阅读说明：本技术 一种离子树脂基催化剂及其催化合成氨苯甲酸的方法 (Ionic resin-based catalyst and method for catalytically synthesizing aminobenzoic acid by using same ) 是由 沈照亮 夏雷 于 2020-06-18 设计创作，主要内容包括：本发明公开了一种离子树脂基催化剂及其催化合成氨苯甲酸的方法,本发明属于化工技术领域,本发明采用聚氯醚和聚苯乙烯组分组成的互穿聚合物网络微球制备离子树脂基催化剂,并采用此催化剂进行催化合成氨苯甲酸,和传统的乌洛托品等催化剂相比,本发明催化剂原料来源广泛,且反应温和,产品纯、收率高,催化剂容易回收再生利用,这种催化合成方法可以作为合成重要有机中间体氨苯甲酸的优选合成方法,本发明具有广泛的工业应用前景和经济实用价值。(The invention discloses an ion resin-based catalyst and a method for catalytically synthesizing aminobenzoic acid by the ion resin-based catalyst, belonging to the technical field of chemical industry.)

1. An ionic resin-based catalyst is characterized in that the catalyst is an anionic resin-based catalyst with an interpenetrating polymer network structure of styrene-divinylbenzene cross-linked copolymer resin and polychloroprene graft copolymer.

2. The ionic resin-based catalyst according to claim 1, characterized in that it is prepared by a process comprising the steps of:

(1) preparation of a polychloroprene graft copolymer: vacuumizing a reaction kettle, filling nitrogen, uniformly mixing 8-10 parts of styrene, 4-8 parts of maleic anhydride, 100 parts of 3, 3' -dichloromethyl propylene oxide and 70-85 parts of chlorobenzene solution dispersed with 0.025-0.05 part of triisobutyl aluminum and 0.01-0.05 part of diisopropyl peroxydicarbonate in the nitrogen atmosphere, carrying out graft copolymerization for 1-2 hours at the temperature of 60-70 ℃ under stirring, and washing, filtering and drying to obtain a polychloro-ether graft copolymer; (2) putting 1-2 parts of benzoyl peroxide in a mixed monomer of 80-85 parts of styrene and 12-15 parts of divinylbenzene in another reaction kettle, adding 450-500 parts of deionized water solution containing 0.05-0.1% of polyvinyl alcohol by mass fraction into the reaction kettle while stirring, uniformly dispersing 15-20 parts of graft copolymer into the reaction kettle, stirring and reacting at 80-85 ℃ for 5-10 hours to obtain polymer spherulites, filtering, washing, and drying at 100-125 ℃ for 2-4 hours to obtain the interpenetrating network structure microspheres; (3) adding 10-13 parts of interpenetrating network structure microspheres and 100-110 parts of xylene into a reaction kettle, swelling for 1-2 hours, adding 10-11 parts of chloroacetyl chloride, slowly adding 12-14 parts of aluminum trichloride under stirring, reacting for 2-4 hours at 25-30 ℃, transferring reactants into an all-glass microporous filter membrane filter after the reaction is finished, sequentially washing and filtering with tetrahydrofuran, glacial hydrochloric acid with the mass fraction of 3% and the temperature of-10 to-5 ℃ and absolute ethanol until the filtrate is free of chloride ions, washing and filtering with acetone for 1-2 times, and drying in vacuum to constant weight to obtain the chloroacetylated network structure microspheres; (4) weighing 10-12 parts of chloroacetylation interpenetrating network structure microspheres obtained in the step (3), placing the weighed microspheres into an impregnation tank, adding 10-20 parts of tetrahydrofuran, impregnating and swelling for 12-24 hours, adding 15-20 parts of trimethylamine, stirring and reacting for 2-3 hours at 25-30 ℃, transferring reactants in the tank into a full-glass microporous filter membrane filter after the reaction is finished, sequentially washing and filtering the reactants by tetrahydrofuran, water, acetone and methanol for 1-2 times respectively, and drying the reactants in vacuum at 30-50 ℃ to constant weight to obtain the ionic resin-based catalyst.

3. A method for catalytically synthesizing aminobenzoic acid by using the ionic resin-based catalyst according to claim 1, which comprises the following steps: (1) adding 0.9-1 part of an ionic resin-based catalyst and 4.5-5 parts of water into an enamel reaction kettle at a certain reaction temperature, adding 0.9-1 part of p-carboxyl substituted benzyl, fully stirring for 1-1.5 hours, dropwise adding 1-2 parts of ammonia water at a constant speed, gradually dissolving the carboxyl substituted benzyl in the dropwise adding process, stirring until the raw materials react completely, filtering out the ionic resin catalyst, recycling, concentrating mother liquor under reduced pressure, evaporating ammonia, concentrating until the pH is 7.5-8, cooling to 25-30 ℃, filtering to obtain a crude product of p-aminomethyl benzoic acid, wherein the yield is 60-70%, and recycling the mother liquor; (2) in a refining tank, heating the obtained p-aminomethyl benzoic acid crude product to 75-80 ℃ by using distilled water with the wet weight of 4-5 times, adding activated carbon for decolorization, filtering the decolorized activated carbon for removal, cooling refined mother liquor, immediately separating out a product, cooling and filtering the product, and recycling the refined mother liquor for reuse to obtain an aminomethylbenzoic acid product.

4. The method for catalytic synthesis of aminobenzoic acid by using the ionic resin-based catalyst according to claim 3, wherein the reaction temperature is 30-50 ℃.

5. The method for catalytically synthesizing aminobenzoic acid by using the ionic resin-based catalyst according to claim 3, wherein the yield of the crude product in the step (1) is 60-70%, the recovery rate of the mother liquor for recycling is 80-90%, the yield of the aminomethylbenzoic acid product in the step (2) is 80-90%, and the recovery rate of the refined mother liquor for recycling is 90-98%.

6. The method for catalytic synthesis of aminobenzoic acid by using the ionic resin-based catalyst according to claim 3, wherein the p-carboxyl substituted benzyl in the step (1) is one of p-chloromethylbenzoic acid or p-bromomethylbenzoic acid.

Technical Field

The invention belongs to the technical field of chemical industry, and particularly relates to an ionic resin-based catalyst and a method for catalytically synthesizing aminobenzoic acid by using the same.

Background

The aminobenzoic acid is also named as p-aminomethyl benzoic acid or aromatic hemostatic acid, is mainly used as an organic synthesis intermediate, a hemostatic drug and a fibrinolysis inhibitor, has similar effects to those of aminocaproic acid in various diseases caused by overhigh lytic enzyme activity of fibrin, has better performance and wider application, is suitable for diseases with strong blood permeability such as abnormal bleeding during surgery and gynecological operations, pneumonocardia hemoptysis, endocrine bleeding and eczema, has particularly obvious hemostatic effect on common chronic blood permeability, and has wide market application prospect. CN2016108096529 discloses a method for producing m-dimethylaminobenzoic acid, which adopts m-nitrobenzoic acid as raw material and palladium carbon as catalyst, but has high price and great recovery difficulty, and is not suitable for the flow line industrial production of aminomethyl benzoic acid. The existing synthesis method of aminomethyl benzoic acid uses urotropine as catalyst, and adopts the processes of substituting carboxyl for benzyl, dripping ammonia water, reacting, evaporating excess ammonia water, cooling and suction-filtering so as to obtain the invented product. At present, a synthesis process of aminomethylbenzoic acid and a corresponding catalyst which are clean and environment-friendly, high in recovery rate, mild in reaction condition and low in cost are not available in the market, and a person skilled in the art needs to develop an ionic resin-based catalyst and a method for catalytically synthesizing the aminobenzoic acid by the ionic resin-based catalyst so as to meet the existing use requirements and market requirements.

Disclosure of Invention

Aiming at the problems, the invention aims to provide an ionic resin-based catalyst and a method for catalytically synthesizing aminobenzoic acid by using the ionic resin-based catalyst.

The invention is realized by the following technical scheme:

an ionic resin-based catalyst is an anionic resin-based catalyst with an interpenetrating network structure of styrene-divinylbenzene cross-linked copolymer resin and polychloroprene graft copolymer.

The preparation method of the ionic resin-based catalyst comprises the following steps:

(1) preparation of a polychloroprene graft copolymer: vacuumizing a reaction kettle, filling nitrogen, uniformly mixing 8-10 parts of styrene, 4-8 parts of maleic anhydride, 100 parts of 3, 3' -dichloromethyl propylene oxide and 70-85 parts of chlorobenzene solution dispersed with 0.025-0.05 part of triisobutyl aluminum and 0.01-0.05 part of diisopropyl peroxydicarbonate in the nitrogen atmosphere, carrying out graft copolymerization for 1-2 hours at the temperature of 60-70 ℃ under stirring, and washing, filtering and drying to obtain a polychloro-ether graft copolymer; (2) putting 1-2 parts of benzoyl peroxide in a mixed monomer of 80-85 parts of styrene and 12-15 parts of divinylbenzene in another reaction kettle, adding 450-500 parts of deionized water solution containing 0.05-0.1% of polyvinyl alcohol by mass fraction into the reaction kettle while stirring, uniformly dispersing 15-20 parts of graft copolymer into the reaction kettle, stirring and reacting at 80-85 ℃ for 5-10 hours to obtain polymer spherulites, filtering, washing, and drying at 100-125 ℃ for 2-4 hours to obtain the interpenetrating network structure microspheres; (3) adding 10-13 parts of interpenetrating network structure microspheres and 100-110 parts of xylene into a reaction kettle, swelling for 1-2 hours, adding 10-11 parts of chloroacetyl chloride, slowly adding 12-14 parts of aluminum trichloride under stirring, reacting for 2-4 hours at 25-30 ℃, transferring reactants into an all-glass microporous filter membrane filter after the reaction is finished, sequentially washing and filtering with tetrahydrofuran, glacial hydrochloric acid with the mass fraction of 3% and the temperature of-10 to-5 ℃ and absolute ethanol until the filtrate is free of chloride ions, washing and filtering with acetone for 1-2 times, and drying in vacuum to constant weight to obtain the chloroacetylated network structure microspheres; (4) weighing 10-12 parts of chloroacetylation interpenetrating network structure microspheres obtained in the step (3), placing the weighed microspheres into an impregnation tank, adding 10-20 parts of tetrahydrofuran, impregnating and swelling for 12-24 hours, adding 15-20 parts of trimethylamine, stirring and reacting for 2-3 hours at 25-30 ℃, transferring reactants in the tank into a full-glass microporous filter membrane filter after the reaction is finished, sequentially washing and filtering the reactants by tetrahydrofuran, water, acetone and methanol for 1-2 times respectively, and drying the reactants in vacuum at 30-50 ℃ to constant weight to obtain the ionic resin-based catalyst.

The method for synthesizing the aminobenzoic acid by adopting the ionic resin-based catalyst comprises the following steps: (1) adding 0.9-1 part of an ionic resin-based catalyst and 4.5-5 parts of water into an enamel reaction kettle at a certain reaction temperature, adding 0.9-1 part of p-carboxyl substituted benzyl, fully stirring for 1-1.5 hours, dropwise adding 1-2 parts of ammonia water at a constant speed, gradually dissolving the carboxyl substituted benzyl in the dropwise adding process, stirring until the raw materials react completely after dropwise adding, filtering out the ionic resin catalyst, recycling, concentrating mother liquor under reduced pressure, evaporating ammonia, concentrating until the pH value is 7.5-8, cooling and filtering to obtain a p-aminomethyl benzoic acid crude product, wherein the yield is 60-70%, and recycling the mother liquor for reuse; (2) in a refining tank, heating the obtained p-aminomethyl benzoic acid crude product to 75-80 ℃ by using distilled water with the wet weight of 4-5 times, adding activated carbon for decolorization, filtering the decolorized activated carbon for removal, cooling refined mother liquor, immediately separating out a product, cooling and filtering the product, and recycling the refined mother liquor for reuse to obtain an aminomethylbenzoic acid product.

Further, the reaction temperature of the step (1) is 30-50 ℃.

Further, the yield of the crude product in the step (1) is 60-70%, the recovery rate of mother liquor for recycling is 80-90%, the yield of aminomethylbenzoic acid products in the step (2) is 80-90%, and the recovery rate of refined mother liquor for recycling is 90-98%.

Further, the p-carboxyl substituted benzyl is one of p-chloromethyl benzoic acid or p-bromomethyl benzoic acid.

The method for recycling the mother liquor comprises the following steps: adding an aminomethylbenzoic acid to-be-purified product and a recovered mother liquor into a reaction kettle, heating to dissolve, filtering, cooling to crystallize, filtering and separating a solid and a filtrate, drying the solid to obtain the aminomethylbenzoic acid purified product, wherein the filtrate is the aminomethylbenzoic acid-containing purified mother liquor before the aminomethylbenzoic acid mother liquor of the batch is recycled and reused

The formula of the reaction for synthesizing the aminobenzoic acid by the catalysis of the ionic resin-based catalyst is as follows:

wherein: x is selected from Br, C1, i.e., the p-carboxy substituted benzyl used herein is one of p-chloromethylbenzoic acid or p-bromomethylbenzoic acid.

The invention has the beneficial effects that:

the invention adopts styrene and maleic anhydride in-situ graft copolymerization in the process of polychloro ether cationic polymerization to prepare polychloro ether graft copolymer, the polychloro ether is grafted with styrene long chain and is introduced into suspension polymerization of styrene-divinylbenzene, and the styrene-maleic anhydride copolymerization plays a part of the role of dispersant, so that liquid drops form a protective film to promote the reaction, and under the copolymerization action of divinylbenzene, the grafted styrene long chain further generates crosslinking reaction to further form interpenetrating network structure microspheres consisting of styrene-divinylbenzene crosslinking copolymer resin and polychloro ether graft copolymer, and the chloroacetylation interpenetrating network structure microspheres are prepared by carrying out Friedel-crafts acylation reaction on the interpenetrating network structure microspheres, and then the chloroacetylation interpenetrating network structure microspheres are quaternized to obtain the anion exchange resin catalyst with strong basicity, the ion resin-based catalyst avoids using carcinogenic substances such as chloromethyl ether and the like in the preparation process of chloromethyl resin, eliminates secondary cross-linking, multiple substitution and other side reactions, realizes in-situ polymerization interpenetrating, and the polychloro ether contained in the interpenetrating network structure microsphere does not need to be methylated due to the inherent property of the structure, can also have ion exchange performance through direct processing of quaternization, further improves the catalytic activity of the ion resin-based catalyst, in addition, the polychloro ether has good comprehensive performance, and in the forming process of interpenetrating network, the polychloro ether graft copolymer not only plays a role in dispersion, but also has thickening effect on the formation of the styrene-divinyl benzene copolymer due to high density and grafted surface activity, and can be uniformly blended with monomer materials and then subjected to suspension polymerization reaction, further improving the mechanical strength of the microspheres and improving the adsorption and catalytic activity thereof, the interpenetrating network microspheres directly carry out a chloromethylation reaction, while in chloroacetylation, a part of polystyrene is interpenetrating, wound and crosslinked in a polymer skeleton network, thereby strengthening the polymer skeleton network, the other part of linear polystyrene is extracted, and the interpenetrating network microspheres are perforated to form a mutually reinforced, perforated and interpenetrating network microspheres, and further carrying out amination reaction by using trimethylamine aqueous solution, so that the anion exchange resin catalyst with an interpenetrating structure of the double-acting components of the polychlorinated ether and the polystyrene can be obtained, has the advantages of large specific gravity, high strength and good adsorption-catalytic performance, has no obvious change in physical and chemical properties in the use of synthesizing the aminobenzoic acid through practical application, and is convenient to recover, the recycling and recycling rate is high. Furthermore, the prepared high-safety ionic resin-based catalyst is used for replacing high-risk urotropine and other catalysts, the yield is high, the synthesis conditions are mild, the sources of the raw materials of the catalyst are wide, the reaction temperature is low, the product is pure, the yield is high, the catalyst is a novel catalytic synthesis route for synthesizing aminobenzoic acid, and the economic benefit is obvious.

Compared with the prior art, the invention has the following advantages:

the invention further adopts the prepared high-safety ionic resin-based catalyst to replace the high-risk urotropine and other catalysts, has higher yield, mild synthesis conditions, wide sources of the raw materials of the catalyst, low reaction temperature, pure product and high yield, is a novel catalytic synthesis route for synthesizing the aminobenzoic acid, and has obvious economic benefit.

Detailed Description

The invention is illustrated by the following specific examples, which are not intended to be limiting.