on silica-gel sulfonic acid.
Embodiment 5：The preparation of ionic liquid (e)
It is added methenamine (0.1mol, 14.0g), halogenated hydrocarbons 1.3- propane sultones in 250mL single-necked flasks
(0.44mol, 53.7g) and 100ml absolute ethyl alcohols react 6 hours at 70 DEG C, wash and be dried to obtain intermediate, are added
(0.4mol, 60.0g) trifluoromethanesulfonic acid reacts 10h using being slowly added dropwise under certain temperature, and flask is rotated at 50 DEG C, is obtained
To yellow viscous liquid, washed twice to obtain four ribozyme ionic liquid of final product with ethyl acetate, structural formula is as follows：
Embodiment 6：Collosol and gel solid-loaded ionic-liquid (f)
Three-necked flask is added in 100ml tetraethyl orthosilicates and 100ml ethyl alcohol, 50 DEG C of heat preservation 3h is heated to, is then added real
The four core azochlorosulfonate acid ion liquid 20g synthesized in example 5 are applied, 2h is stirred, until forming uniform mixed phase.It is added 40ml moles
Volume is the hydrochloric acid of 6mol/L, is vigorously stirred to form gel.The gel of formation is put into constant temperature pot aging for 24 hours, the primiparity of generation
Product vacuum drying is to get four ribozyme ionic-liquid catalyst of supported on silica-gel sulfonic acid.
Embodiment 7：The preparation of ionic liquid (g)
It is added methenamine (0.1mol, 14.0g), halogenated hydrocarbons 1.3- propane sultones in 250mL single-necked flasks
(0.5mol, 61.0g) and 100ml absolute ethyl alcohols react 6 hours at 70 DEG C, wash and be dried to obtain intermediate, are added
(0.4mol, 39.2g) concentrated sulfuric acid, the concentrated sulfuric acid react 10h under certain temperature, flask are rotated at 50 DEG C using being slowly added dropwise,
Yellow viscous liquid is obtained, is washed twice to obtain four ribozyme ionic liquid of final product with ethyl acetate, structural formula is as follows：
Embodiment 8：Collosol and gel solid-loaded ionic-liquid (h)
Three-necked flask is added in 100ml tetraethyl orthosilicates and 100ml ethyl alcohol, 50 DEG C of heat preservation 3h is heated to, is then added real
It applies and synthesizes four core azochlorosulfonate acid ion liquid 15g in example 7, be stirred 2h, until forming uniform mixed phase.40ml moles of body is added
Product is the hydrochloric acid of 6mol/L, is vigorously stirred to form gel.The gel of formation is put into constant temperature pot aging for 24 hours, the head product of generation
Vacuum drying is to get four ribozyme ionic-liquid catalyst of supported on silica-gel sulfonic acid.
Embodiment 9：Collosol and gel solid-loaded ionic-liquid (i)
Three-necked flask is added in 100ml tetraethyl orthosilicates and 100ml ethyl alcohol, 50 DEG C of heat preservation 3h is heated to, is then added real
It applies and synthesizes four core azochlorosulfonate acid ion liquid 25g in example 7, be stirred 2h, until forming uniform mixed phase.40ml moles of body is added
Product is the hydrochloric acid of 6mol/L, is vigorously stirred to form gel.The gel of formation is put into constant temperature pot aging for 24 hours, the head product of generation
Vacuum drying is to get four ribozyme ionic-liquid catalyst of supported on silica-gel sulfonic acid.
Embodiment 10：Collosol and gel solid-loaded ionic-liquid (j)
Three-necked flask is added in 100ml tetraethyl orthosilicates and 100ml ethyl alcohol, 50 DEG C of heat preservation 3h is heated to, is then added real
It applies and synthesizes four core azochlorosulfonate acid ion liquid 20g in example 7, be stirred 2h, until forming uniform mixed phase.60ml moles of body is added
Product is the hydrochloric acid of 6mol/L, is vigorously stirred to form gel.The gel of formation is put into constant temperature pot aging for 24 hours, the head product of generation
Vacuum drying is to get four ribozyme ionic-liquid catalyst of supported on silica-gel sulfonic acid.
Embodiment 11：
The addition phthalic anhydride (0.1mol, 148.1g) in 100mL single-necked flasks, methanol (0.4mol, 12.8g),
Immobilized ionic-liquid catalyst 2g prepared by embodiment 2, is during the reaction detached the water of generation using separator in time
It removes.In 85 DEG C of synthesis under normal pressure 10h, reaction finishes standing to room temperature, filters out solid catalyst, depressurizes rotary evaporation, removes
Excessive methanol and the moisture of generation are dried to obtain the neighbour without (low) color and luster, high-quality respectively after alkali cleaning, being washed to neutrality
Rutgers, esterification yield about 96%.Catalyst is dried in vacuo after ethyl acetate washs, the ionic liquid being recycled
Body, and use it in the investigation experiment of catalytic cycle.
Embodiment 12：
The addition phthalic anhydride (0.1mol, 148.1g) in 100mL single-necked flasks, methanol (0.5mol, 16.1g),
Immobilized ionic-liquid catalyst 2g prepared by embodiment 2, is during the reaction detached the water of generation using separator in time
It removes.In 85 DEG C of synthesis under normal pressure 10h, reaction finishes standing to room temperature, filters out solid catalyst, depressurizes rotary evaporation, removes
Excessive methanol and the moisture of generation are dried to obtain the neighbour without (low) color and luster, high-quality respectively after alkali cleaning, being washed to neutrality
Rutgers, esterification yield about 97%.Catalyst is dried in vacuo after ethyl acetate washs, the ionic liquid being recycled
Body.
Embodiment 13：
The addition phthalic anhydride (0.1mol, 148.1g) in 100mL single-necked flasks, methanol (0.4mol, 12.8g),
Immobilized ionic-liquid catalyst 4g prepared by embodiment 2, is during the reaction detached the water of generation using separator in time
It removes.In 85 DEG C of synthesis under normal pressure 10h, reaction finishes standing to room temperature, filters out solid catalyst, depressurizes rotary evaporation, removes
Excessive methanol and the moisture of generation are dried to obtain the neighbour without (low) color and luster, high-quality respectively after alkali cleaning, being washed to neutrality
Rutgers, esterification yield about 97%.Catalyst is dried in vacuo after ethyl acetate washs, the ionic liquid being recycled
Body.
Embodiment 14：
The addition phthalic anhydride (0.1mol, 148.1g) in 100mL single-necked flasks, methanol (0.4mol, 12.8g),
Immobilized ionic-liquid catalyst 1.5g prepared by embodiment 2 utilizes separator by the water of generation and time-division during the reaction
From removal.In 85 DEG C of synthesis under normal pressure 10h, reaction finishes standing to room temperature, filters out solid catalyst, depressurizes rotary evaporation, remove
Excessive methanol and the moisture of generation are removed, respectively after alkali cleaning, being washed to neutrality, is dried to obtain without (low) color and luster, high-quality
Repefral, esterification yield about 90%.Catalyst is dried in vacuo after ethyl acetate washs, the ionic liquid being recycled
Body.
Embodiment 15：
The addition phthalic anhydride (0.1mol, 148.1g) in 100mL single-necked flasks, methanol (0.4mol, 12.8g),
Immobilized ionic-liquid catalyst 2g prepared by embodiment 2, is during the reaction detached the water of generation using separator in time
It removes.In 100 DEG C of synthesis under normal pressure 10h, reaction finishes standing to room temperature, filters out solid catalyst, depressurizes rotary evaporation, removes
Excessive methanol and the moisture of generation are dried to obtain the neighbour without (low) color and luster, high-quality respectively after alkali cleaning, being washed to neutrality
Rutgers, esterification yield about 93%.Catalyst is dried in vacuo after ethyl acetate washs, the ionic liquid being recycled
Body.
Embodiment 16：
The addition phthalic anhydride (0.1mol, 148.1g) in 100mL single-necked flasks, methanol (0.4mol, 12.8g),
Immobilized ionic-liquid catalyst 2g prepared by embodiment 2, is during the reaction detached the water of generation using separator in time
It removes.In 70 DEG C of synthesis under normal pressure 10h, reaction finishes standing to room temperature, filters out solid catalyst, depressurizes rotary evaporation, removes
Excessive methanol and the moisture of generation are dried to obtain the neighbour without (low) color and luster, high-quality respectively after alkali cleaning, being washed to neutrality
Rutgers, esterification yield about 86%.Catalyst is dried in vacuo after ethyl acetate washs, the ionic liquid being recycled
Body.
Embodiment 17：
The addition phthalic anhydride (0.1mol, 148.1g) in 100mL single-necked flasks, methanol (0.4mol, 12.8g),
Immobilized ionic-liquid catalyst 2g prepared by embodiment 2, is during the reaction detached the water of generation using separator in time
It removes.In 85 DEG C of synthesis under normal pressure 15h, reaction finishes standing to room temperature, filters out solid catalyst, depressurizes rotary evaporation, removes
Excessive methanol and the moisture of generation are dried to obtain the neighbour without (low) color and luster, high-quality respectively after alkali cleaning, being washed to neutrality
Rutgers, esterification yield about 95%.Catalyst is dried in vacuo after ethyl acetate washs, the ionic liquid being recycled
Body.
Embodiment 18：
The addition phthalic anhydride (0.1mol, 148.1g) in 100mL single-necked flasks, methanol (0.4mol, 12.8g),
Immobilized ionic-liquid catalyst 2g prepared by embodiment 2, is during the reaction detached the water of generation using separator in time
It removes.In 85 DEG C of synthesis under normal pressure 5h, reaction finishes standing to room temperature, filters out solid catalyst, depressurizes rotary evaporation, removed
The methanol of amount and the moisture of generation are dried to obtain the adjacent benzene without (low) color and luster, high-quality respectively after alkali cleaning, being washed to neutrality
Dicarboxylic acid dimethyl ester, esterification yield about 69%.Catalyst is dried in vacuo after ethyl acetate washs, the ionic liquid being recycled.
Embodiment 19：
The addition phthalic anhydride (0.1mol, 148.1g) in 100mL single-necked flasks, methanol (0.4mol, 12.8g),
Used immobilized ionic-liquid catalyst 2g, is during the reaction detached the water of generation using separator in time in embodiment 4
It removes.In 85 DEG C of synthesis under normal pressure 10h, reaction finishes standing to room temperature, filters out solid catalyst, depressurizes rotary evaporation, removes
Excessive methanol and the moisture of generation are dried to obtain the neighbour without (low) color and luster, high-quality respectively after alkali cleaning, being washed to neutrality
Rutgers, esterification yield about 89%.Catalyst is dried in vacuo after ethyl acetate washs, the ionic liquid being recycled
Body.
Embodiment 20：
The addition phthalic anhydride (0.1mol, 148.1g) in 100mL single-necked flasks, methanol (0.4mol, 12.8g),
Used immobilized ionic-liquid catalyst 2g, is during the reaction detached the water of generation using separator in time in embodiment 6
It removes.In 85 DEG C of synthesis under normal pressure 10h, reaction finishes standing to room temperature, filters out solid catalyst, depressurizes rotary evaporation, removes
Excessive methanol and the moisture of generation are dried to obtain the neighbour without (low) color and luster, high-quality respectively after alkali cleaning, being washed to neutrality
Rutgers, esterification yield about 82%.Catalyst is dried in vacuo after ethyl acetate washs, the ionic liquid being recycled
Body.
Embodiment 21
The addition phthalic anhydride (0.1mol, 148.1g) in 100mL single-necked flasks, methanol (0.4mol, 12.8g),
Used immobilized ionic-liquid catalyst 2g, is during the reaction detached the water of generation using separator in time in embodiment 8
It removes.In 85 DEG C of synthesis under normal pressure 10h, reaction finishes standing to room temperature, filters out solid catalyst, depressurizes rotary evaporation, removes
Excessive methanol and the moisture of generation are dried to obtain the neighbour without (low) color and luster, high-quality respectively after alkali cleaning, being washed to neutrality
Rutgers, esterification yield about 86%.Catalyst is dried in vacuo after ethyl acetate washs, the ionic liquid being recycled
Body.
Embodiment 21：The cycle of catalyst
The addition phthalic anhydride (0.1mol, 148.1g) in 100mL single-necked flasks, methanol (0.4mol, 12.8g),
Used immobilized ionic-liquid catalyst 2g, is during the reaction detached the water of generation using separator in time in embodiment 20
It removes.In 85 DEG C of synthesis under normal pressure 10h, reaction finishes standing to room temperature, filters out solid catalyst, depressurizes rotary evaporation, removes
Excessive methanol and the moisture of generation are dried to obtain the neighbour without (low) color and luster, high-quality respectively after alkali cleaning, being washed to neutrality
Rutgers, esterification yield about 95%.Catalyst is dried in vacuo after ethyl acetate washs, the ionic liquid being recycled
Body, and the investigation experiment of catalytic cycle is used it for, same operation 7 times is repeated, obtaining its experiment, the results are shown in Table 1.
| Number | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Esterification yield % | 97 | 97 | 96 | 96 | 95 | 95 | 95 | 95 |
Table 1.
Claims (6)
1. a kind of supported on silica-gel multinuclear sulfonic group acidic ion liquid, the multinuclear sulfonic group acidic ion liquid structure such as formula
(I) shown in：
Wherein R is-CH2CH2Or-CH2CH2CH2, X=CF3SO3 -Or HSO4 -；
The supported on silica-gel multinuclear sulfonic group acidic ion liquid prepares by the following method：
(1) methenamine and halogenated hydrocarbons 1.3- propane sultones or 1.4- butyl sultones are occurred in the case where ethyl alcohol is as solvent
The molar ratio of reaction, methenamine and halogenated hydrocarbons is 1:4-6, obtain intermediate again with strong sulfuric acid response, intermediate and the concentrated sulfuric acid
Molar ratio be 1:4-6 obtains four core azochlorosulfonate acid ion liquid；
(2) the four core azochlorosulfonate acid ion liquid by the synthesis of tetraethyl orthosilicate, ethyl alcohol and step (1) mix, tetraethyl orthosilicate and ethyl alcohol
Volume ratio be 1:0.2~1:10, the mass ratio of four core azochlorosulfonate acid ion liquid and tetraethyl orthosilicate is 5%~25%；
(3) after step (2) mixture stirs evenly, it is 1 to be added with tetraethyl orthosilicate volume ratio:0.1~1:2 molal volumes are
The hydrochloric acid of 6mol/L is vigorously stirred to form gel, and the gel of formation is put into aging certain time in constant temperature pot, then vacuumizes dry
It is dry to get the supported on silica-gel multinuclear sulfonic group acidic ion liquid.
2. supported on silica-gel multinuclear sulfonic group acidic ion liquid answering in preparing repefral described in claim 1
With.
3. preparing the side of repefral using supported on silica-gel multinuclear sulfonic group acidic ion liquid described in claim 1
Method, the method includes：Phthalic anhydride and methanol are put into reactor, suitable supported on silica-gel multinuclear sulfonic group is added
Acidic ion liquid carries out 5~20h of esterification, after reaction, reaction solution as catalyst, 70~120 DEG C of reaction temperature
Through isolating and purifying to obtain repefral.
4. method as claimed in claim 3, it is characterised in that the catalyst quality dosage is the quality of phthalic anhydride
1%~20%.
5. method as claimed in claim 3, it is characterised in that the methanol with the amount of the substance of phthalic anhydride it
Than being 2~10:1.
6. method as claimed in claim 3, it is characterised in that the isolation and purification method is as follows：After reaction, mistake while hot
Catalyst is filtered, filtrate removes methanol and water, obtains repefral.
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| CN114588935A (en) * | 2022-03-04 | 2022-06-07 | 浙江大学 | Preparation of sulfonic acid type supported catalyst for phthalic anhydride esterification |
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| CN106916059A (en) * | 2015-12-25 | 2017-07-04 | 上虞新和成生物化工有限公司 | A kind of method that multi-sulfonic catalysis of functional ionic liquid prepares raspberry ketone |
| CN106674005A (en) * | 2016-11-15 | 2017-05-17 | 浙江工商大学 | Method for preparing advanced fatty acid ester by using catalysis of solid-supported ionic liquid catalyst |
| CN106694036A (en) * | 2016-11-15 | 2017-05-24 | 浙江工商大学 | Method for preparing immobilized ionic liquid catalyst |
| CN107162970A (en) * | 2017-06-30 | 2017-09-15 | 马鞍山市泰博化工科技有限公司 | A kind of ionic liquid-catalyzed synthesis dihydro 4 of 2 aryl 2,3 of highly acidity（1H）The method of qualone derivative |
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| CN114588935A (en) * | 2022-03-04 | 2022-06-07 | 浙江大学 | Preparation of sulfonic acid type supported catalyst for phthalic anhydride esterification |
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Application publication date: 20180921 |