CN112495438B - Preparation method of super-strong fiber loaded acid-base bifunctional catalyst - Google Patents
Preparation method of super-strong fiber loaded acid-base bifunctional catalyst Download PDFInfo
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- CN112495438B CN112495438B CN202011572257.6A CN202011572257A CN112495438B CN 112495438 B CN112495438 B CN 112495438B CN 202011572257 A CN202011572257 A CN 202011572257A CN 112495438 B CN112495438 B CN 112495438B
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
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- 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
Abstract
The invention relates to a preparation method of a super-strong fiber loaded acid-base bifunctional catalyst; taking polyether-ether-ketone super strong fiber as a matrix, grafting and neutralizing chloromethyl functionalized polyether-ether-ketone fiber and polyamine, and carrying out ring opening reaction on the polyamine functionalized super strong fiber and 1, 3-propane sultone to prepare a super strong fiber loaded acid-base bifunctional catalyst with acid-base active sites of sulfonic acid groups and primary, secondary and tertiary amino groups respectively; the polyether-ether-ketone fiber loaded acid-base bifunctional catalyst is simple to prepare, is suitable for the reaction of multiple acid and base concerted catalysis, is convenient to separate, recover and circularly apply, and provides a new way for industrial catalytic synthesis by virtue of good flexibility, high mechanical strength and excellent reprocessing performance.
Description
Technical Field
The invention relates to a preparation method of a super-strong fiber loaded acid-base bifunctional catalyst, in particular to a bifunctional catalyst suitable for one-pot series reaction of acid-base concerted catalysis, and belongs to the technical field of green catalysis.
Background
In recent years, green catalysis technology is taken as the frontier of international chemical science research, is widely concerned by chemists around the world, and also plays a remarkable role in promoting the sustainable development of economy and society. However, the fine chemical catalytic technology mainly used for synthesizing high value-added chemicals and drug intermediates is relatively dispersed and slow in development, the level of clean production and comprehensive utilization is far away from the requirement of ecological civilization construction, and the sustainable development of the industry faces a plurality of challenges. Advanced catalytic technology will certainly promote significant progress in the production process, and improvements in catalytic technology will be based on innovations in catalysts or catalytic materials. Therefore, designing and developing novel, efficient, economic and environment-friendly catalysts or catalytic materials are still a hotspot and a key point in the industrial catalytic research field in a future period, and are also a basic way for implementing energy conservation and emission reduction in the chemical industry of China during the period of fourteen five times.
The synthesis process of fine chemicals is mostly realized through two-step or multi-step reactions, most reactions require catalysis of acid or alkali, and if single-function acid or alkali catalysts are used successively, tedious operations such as feeding, reaction, separation and the like must be repeated, so that the development of the acid-base bifunctional catalyst has important significance. In a chemical reaction system, the acid-base bifunctional catalyst can centralize two-step or multi-step chemical reactions in one reaction container to complete at one time, and simplifies the operation procedure and improves the catalytic efficiency through the synergistic catalytic action of acid and base. Tomotaka et al report that a bifunctional thiourea is used for catalyzing Michael reaction and shows good acid-base synergistic catalytic performance, however, the homogeneous micromolecule acid-base bifunctional catalyst still has many disadvantages of difficult separation of products and catalysts, incapability of repeatedly using the catalysts and the like in the reaction process; leather and leather, etc. load acid-base double active sites on mesoporous materials or organic-inorganic hybrid materials, and the prepared acid-base double-functional catalysts also show good effects in aldol condensation and other reactions, but the preparation process is complex, and the reprocessing and utilization performance of catalytic materials is insufficient; dujian et al reported that the acid-base bifunctional catalyst loaded on the common polypropylene fiber as the carrier is used for nucleophilic addition reaction,however, the performance of acid-base concerted catalysis tandem reaction is poor, and the service temperature of the polypropylene substrate is difficult to exceed 100 DEG C o C; the polyether-ether-ketone fiber as a novel super strong fiber has unique advantages in reprocessing performance and high temperature resistance when being used as an acid-base bifunctional catalyst carrier by virtue of higher mechanical strength and good flexibility.
Disclosure of Invention
The invention aims to provide a preparation method of a super-strong fiber loaded acid-base bifunctional catalyst, wherein the super-strong fiber catalyst takes polyether-ether-ketone fibers as a matrix and is characterized in that sulfonic acid groups and primary, secondary and tertiary amino groups are covalently bonded on the matrix (figure 1). The functional fiber catalyst can efficiently catalyze a series of pot-to-pot series reactions in a rotating frame type reactor, and can be recycled for more than 20 times.
The technical scheme of the invention is as follows: a super strong fiber loaded acid-base bifunctional catalyst is prepared by taking polyether-ether-ketone super strong fibers as a matrix and preparing a functional fiber catalytic material with acid-base active sites of covalently bonded sulfonic acid groups and three amino groups, namely primary amino groups, secondary amino groups and tertiary amino groups respectively in a chemical grafting manner.
The preparation method of the super-strong fiber supported acid-base bifunctional catalyst preferably comprises the following steps.
1) Mixing polyether-ether-ketone fibers with 25% of chloromethyl functional weight increment and polyamine in acetonitrile according to the mass ratio of 1 to 20 to 40, carrying out reflux reaction under the stirring condition, cooling to room temperature, taking out the super-strong fibers, sequentially washing with alkali liquor and deionized water until the filtrate is neutral, and then washing with 80 parts of deionized water to obtain the polyether-ether-ketone fibers with 25% of chloromethyl functional weight increment o And C, drying to constant weight to obtain the polyamine functional super strong fiber.
2) Mixing the polyamine functionalized super-strong fiber and 1, 3-propane sultone in toluene according to the mass ratio of 1 to 2, carrying out reflux reaction under the stirring condition, cooling to room temperature, taking out the super-strong fiber, washing with toluene and ethanol respectively, and then washing with 80 parts of ethanol o And C, drying to constant weight to obtain the super-strong fiber loaded acid-base bifunctional catalyst.
The preferable polyamine in the step 1) is diethylenetriamine, triethylene tetramine or tetraethylene pentamine, and the reflux reaction time is 12 to 24 hours.
The preferable refluxing reaction time in the step 2) is 12 to 36 hours.
The invention has the advantages that acidic sulfonic acid groups and basic primary, secondary and tertiary amino groups are chemically bonded on the surface layer of the super-strong fiber polyether-ether-ketone, and acid-base double-activity sites and the excellent mechanical properties of fiber materials are utilized to realize acid-base synergy and circulated (more than 20 times) high-efficiency catalysis of multiple one-pot series reactions in a rotating frame type reactor.
Drawings
FIG. 1: super strong fiber loaded acid-base bifunctional catalyst structure diagram.
FIG. 2: the super-strong fiber loaded acid-base bifunctional catalyst has a circulating catalytic effect in a one-pot series reaction of benzaldehyde dimethyl acetal and nitromethane.
FIG. 3: the super-strong fiber loaded acid-base bifunctional catalyst has a circulating catalytic effect in a one-pot series reaction of benzaldehyde dimethyl acetal and ethyl cyanoacetate.
Detailed Description
The specific examples further illustrate the practice of the invention.
Example 1.
Adding 0.5 g of dry chloromethyl functional polyether ether ketone fiber, 20.0 g of diethylenetriamine and 10.0 mL of acetonitrile into a 100 mL three-neck flask, stirring, refluxing for reaction for 12 h, cooling to room temperature, taking out super-strong fiber, sequentially washing with 5% sodium carbonate solution and deionized water until the filtrate is neutral, and then washing at 80 ℃ to obtain the nano-composite material o And C, drying in a drying box in vacuum to constant weight to obtain the diethylenetriamine functionalized super-strong fiber.
Adding the dried diethylenetriamine functionalized super-strong fiber, 0.6 g of 1, 3-propane sultone and 40 mL of toluene into a 100 mL three-neck flask, stirring and refluxing for reaction for 36 h, cooling to room temperature, taking out the super-strong fiber, washing with toluene and ethanol respectively, and then washing at the temperature of 80 DEG C o And C, drying in a drying box in vacuum to constant weight to obtain the polyether-ether-ketone fiber loaded acid-base dual-functional catalyst.
Example 2.
A100 mL three-necked flask was charged with 0.5 g of dry matterStirring and refluxing the chloromethyl functional polyether ether ketone fiber, 15.0 g of diethylenetriamine and 10.0 mL of acetonitrile for 24 hours, cooling to room temperature, taking out the super-strong fiber, sequentially washing with 5% sodium carbonate solution and deionized water until the filtrate is neutral, and then washing at the temperature of 80 DEG C o And C, drying in a drying box in vacuum to constant weight to obtain the diethylenetriamine functionalized super-strong fiber.
Adding the dried diethylenetriamine functionalized super-strong fiber, 0.6 g of 1, 3-propane sultone and 40 mL of toluene into a 100 mL three-neck flask, stirring and refluxing for reaction for 24 h, cooling to room temperature, taking out the super-strong fiber, washing with toluene and ethanol respectively, and then washing at the temperature of 80 DEG C o And C, drying in a drying box in vacuum to constant weight to obtain the polyether-ether-ketone fiber loaded acid-base dual-functional catalyst.
Example 3.
Adding 0.5 g of dry chloromethyl functionalized polyether ether ketone fiber, 15.0 g of triethylene tetramine and 10.0 mL of acetonitrile into a 100 mL three-neck flask, stirring, carrying out reflux reaction for 24 hours, cooling to room temperature, taking out the super-strong fiber, sequentially washing with 5% sodium carbonate solution and deionized water until the filtrate is neutral, and then washing at 80 ℃ to obtain the cellulose acetate fiber o And C, drying in a drying box in vacuum to constant weight to obtain the triethylene tetramine functionalized super-strong fiber.
Adding the dried diethylenetriamine functionalized super-strong fiber, 1.2 g of 1, 3-propane sultone and 40 mL of toluene into a 100 mL three-neck flask, stirring and refluxing for reaction for 12 h, cooling to room temperature, taking out the super-strong fiber, washing with toluene and ethanol respectively, and then washing at the temperature of 80 DEG C o And C, drying in a drying box in vacuum to constant weight to obtain the polyether-ether-ketone fiber loaded acid-base dual-functional catalyst.
Example 4.
[ 0.5 g of dry chloromethyl functionalized polyether ether ketone fiber, 10.0 tetraethylenepentamine and 10.0 mL of acetonitrile are added into a 100 mL three-neck flask, stirred and refluxed for reaction for 12 hours, cooled to room temperature, taken out of super-strong fiber, washed by 5% sodium carbonate solution and deionized water in sequence until the filtrate is neutral, and then washed at the temperature of 80 DEG C o And C, drying in a drying box in vacuum to constant weight to obtain the tetraethylenepentamine functional super-strong fiber.
In three 100 mL portsAdding the dried diethylenetriamine functionalized super-strong fiber, 0.6 g of 1, 3-propane sultone and 40 mL of toluene into a flask, stirring, refluxing for reaction for 24 hours, cooling to room temperature, taking out the super-strong fiber, washing with toluene and ethanol in sequence, and then washing at the temperature of 80 DEG C o And C, drying in a drying box in vacuum to constant weight to obtain the polyether-ether-ketone fiber loaded acid-base dual-functional catalyst.
0.1 g of the super-strong fiber-supported acid-base bifunctional catalyst obtained in example 1 was wound around a stirring paddle of a reactor (a simulated rotating frame reaction operation) and used for a one-pot series reaction of benzaldehyde dimethyl acetal and nitromethane (reaction conditions: 10.0 mmol of benzaldehyde dimethyl acetal, 10 mL of nitromethane, 80:. Sup. o C, reacting for 12 hours), and obtaining 1.47 g of beta-nitrostyrene through post-treatment, wherein the yield of the product reaches 98 percent. The above operation was repeated 20 times, and no significant decrease in product yield was observed (FIG. 2).
0.1 g of the super-strong fiber supported acid-base bifunctional catalyst obtained in example 3 was wound around a stirring paddle of a reactor (simulated rotating frame reaction operation) and used for one-pot series reaction of benzaldehyde dimethyl acetal and ethyl cyanoacetate (reaction conditions: 10.0 mmol of benzaldehyde dimethyl acetal, 10.0 mmol of ethyl cyanoacetate and 10 mL of toluene, 105 mL of 105 mL of benzaldehyde dimethyl acetal and ethyl cyanoacetate o C, reacting for 6 hours), and obtaining 1.94 g (E) The yield of the product of the (E) -2-cyano-3-phenyl ethyl acrylate reaches 96 percent. The catalyst was cycled 20 times in the above procedure without significant decrease in product yield (FIG. 3).
The invention discloses and provides a preparation method of a super-strong fiber loaded acid-base bifunctional catalyst, which can be realized by appropriately changing links such as raw materials, process parameters, structural design and the like by referring to the contents in the text. While the methods and techniques of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and techniques described herein may be made and equivalents employed to practice the techniques of this invention without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (5)
1. A preparation method of a super-strong fiber loaded acid-base bifunctional catalyst is characterized in that polyether-ether-ketone super-strong fibers are used as a matrix, a chemical grafting mode is adopted to prepare a functional fiber catalytic material with acid-base active sites respectively being covalently bonded sulfonic acid groups and primary, secondary and tertiary amino groups, and a schematic diagram of a fiber structure is as follows.
2. The preparation method of the super strong fiber supported acid-base bifunctional catalyst according to claim 1, characterized by comprising the following steps:
1) Mixing polyether-ether-ketone fibers with 25% of chloromethyl functional weight increment and polyamine in acetonitrile according to the mass ratio of 1 to 20 to 40, carrying out reflux reaction under the stirring condition, cooling to room temperature, taking out the super-strong fibers, sequentially washing with alkali liquor and deionized water until the filtrate is neutral, and then washing with 80 parts of deionized water to obtain the polyether-ether-ketone fibers with 25% of chloromethyl functional weight increment o C, drying to constant weight to obtain polyamine functional super strong fiber;
2) Mixing the polyamine functionalized super-strong fiber and 1, 3-propane sultone in toluene according to the mass ratio of 1.5-2, carrying out reflux reaction under the stirring condition, cooling to room temperature, taking out the super-strong fiber, washing with toluene and ethanol respectively, and then washing with 80 parts of ethanol o And C, drying to constant weight to obtain the super-strong fiber loaded acid-base bifunctional catalyst.
3. The method of claim 2, wherein the polyamine of step 1) is diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
4. The method as claimed in claim 2, wherein the reflux reaction time in step 1) is 12 to 24 hours.
5. The method as claimed in claim 2, wherein the reflux reaction time in step 2) is 12 to 36 hours.
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