CN108794662B - Preparation method and application of macroporous strong-acid resin - Google Patents
Preparation method and application of macroporous strong-acid resin Download PDFInfo
- Publication number
- CN108794662B CN108794662B CN201810507489.XA CN201810507489A CN108794662B CN 108794662 B CN108794662 B CN 108794662B CN 201810507489 A CN201810507489 A CN 201810507489A CN 108794662 B CN108794662 B CN 108794662B
- Authority
- CN
- China
- Prior art keywords
- acid
- divinylbenzene
- macroporous
- resin
- reaction
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
-
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
- C07C51/38—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by decarboxylation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method and application of macroporous strong-acid resin, wherein the macroporous strong-acid resin takes p-nitrostyrene as a main monomer raw material and divinylbenzene as a cross-linking agent, and is subjected to a co-reaction with a dispersing agent, an initiator, a pore-forming agent and the like to prepare microspheres of the p-nitrostyrene-divinylbenzene, and then the microspheres are subjected to a sulfonation reaction of chlorosulfonic acid to prepare the macroporous strong-acid resin. The prepared macroporous strong-acid resin has good thermal stability and can be used as a high-efficiency catalyst of the following system: catalyzing isoamylene and methanol to react and synthesize methyl tert-amyl ether (TAME), isopentene and ethanol to react and synthesize ethyl tert-amyl ether (ETBE), and cyclopentene and methanol to react and synthesize cyclopentyl methyl ether (CPME); and has extremely high catalytic activity for reactions such as the synthesis of loxoprofen acid which is a precursor of loxoprofen sodium. In addition, the macroporous strong-acid resin after catalytic reaction can be recycled, and is a green and environment-friendly high-efficiency catalytic material.
Description
Technical Field
The invention belongs to the technical field of polymer resin, and particularly relates to a preparation method and application of macroporous strong-acid resin.
Background
The ion exchange resin is widely applied to the fields of industrial water treatment, medicine and food industry, fine chemical industry such as pesticides, dyes, coatings, detergents and the like, ore dressing, environmental protection and the like. In the field of organic synthesis, strongly acidic ion exchange resins are used as catalysts for organic reactions such as epoxidation, addition and esterification reactions. Published article "Ce" in Zhou Jie, ren Qing Gong4+Study on catalytic epoxidation reaction of modified cation exchange resin (Zhoujie, Ningqinggong, Panjing, etc.. Ce4+Study of modified cation exchange resin catalyzed epoxidation reaction [ J]Ion exchange and adsorption 2015(4) 359-4+The modified cation exchange resin is used for catalyzing the biodiesel epoxy reaction and replacing liquid acid catalysts such as concentrated sulfuric acid, phosphoric acid and the like commonly used in the traditional industrial production, the catalyst has the advantages of environmental protection, high catalytic activity, low price and the like, and the epoxy value of the epoxy methyl ester catalytically synthesized can reach 5.85%.
With the continuous research, the macroporous strong-acid ion exchange resin gradually exposes some problems. Sulfonic acid groups connected with benzene rings are easy to fall off at higher temperature, and the thermal stability is poor. In the case of xiong, Zhu Shi Hua, etcThe table "study of deactivation mechanism of cation exchange resin catalyst for esterification reaction" (bear Ting, Zhushihua, Zhang Jingliang, etc.. study of deactivation mechanism of cation exchange resin catalyst for esterification reaction [ J]Industrial catalysis, 2012, 20(5): 36-40.) the esterification of acetic acid with isopropanol was catalyzed at 60 ℃ using strong acid cation exchange resins and studies found that loss of active sulfonic acid groups was the major factor leading to a decrease in catalyst activity. The use of the macroporous strong acid ion resin on the market at present can only be used below 140 ℃ and can be deactivated by volatilizing sulfonic acid groups at 140-150 ℃, thus greatly limiting the use of the ion exchange resin. For some reactions which need to be carried out at higher temperature, the falling off can cause the reduction of catalytic activity, the prolonging of the required reaction time, even the complete failure of the catalyst, the pollution to a reaction system, the complex post-treatment process of residual liquid after the reaction and the large discharge of three wastes. Shuoshi academic thesis published in Zuocun, namely methyl acetate produced by ion exchange resin catalytic esterification rectification (Zuocun. methyl acetate produced by ion exchange resin catalytic esterification rectification)]Xiangtan university 2015), a polymer with styrene as a polymerization monomer and divinylbenzene as a crosslinking agent is adopted as a substrate, and sulfonic acid groups (-SO) with main exchange groups are obtained after sulfonation with concentrated sulfuric acid or fuming sulfuric acid3H) The strongly acidic ion exchange resin of (1). Concentrated sulfuric acid or fuming sulfuric acid is used as a sulfonating agent of the resin, and the concentrated sulfuric acid and SO in the concentrated sulfuric acid3The sulfonation reaction is violent, local overheating, oxidation, coking and other phenomena are easy to occur, and a large amount of byproducts are generated in the reaction process.
The stability of C-S bond between sulfonic acid group and aromatic ring determines the thermal stability of polystyrene resin, if electron-withdrawing group is introduced into polystyrene resin, the bond energy between benzene ring and sulfonic group is increased, the C-S bond between benzene ring and sulfonic group is more stable, thus increasing the service temperature of styrene resin.
The conversion of the sulfonating agent from concentrated sulfuric acid to chlorosulfonic acid has a number of advantages. A paper published in Muly Li, Drift and economic theory of New ordered mesoporous sulfonated phenol-formaldehyde resin FDU-16-SO3H Synthesis and acid catalysis Property (Muli, economic; King Chun Yan., novel ordered mesoporous sulfonated phenolic resin FDU-16-SO)3Synthesis of H and acid catalysis Properties [ J]2010, 31(8): 1643-1646.) A novel ordered mesoporous solid acid catalyst FDU-16-SO is prepared by sulfonating ordered mesoporous phenolic resin (FDU-16) with chlorosulfonic acid3The experiment result shows that the sulfonated solid acid catalyst still maintains high orderliness and shows higher catalytic activity in esterification reaction and acylation reaction. Chlorosulfonic acid can be regarded as SO3The complex of HCl is easily dissolved in organic solvents of chloroform, carbon tetrachloride and nitrobenzene and liquid sulfur trioxide, and chlorosulfonic acid is used as a sulfonating agent, so that the method has the advantages of strong reaction capability, easy discharge of generated HCl and contribution to complete reaction; in addition to chlorosulfonic acid alone, a solvent may also be added.
In organic synthesis, strong acids are commonly used as catalysts for esterification, hydrolysis, transesterification, hydration, and the like. The same catalysis of the above reaction is possible and advantageous even more by replacing the above acid with an acidic resin. Such as the resin can be repeatedly used, the environment is protected, the catalytic reaction is easy to control, and the like. For example, in the preparation of t-amyl methyl ether (TAME), t-amyl ethyl ether (ETBE), cyclopentyl methyl ether (CPME) and loxoprofen acid, a strongly acidic resin can be used as a catalyst. Such as: isobutene reacts with methanol and ethanol to generate an ether organic solvent. For another example, concentrated sulfuric acid or p-toluenesulfonic acid is commonly used as a catalyst in esterification and hydrolysis reactions in the process of preparing the anti-inflammatory analgesic medicament loxoprofen acid. The oxidation of the raw material 2- (4-bromomethylphenyl) propionic acid is easily caused by the oxidation of concentrated sulfuric acid, so that the problem that industrial wastewater which is difficult to treat is easily generated by adding p-toluenesulfonic acid as an esterification catalyst in the traditional industry is solved. In the reactions of organic esterification and ester hydrolysis, strong acid resin is adopted to replace concentrated sulfuric acid or p-toluenesulfonic acid, so that the reaction can be effectively catalyzed, and the problems of impurities introduced by oxidation of raw materials or products by concentrated sulfuric acid, equipment corrosion, more industrial wastewater generation and the like caused by the traditional concentrated sulfuric acid catalysis process method are solved.
In order to solve the negative effects caused by using concentrated sulfuric acid or fuming sulfuric acid in the preparation process of the existing strong acid resin and the limitations of the existing strong acid resin in the aspects of poor thermal stability and the like in the aspect of use, expand the use range of the strong acid resin and further meet the requirements of using a catalyst in an organic synthesis reaction under harsh conditions (conditions such as high temperature, high pressure, strong corrosive solvent and the like), the applicant of the invention adopts p-nitrostyrene as a main monomer raw material and divinyl benzene as a cross-linking agent, and repeatedly practices through continuous exploration, and very surprised discovers that: the method obtains a p-nitrostyrene-p-divinylbenzene polymer through a synthesis process method, obtains a novel strong acid resin through sulfonation of chlorosulfonic acid and a series of post-treatment processes, and shows that the strong acid resin has extremely high thermal stability and thermal performance greatly superior to the prior resin through thermal performance test analysis.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and the invention uses p-nitrostyrene as a main monomer, uses divinylbenzene as a cross-linking agent, is mixed with a dispersant, an initiator and a pore-forming agent to prepare a microspherical solid, is washed in petroleum ether to remove the pore-forming agent, and finally prepares macroporous strong-acid resin through sulfonation of chlorosulfonic acid, so as to improve the defect that the existing acid resin is easy to inactivate at high temperature. Meanwhile, as the inventor continuously researches and explores and tests, the macroporous strong-acid resin is unexpectedly found to have ultrahigh catalytic activity on a plurality of synthesis reactions when being used as a catalyst! For example: the macroporous strong acid resin prepared by the invention is used as a catalyst, the supercritical technology is adopted to catalyze the reactions of isoamylene and methanol for synthesizing TAME, isoamylene and ethanol for synthesizing ETBE, cyclopentene and methanol for synthesizing CPME, and the reactions of synthesizing loxoprofen acid serving as a precursor of the loxoprofen sodium and the like have extremely high catalytic activity, and are easy to recycle after being used. Can be repeatedly used.
In order to achieve the purpose, the invention adopts the technical scheme that:
a macroporous strong acid resin is characterized in that: the macroporous strong acid resin is prepared by mixing p-nitrostyrene serving as a main monomer and divinylbenzene serving as a cross-linking agent with a dispersing agent, an initiator and a pore-forming agent to prepare microspheres, washing the microspheres in petroleum ether to remove the pore-forming agent, and finally under the action of a sulfonating agent.
A preparation method of macroporous strong acid resin is characterized by comprising the following steps:
the method comprises the following steps: weighing a certain amount of p-nitrostyrene, divinyl benzene, a pore-foaming agent and an initiator. Mixing p-nitrostyrene and divinylbenzene, and washing with 5% NaOH solution for 2 times; washing with water for 2 times to remove polymerization inhibitor; distilling under reduced pressure at the absolute pressure of 10-100Pa and the temperature of 45 ℃ to obtain a purified mixture of p-nitroaniline and divinylbenzene, adding a pore-forming agent and an initiator into the mixture of the p-nitroaniline and the divinylbenzene, and pouring the mixture into a three-neck flask filled with 0.2-1.5% of a dispersant solution after the initiator is dissolved;
step two: controlling the rotating speed to raise the temperature to 65 ℃ under the condition of 1000r/min to 4000r/min, and preserving the temperature for 1h to 3 h; then heating to 75 ℃, and preserving the heat for 4-8 h; then the temperature is raised to 90 ℃, and the temperature is kept for 0.5 to 2 hours. Cooling, filtering, washing with water, drying, and washing with petroleum ether to obtain a p-nitrostyrene-divinylbenzene microsphere solid;
step three: putting the p-nitrostyrene-divinylbenzene white spheres prepared in the step two in CCl4Swelling for 1-4 h, adding chlorosulfonic acid with the mass ratio of 1: 0.5-2 to the p-nitrostyrene-divinylbenzene microspheres under the stirring condition, reacting for 3h, then sequentially washing with ethanol and water to neutrality, soaking in deionized water at the room temperature of 15-25 ℃ for 24h, filtering, and vacuum drying to obtain the macroporous strong-acid resin.
The preferable mass ratio of the p-nitrostyrene to the divinylbenzene to the porogen to the initiator is 1: 0.05 to 0.3: 0.05 to 1.5: 0.005 to 0.03.
The preferable dispersant is any one or more of polyvinyl alcohol, methyl cellulose, sodium dodecyl sulfate and active calcium phosphate.
The preferable initiator is one or more than one of azodiisobutyronitrile AIBN, azodiisoheptonitrile ABVN, azodiisobutyronitrile dimethyl ester, benzoyl peroxide BPO, benzoyl peroxide tert-butyl ester BPB and chloracetic acid pentaerythritol tetraester.
The preferred porogenic agent is any one or a mixture of toluene and paraffin oil.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:
according to the invention, the electron-withdrawing group nitro is introduced into the polystyrene resin, so that the bond energy between the benzene ring and the sulfonic group is increased, and the sulfonic group on the benzene ring is more stable, thereby enhancing the thermal stability. The upper limit of the using temperature of the prior polystyrene resin is 140 ℃, the polystyrene resin is decomposed at 140-150 ℃, the using temperature of the macroporous strong-acid resin prepared by the invention can reach 260 ℃, and the macroporous strong-acid resin is obviously inactivated at 300 ℃.
The macroporous strong acid resin is used as a catalyst to efficiently catalyze reactions such as synthesis of TAME by reaction of isoamylene and methanol, synthesis of ETBE by reaction of isoamylene and ethanol, synthesis of CPME by reaction of cyclopentene and methanol and synthesis of loxoprofen acid serving as a precursor of loxoprofen sodium, and the like, and is easy to recycle after use. Can be repeatedly used in a high-temperature environment for many times, and expands the application range of the macroporous strong-acid resin in the field of catalytic reaction.
In addition, the sulfonation of the polyethylene ionic resin is realized by adopting chlorosulfonic acid instead of concentrated sulfuric acid or fuming sulfuric acid, and the sulfonated polyethylene ionic resin has the following beneficial effects: chlorosulfonic acid can be regarded as SO3The complex of HCl is easily dissolved in organic solvents such as chloroform, carbon tetrachloride, nitrobenzene and the like and liquid sulfur trioxide, and chlorosulfonic acid is used as a sulfonating agent, so that the method has the advantages of strong reaction capability, easy discharge of generated HCl and contribution to complete reaction. The invention increases the bond energy between benzene ring and sulfonic group by introducing electron-withdrawing group nitryl on polystyrene resin, benzeneThe sulfonic acid group on the ring is more stable, so that the thermal stability is enhanced. The enhanced thermal stability can lead the resin to be repeatedly used as a catalyst in organic high-temperature reaction for many times, and expands the application range of the macroporous strong-acid resin in the field of catalytic reaction.
Drawings
FIG. 1 is a TG diagram of a macroporous strongly acidic resin prepared by the present invention.
FIG. 2 is a DSC of a macroporous strongly acidic resin prepared by the present invention.
Figure 3 is a scheme showing the synthesis of loxoprofen acid.
Detailed Description
In order to better understand the present invention, the following examples are given to better illustrate the present invention, but the present invention is not limited to the following examples and should not be construed as being limited thereto.
Examples 1 to 5 below are examples of the production of macroporous strongly acidic resins A1 to A5, respectively.
Example 1
A preparation method of macroporous strong acid resin comprises the following specific steps:
the method comprises the following steps: weighing p-nitrostyrene, divinylbenzene, toluene and azobisisoheptonitrile at a mass ratio of 1: 0.05: 0.005, wherein the mass of the selected p-nitrostyrene is 7.458 g. Mixing p-nitroarene and divinylbenzene, washing with 5% (mass fraction, the same below) NaOH solution for 2 times, washing with water for 2 times to remove the p-phenylenediamine polymerization inhibitor, and distilling under reduced pressure at 10Pa (absolute pressure, the same below) and 45 ℃ to obtain a purified mixture of p-nitroarene and divinylbenzene. Adding toluene and azodiisoheptonitrile into a mixture of p-nitrostyrene and divinylbenzene, stirring and mixing uniformly, and then pouring into a three-neck flask filled with 30ml of 0.2% (mass fraction, the same below) methyl cellulose solution;
step two: controlling the rotating speed to raise the temperature to 65 ℃ under the condition of 1000r/min, and keeping the temperature for 1 h; then heating to 75 ℃, and preserving the heat for 4 hours; then the temperature is raised to 90 ℃ and the temperature is kept for 0.5 h. Cooling, filtering, washing with water, drying, washing with about 30mL of petroleum ether, and drying to obtain the crosslinked poly-p-nitrophenylethylene microspheres;
step three: placing the cross-linked poly-p-nitroaniline microspheres prepared in the step two in CCl4Swelling for 1h, adding chlorosulfonic acid with the mass ratio of 1: 0.5 to the p-nitrostyrene-divinylbenzene microspheres under the condition of stirring, reacting for 3h, sequentially washing with ethanol and water to neutrality, soaking with deionized water at room temperature for 24h, filtering, and vacuum drying to obtain the macroporous strong-acid resin A1.
Example 2
A preparation method of macroporous strong acid resin comprises the following specific steps:
the method comprises the following steps: weighing p-nitrostyrene, divinylbenzene, paraffin oil and dibenzoyl peroxide at a mass ratio of 1: 0.3: 1.5: 0.03, wherein the mass of the selected p-nitrostyrene is 7.458 g. Washing with 5% NaOH water solution for 2 times, washing with water for 2 times to remove p-phenylenediphenol polymerization inhibitor, and distilling under reduced pressure at 10Pa and 45 deg.C to obtain purified mixture of p-nitrophenylethylene and divinylbenzene. Adding paraffin oil and dibenzoyl peroxide (BPO) into a mixture of p-nitrostyrene and divinylbenzene, and pouring into a three-neck flask filled with 30ml of 1.5% methyl cellulose solution;
step two: controlling the rotating speed to rise to 65 ℃ under the condition of 4000r/min, and preserving heat for 3 hours; then heating to 75 ℃, and preserving the heat for 8 hours; then the temperature is raised to 90 ℃ and the temperature is kept for 2 h. Cooling, filtering, washing with water, drying, washing with about 30mL of petroleum ether, and drying to obtain crosslinked poly-p-nitroaniline microspheres;
step three: placing the cross-linked poly-p-nitroaniline microspheres prepared in the step two in CCl4Swelling for 4h, adding chlorosulfonic acid with the mass ratio of 1: 2 to the p-nitrostyrene-divinylbenzene microspheres, reacting for 3h, sequentially washing with ethanol and water to neutrality, soaking with deionized water at room temperature for 24h, filtering, and vacuum drying to obtain macroporous strong-acid resin A2.
Example 3
A preparation method of macroporous strong acid resin comprises the following specific steps:
the method comprises the following steps: weighing the p-nitrostyrene, the divinylbenzene, the paraffin oil and the dimethyl azodiisobutyrate in a mass ratio of 1: 0.16: 0.75: 0.015, wherein the mass of the selected p-nitrostyrene is 7.458 g. Mixing p-nitroarene and divinylbenzene, washing with 5% NaOH solution for 2 times, washing with water for 2 times to remove p-phenylenediphenol polymerization inhibitor, and distilling under reduced pressure at 10Pa and 45 ℃ to obtain a purified mixture of p-nitroarene and divinylbenzene. Adding paraffin oil and dimethyl azodiisobutyrate into a mixture of p-nitrostyrene and divinylbenzene, and pouring into a three-neck flask filled with 30ml of 0.85% polyvinyl alcohol solution;
step two: controlling the rotating speed to raise the temperature to 65 ℃ under the condition of 2500r/min, and keeping the temperature for 2 h; then heating to 75 ℃, and preserving the heat for 6 hours; then the temperature is raised to 90 ℃ and the temperature is kept for 1.25 h. Cooling, filtering, washing with water, drying, washing with about 30mL of petroleum ether, and drying to obtain the crosslinked poly-p-nitrophenylethylene microspheres;
step three: placing the cross-linked poly-p-nitroaniline microspheres prepared in the step two in CCl4Swelling for 2.5h, adding chlorosulfonic acid with the mass ratio of the p-nitrostyrene-divinylbenzene microspheres being 1: 1.25 under the condition of stirring, reacting for 3h, then sequentially washing with ethanol and water to neutrality, soaking with deionized water at room temperature for 24h, filtering, and vacuum drying to obtain the macroporous strong-acid resin A3.
Example 4
A preparation method of macroporous strong acid resin comprises the following specific steps:
the method comprises the following steps: weighing p-nitrostyrene, divinylbenzene, toluene and benzoyl peroxide tert-butyl ester at a mass ratio of 1: 0.3: 0.65: 0.025, wherein the mass of the selected p-nitrostyrene is 7.458 g. Mixing p-nitroarene and divinylbenzene, washing with 5% NaOH solution for 2 times, washing with water for 2 times to remove p-phenylenediphenol polymerization inhibitor, and distilling under reduced pressure at 10Pa and 45 ℃ to obtain a purified mixture of p-nitroarene and divinylbenzene. Toluene and benzoyl peroxide were added to a mixture of p-nitrostyrene and divinylbenzene, and then the mixture was poured into a three-necked flask containing 30ml of 0.6% polyvinyl alcohol solution.
Step two: controlling the rotating speed to raise the temperature to 65 ℃ under the condition of 2000r/min, and keeping the temperature for 1.5 h; then heating to 75 ℃, and preserving the heat for 5 hours; then the temperature is raised to 90 ℃ and the temperature is kept for 1 h. Cooling, filtering, washing with water, drying, washing with about 30mL of petroleum ether, and drying to obtain the crosslinked poly-p-nitrophenylethylene microspheres;
step three: placing the cross-linked poly-p-nitroaniline microspheres prepared in the step two in CCl4Swelling for 2h, adding chlorosulfonic acid with the mass ratio of the p-nitrostyrene-divinylbenzene microspheres being 1: 1 under the stirring condition, reacting for 3h, then sequentially washing with ethanol and water to neutrality, soaking with deionized water at room temperature for 24h, filtering, and vacuum drying to obtain the macroporous strong-acid resin A4.
Example 5
A preparation method of macroporous strong acid resin comprises the following specific steps:
the method comprises the following steps: weighing p-nitrostyrene, divinylbenzene, toluene and azobisisobutyronitrile at a mass ratio of 1: 0.3: 1.5: 0.03, wherein the mass of the selected p-nitrostyrene is 7.458 g. Mixing p-nitroarene and divinylbenzene, washing with 5% NaOH solution for 2 times, washing with water for 2 times to remove p-phenylenediphenol polymerization inhibitor, and distilling under reduced pressure at 10Pa and 45 ℃ to obtain a purified mixture of p-nitroarene and divinylbenzene. Toluene and azobisisobutyronitrile were added to a mixture of p-nitrostyrene and divinylbenzene, and then the mixture was poured into a three-necked flask containing 30ml of a 0.6% polyvinyl alcohol solution.
Step two: controlling the rotating speed to raise the temperature to 65 ℃ under the condition of 2000r/min, and preserving the heat for 3 hours; then heating to 75 ℃, and preserving the heat for 8 hours; then the temperature is raised to 90 ℃ and the temperature is kept for 2 h. Cooling, filtering, washing with water, drying, washing with about 30mL of petroleum ether, and drying to obtain the crosslinked poly-p-nitrophenylethylene microspheres;
step three: placing the cross-linked poly-p-nitroaniline microspheres prepared in the step two in CCl4Swelling for 2h, adding chlorosulfonic acid at a mass ratio of 1: 1.5 to the p-nitrostyrene-divinylbenzene microspheres under stirring, reacting for 3h, sequentially washing with ethanol and water to neutrality, soaking in deionized water at room temperature for 24h, filtering, and vacuum drying to obtain macroporous strong acid treeLipid a 5.
Examples 6 to 9 below are examples of the use of macroporous strongly acidic resins A1 to A5 as catalysts, respectively.
Example 6
The method comprises the following steps of catalytically synthesizing methyl tert-amyl ether (TAME) by using macroporous strong acid resin:
weighing 3.4 g of macroporous strong acid resin A1, adding into a 500mL stainless steel high-pressure reaction kettle, and rapidly adding 40mL methanol and 210mL isoamylene into the reaction kettle in sequence; and adjusting the pressure in the reaction kettle to be 8Mpa, quickly heating the reaction system to 250 ℃, and reacting at constant temperature for 4 hours to obtain the TAME. The results obtained by changing the kind of the macroporous strongly acidic resin are shown in Table 1.
TABLE 1 Effect of different macroporous strongly acidic resins on TAME Synthesis reactions
| Resin sample | Resin catalyst/g | Conversion of isoamylene/%) | TAME molar yield/% | Selectivity/%) |
| A1 | 3.4 | 98.93 | 97.77 | 98.83 |
| A2 | 3.4 | 98.00 | 95.81 | 97.77 |
| A3 | 3.4 | 98.25 | 95.49 | 97.19 |
| A4 | 3.4 | 98.47 | 95.66 | 97.15 |
| A5 | 3.4 | 98.98 | 97.18 | 98.18 |
The patent CN103787842B takes isoamylene and methanol as raw materials, adopts heteropoly acid/aluminum-based composite metal oxide as a catalyst, has the reaction temperature of 60-120 ℃, the pressure of 0.05-3.0 Mpa, the operation time of 50-1000 hours and the conversion rate of the isoamylene of 97.6-98.6 percent. The macroporous strong-acid resin prepared by the invention has the harsh conditions of high temperature resistance, high pressure resistance, strong corrosion resistance solvent and the like, in the preparation of TAME by the reaction of isoamylene and methanol, a supercritical reaction technology is adopted, methanol is reacted in a supercritical state under high temperature and high pressure, the contact area of methanol, isoamylene and a catalyst is increased, the catalytic reaction efficiency is greatly improved, the reaction time is also reduced, and the method is favorable for industrial production.
Example 7
The macroporous strong-acid resin is used for catalyzing and synthesizing ethyl tert-amyl ether (ETBE) and specifically comprises the following steps:
weighing 4.7 g of macroporous strong acid resin A1, adding into a 500mL stainless steel high-pressure reaction kettle, and rapidly adding 58mL of ethanol and 210mL of isoamylene into the reaction kettle in sequence; adjusting the pressure in the reaction kettle to be 8Mpa, quickly heating the reaction system to 260 ℃, and reacting at constant temperature for 5h to obtain ETBE. The results obtained by changing the kind of the macroporous strongly acidic resin are shown in Table 2.
TABLE 2 influence of different macroporous strongly acidic resins on the Synthesis reaction of ETBE
| Resin sample | Resin catalyst/g | Conversion of isoamylene/%) | TAME molar yield/% | Selectivity/%) |
| A1 | 4.7 | 97.55 | 96.36 | 98.78 |
| A2 | 4.7 | 97.78 | 96.69 | 98.89 |
| A3 | 4.7 | 98.11 | 96.33 | 98.19 |
| A4 | 4.7 | 97.32 | 95.84 | 98.48 |
| A5 | 4.7 | 97.99 | 96.99 | 98.98 |
CN103787841B takes isoamylene and ethanol as raw materials, takes aluminum-based composite metal oxide of cesium phosphotungstate acid salt as a catalyst, the reaction temperature is 100-180 ℃, the pressure is 2.0-6.0 Mpa, the operation time is 50-1000 hours, and the conversion rate of the isoamylene is 88.4-79.5%. The macroporous strong-acid resin prepared by the invention has the harsh conditions of high temperature resistance, high pressure resistance, strong corrosion resistance solvent and the like, in the preparation of ETBE by the reaction of isoamylene and ethanol, a supercritical reaction technology is adopted, ethanol is reacted in a supercritical state under high temperature and high pressure, the contact area of ethanol, isoamylene and a catalyst is increased, the catalytic reaction efficiency is greatly improved, the reaction time is also reduced, and the industrial production is facilitated.
Example 8
The CPME is synthesized by the catalysis of the macroporous strong acid resin, and the method comprises the following steps:
weighing 4.2 g of macroporous strong acid resin A1, adding into a 500mL stainless steel high-pressure reaction kettle, and rapidly adding 40mL methanol and 88mL cyclopentene into the reaction kettle in sequence; and adjusting the pressure in the reaction kettle to be 8Mpa, quickly heating the reaction system to 250 ℃, and reacting for 5 hours at constant temperature to obtain the CPME. The results obtained by changing the kind of the macroporous strongly acidic resin are shown in Table 3.
TABLE 3 Effect of macroporous strongly acidic resins on CPME Synthesis reactions
| Resin sample | Resin catalyst/g | Conversion of cyclopentene/%) | CPME molar yield/% | Selectivity/%) |
| A1 | 4.2 | 97.55 | 93.46 | 95.81 |
| A2 | 4.2 | 98.12 | 92.35 | 94.12 |
| A3 | 4.2 | 98.36 | 93.33 | 94.89 |
| A4 | 4.2 | 97.88 | 93.10 | 95.12 |
| A5 | 4.2 | 98.44 | 94.06 | 95.55 |
Cyclopentene reacts with methanol to obtain an environment-friendly solvent CPME, which is a novel hydrophobic ether solvent, and compared with ether solvents such as tetrahydrofuran, methyl tert-butyl ether and dioxane, the solvent is easier to separate water and recycle, and sewage discharge is reduced. As the reaction solvent, a coupling reaction, a Grignard reaction, a coupling amination reaction, an n-BuLi reaction, a metal reduction reaction, a Lewis acid reaction, a Friedel-Grafts reaction or the like can be used. Meanwhile, cyclopentyl methyl ether can be used in the processes of extraction, crystallization, surface treatment and polymerization. At present, only a few studies on the synthesis of cyclopentyl methyl ether are reported. CN103787841B takes cyclopentene and methanol as raw materials, adopts general strong acid resin as a catalyst, the reaction temperature is 20-80 ℃, the pressure is 0.3-1.0 Mpa, the operation time is 300 hours, and the conversion rate of the cyclopentene is only 14.5-14.7%. The macroporous strong-acid resin prepared by the invention has the harsh conditions of high temperature resistance, high pressure resistance, strong corrosion resistance solvent and the like, and in the preparation of CPME by the reaction of cyclopentene and methanol, a supercritical reaction technology is adopted, ethanol is reacted in a supercritical state under high temperature and high pressure, the contact area of methanol, cyclopentene and a catalyst is increased, the catalytic reaction efficiency is greatly improved, the reaction time is reduced, and the method is favorable for industrial production.
Experimental example 9
The synthesis route of the loxoprofen acid catalyzed and synthesized by the macroporous strong acid resin is shown in figure 3 and specifically comprises the following steps:
25ml of methanol, 6.14g of 2- (4-bromomethylphenyl) propionic acid and 2.5g of a strongly acidic resin A1 were taken, and the mixture was put into a three-necked flask, stirred and reacted at 60 ℃ for 8 hours. Filtering, and vacuum concentrating the filtrate to remove methanol. Then 10ml of water and 15ml of toluene are added to extract the reaction solution; an appropriate amount of anhydrous sodium sulfate was added to the organic phase to remove the residual water in the organic phase. And filtering again, and removing the toluene by rotary evaporation to obtain colorless oily liquid, namely the methyl 2- (4-bromomethylphenyl) propionate.
1.5ml of 2-oxocyclopentecarboxylic acid ethyl ester, 10ml of toluene and 1.40g of potassium carbonate were taken, and they were successively charged in a three-necked flask. The temperature is increased to 90 ℃ and the mixture is refluxed, 2.57g of 2- (4-bromomethylphenyl) methyl propionate solution in 5ml of toluene is slowly added dropwise, and the reflux reaction is continued for 12h at the temperature of 90 ℃. Filtering, adding 10ml of distilled water into the filtrate for washing and liquid separation, drying an organic layer by using anhydrous sodium sulfate, filtering again, and removing toluene by rotary evaporation to obtain yellow oily liquid, namely 2- [4- (1-ethoxycarbonyl-2-oxo-1-cyclopentylmethyl) phenyl ] methyl propionate.
3.32g of 2- [4- (1-ethoxycarbonyl-2-oxo-1-cyclopentylmethyl) phenyl ] methyl propionate, 5ml of acetic acid and 0.33g of strong acid resin A1 were put in a single-neck flask in this order, and the temperature was raised to 90 ℃ to conduct a reflux reaction for 10 hours. Filtering and recovering the resin, extracting the filtrate by using toluene, washing the filtrate by using a saturated sodium chloride solution, adding 0.05g of activated carbon for decoloring, and removing the toluene by carrying out reduced pressure concentration to obtain yellow oily viscous liquid, namely the loxoprofen acid.
Compared with the traditional method, the method adds concentrated sulfuric acid as an esterification catalyst, thereby avoiding the problems that the raw material 2- (4-bromomethylphenyl) propionic acid is easily oxidized by the concentrated sulfuric acid, the product is yellow in color, and the product can reach the standard after being treated for many times. Compared with the traditional method which adopts p-toluenesulfonic acid as the hydrolysis catalyst of ester, the method solves the problem that the p-toluenesulfonic acid is easy to generate industrial wastewater which is difficult to treat.
Compared with the prior art, the specific implementation mode has the following positive effects:
according to the invention, the electron-withdrawing group nitro is introduced into the polystyrene resin, so that the bond energy between the benzene ring and the sulfonic group is increased, and the sulfonic group on the benzene ring is more stable, thereby enhancing the thermal stability. The upper limit of the use temperature of the prior polystyrene resin is 140 ℃, and the polystyrene resin is completely inactivated at 140 ℃; the macroporous strong acid resin prepared by the invention can be normally used at a high temperature of about 260 ℃ without separation of sulfonic groups, and the application range of the macroporous strong acid resin in industrial production is enlarged.
FIG. 1 is a TG diagram of a macroporous strongly acidic resin A1 prepared by the present invention. As can be seen from the figure, a dip occurs at a temperature of 100 ℃ which indicates the elimination of water and associated associations in the resin; a sharp drop appears at 300 ℃, which indicates that the sulfonic acid group in the resin is removed; a further decrease in the curve at 400 ℃ is observed, which indicates that the styrene-divinylbenzene copolymer begins to decompose; after 400 ℃ and even after 500 ℃, the slope of the curve becomes flat, which indicates that all the effective groups in the resin are removed and the weight is basically kept unchanged. These show that the macroporous strong acid resin has good thermal stability and great advantages in the aspect of high-temperature catalytic reaction.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (6)
1. The application of the macroporous strong-acid resin as a catalytic material is characterized in that the macroporous strong-acid resin is used for catalyzing the synthesis of methyl tert-amyl ether by the reaction of isoamylene and methanol, the synthesis of ethyl tert-amyl ether by the reaction of isoamylene and ethanol, and the synthesis of cyclopentyl methyl ether or loxoprofen acid by the reaction of cyclopentene and methanol; the macroporous strong acid resin is prepared by mixing and reacting p-nitrostyrene serving as a monomer and divinylbenzene serving as a cross-linking agent with a dispersant, an initiator and a pore-forming agent to prepare a microspherical solid, washing the microspherical solid in petroleum ether to remove the pore-forming agent, and finally sulfonating chlorosulfonic acid.
2. The use of a macroporous strongly acidic resin as a catalytic material according to claim 1, characterized in that the preparation method of the macroporous strongly acidic resin comprises the steps of:
the method comprises the following steps: weighing a certain amount of p-nitrostyrene, divinylbenzene, a pore-forming agent and an initiator, then mixing the p-nitrostyrene and the divinylbenzene, and washing for 2 times by using NaOH solution with the mass fraction of 5.0%; washing with water for 2 times to remove polymerization inhibitor, and distilling under reduced pressure at absolute pressure of 10-100Pa and 45 deg.C to obtain purified mixture of p-nitrophenylethylene and divinylbenzene; adding a pore-foaming agent and an initiator into a mixture of p-nitrostyrene and divinylbenzene, and then pouring the mixture into a three-neck flask filled with a dispersant water solution with the mass fraction of 0.2-1.5% to form a reaction system;
step two: controlling the rotating speed to be 1000 r/min-4000 r/min, heating the reaction system to 65 ℃, and preserving the temperature for 1 h-3 h; then heating to 75 ℃, and preserving the heat for 4-8 h; then heating to 90 ℃, and preserving the heat for 0.5-2 h; cooling, filtering, washing with water, drying, washing with petroleum ether, and drying to obtain a p-nitrophenylethylene-divinylbenzene polymer microsphere solid;
step three: putting the polymer microsphere solid of the p-nitrophenylethylene-divinylbenzene prepared in the step two in CCl4Swelling for 1-4 h, adding chlorosulfonic acid with the mass ratio of 1: 0.5-2 to the p-nitrostyrene-divinylbenzene polymer microspheres under a good stirring condition, reacting for 1-2 h at a reflux temperature, then sequentially washing with ethanol and water to neutrality, soaking for 24h with deionized water at the room temperature of 15-25 ℃, filtering, and carrying out vacuum drying to obtain the macroporous strong-acid resin.
3. The use of the macroporous strong-acid resin as a catalytic material according to claim 1 or 2, wherein the mass ratio of the p-nitrostyrene to the divinylbenzene to the porogen to the initiator is 1: 0.05 to 0.3: 0.05 to 1.5: 0.005 to 0.03.
4. The use of macroporous, strongly acidic resin as a catalytic material according to claim 1 or 2, characterized in that the dispersing agent is one or a mixture of more than one of polyvinyl alcohol, methylcellulose, sodium lauryl sulfate or activated calcium phosphate.
5. The use of macroporous, strongly acidic resin as catalytic material according to claim 1 or 2, characterized in that the initiator is one or a mixture of more than one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide tert-butyl ester and pentaerythritol chloroacetate.
6. The use of macroporous, strongly acidic resin as a catalytic material according to claim 1 or 2, characterized in that the porogen is a mixture of toluene and/or paraffin oil having a freezing point of-20 ℃ to 10 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810507489.XA CN108794662B (en) | 2018-05-24 | 2018-05-24 | Preparation method and application of macroporous strong-acid resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810507489.XA CN108794662B (en) | 2018-05-24 | 2018-05-24 | Preparation method and application of macroporous strong-acid resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108794662A CN108794662A (en) | 2018-11-13 |
| CN108794662B true CN108794662B (en) | 2021-07-27 |
Family
ID=64091625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810507489.XA Active CN108794662B (en) | 2018-05-24 | 2018-05-24 | Preparation method and application of macroporous strong-acid resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108794662B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112194752A (en) * | 2020-10-15 | 2021-01-08 | 江西赣江新区有机硅创新研究院有限公司 | Polyacrylic acid microsphere catalyst and preparation method and application thereof |
| CN114106398A (en) * | 2021-01-04 | 2022-03-01 | 河南省驼人医疗科技有限公司 | Preparation method of macroporous resin |
| CN115322278B (en) * | 2022-08-03 | 2024-06-07 | 杭摩科技新材料(阜阳)有限公司 | Sulfonated nitrostyrene resin and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3256250A (en) * | 1961-09-26 | 1966-06-14 | Socony Mobil Oil Co Inc | Sulfonated ion exchange resin having an electronegative no2 substituent |
| CN1076385A (en) * | 1992-03-13 | 1993-09-22 | 中国石油化工总公司抚顺石油化工研究院 | Method for preparing high-temp-resistant strong acid type cation exchange resin catalyst |
| CN105037783A (en) * | 2015-07-09 | 2015-11-11 | 安徽皖东化工有限公司 | Preparation method for rare earth modified strongly acidic styrene cation exchange resin |
-
2018
- 2018-05-24 CN CN201810507489.XA patent/CN108794662B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3256250A (en) * | 1961-09-26 | 1966-06-14 | Socony Mobil Oil Co Inc | Sulfonated ion exchange resin having an electronegative no2 substituent |
| CN1076385A (en) * | 1992-03-13 | 1993-09-22 | 中国石油化工总公司抚顺石油化工研究院 | Method for preparing high-temp-resistant strong acid type cation exchange resin catalyst |
| CN105037783A (en) * | 2015-07-09 | 2015-11-11 | 安徽皖东化工有限公司 | Preparation method for rare earth modified strongly acidic styrene cation exchange resin |
Non-Patent Citations (2)
| Title |
|---|
| 对氟苯乙烯-二乙烯基苯强酸性阳离子交换树脂的合成及其热稳定性研究;何明阳等;《离子交换与吸附》;20020430;第18卷(第2期);第119-124页 * |
| 氯磺酸磺化聚苯乙烯-二乙烯基苯树脂;周蕊等;《化工学报》;20100430;第61卷(第4期);第1047-1051页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108794662A (en) | 2018-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108794662B (en) | Preparation method and application of macroporous strong-acid resin | |
| Gu et al. | Glycerol as an efficient promoting medium for organic reactions | |
| CN103483154B (en) | The manufacture method of bisphenol compound | |
| JP5360719B2 (en) | Method for producing solid acid catalyst comprising sulfonic acid group-containing carbonaceous material and use thereof | |
| TW200301244A (en) | Metal-doped sulfonated ion exchange resin catalysts | |
| CN101863763A (en) | Method for catalytically synthesizing isobornyl methacrylate by activated carbon supported stannic chloride | |
| CN105618137A (en) | Porous acidic resin catalyst, preparation method and applications thereof | |
| Liu et al. | Facile synthesis of fructone from ethyl acetoacetate and ethylene glycol catalyzed by SO 3 H-functionalized Brønsted acidic ionic liquids | |
| Khaligh et al. | Aldol condensations of a variety of different aldehydes and ketones under ultrasonic irradiation using poly (N-vinylimidazole) as a new heterogeneous base catalyst under solvent-free conditions in a liquid-solid system | |
| CN107899612B (en) | Functionalized polyacid ionic liquid catalyst, preparation method and method for catalytically synthesizing isobornyl acetate by using functionalized polyacid ionic liquid catalyst | |
| CN101293824B (en) | Method for preparing sec-butyl acetate with direct esterification of acetic acid and butylene | |
| CN101863761A (en) | Method for preparing dipropylene glycol methyl ether acetate | |
| JP4855014B2 (en) | Process for producing α, β-unsaturated carboxylic acid ester and α, β-unsaturated carboxylic acid ester | |
| CN101985418B (en) | Method for preparing 2-methoxy-1-propanol ether acetate | |
| CN102452935A (en) | Preparation method of p-acetoxyacetophenone, and hydrogenation and dehydration products thereof | |
| CN102617849A (en) | Method for preparing alkyl polyoxyethylene ether acrylate or alkyl polyoxyethylene ether methacrylic ester | |
| CN102264685A (en) | Method for producing acetic acid ester | |
| JP7197172B2 (en) | Method for producing cinnamic acid ester compound | |
| AU2011201724B2 (en) | A process for producing C1-C4 alkyl nitrite | |
| CN108863793B (en) | Preparation method of isopropyl acetate | |
| JP6675492B2 (en) | Method for preparing liquid phase of acrylic ester | |
| Yagyu et al. | Recovery of acetic acid from dilute aqueous solutions using catalytic dehydrative esterification with ethanol | |
| CN112174927B (en) | Preparation method of glycerol formal | |
| CN101735053B (en) | Method for preparing maleic acid diethylene glycol monoethyl ether ester | |
| CN112574229B (en) | Method for preparing isosorbide by dehydrating sorbitol and preparation method of copolymer-based catalyst thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220113 Address after: 431700 No. 1095, Laojie, Zhanggang Town, Hubei Province Patentee after: Tianmen Runcheng Biotechnology Co.,Ltd. Address before: 430081 Wuhan University of science and technology, 947 Heping Avenue, Qingshan District, Wuhan City, Hubei Province Patentee before: WUHAN University OF SCIENCE AND TECHNOLOGY |