阅读说明：本技术 通用耐温酸性强化型树脂催化剂及其制备方法 (General temperature-resistant acidic reinforced resin catalyst and preparation method thereof ) 是由 王义成 冷东斌 吕晓东 张伟 彭慧敏 王英杰 管秀明 吴万春 于 2021-01-26 设计创作，主要内容包括：本发明专利提供一种通用耐温酸性强化型树脂催化剂及其制备方法。其通用耐温酸性强化型树脂催化剂,是苯乙烯和二乙烯基苯单体系聚合后,经抽提、干燥为树脂基球,再经氯化、磺化和活性基团稳定改性、洗涤制得,其中所述的苯乙烯和二乙烯基苯单体重量份比为60：(6-7.2)。本技术方案具有更为优良的耐温性能,且具有广泛适用于醚化、酯化、水合等有机催化反应的技术优点。(The invention provides a general temperature-resistant acid-reinforced resin catalyst and a preparation method thereof. The general temperature-resistant acid-reinforced resin catalyst is prepared by polymerizing styrene and divinylbenzene monomer systems, extracting and drying the polymerized styrene and divinylbenzene monomer systems to obtain resin-based spheres, and then performing chlorination, sulfonation, active group stabilization modification and washing, wherein the weight ratio of the styrene to the divinylbenzene monomer is 60: (6-7.2). The technical scheme has more excellent temperature resistance and has the technical advantages of being widely applicable to organic catalytic reactions such as etherification, esterification, hydration and the like.)

1. A general temperature-resistant acidic reinforced resin catalyst is prepared by suspension copolymerization of styrene and divinylbenzene monomer systems coexisting with a pore-forming agent and a dispersing agent, extracting and drying to obtain resin-based spheres, chlorination, sulfonation, active group stabilization modification and washing, and is characterized in that an initiator in the suspension system is benzyl peroxide, the pore-forming agent is sec-butyl alcohol, the dispersing agent is polyvinyl alcohol, a halogenating agent is chlorine, and a sulfonating agent is fuming sulfuric acid and chlorosulfonic acid, wherein the weight part ratio of the styrene to the divinylbenzene monomers is 60: (6-7.2).

2. The universal temperature-acid resistant reinforced resin catalyst as claimed in claim 1, wherein the weight ratio of styrene to divinylbenzene monomer to pore-forming agent to initiator to dispersant to water is 60: (6-7.2): (20-50): (0.3-0.6): (1.0-2.0): (300-500).

3. The universal temperature-resistant acid-reinforced resin catalyst according to claim 1, wherein the chlorination reaction is: soaking the resin-based ball in dichloromethane solvent for 6 hr, taking out, contacting with catalyst iron chloride powder, halogenating at 70 deg.c under 0.2MPa chlorine pressure for 7 hr, and washing to obtain halogenated resin ball.

4. The general temperature-resistant acidic reinforced resin catalyst according to claim 1 or 2, wherein a clean resin-based sphere is extracted, dried to a water content of 5 to 10 wt%, and screened to have a particle size of 0.3 to 1.2mm as the resin-based sphere.

5. The general temperature-resistant acid-reinforced resin catalyst according to claim 1, wherein the sulfonation process comprises: immersing the halogenated resin balls in fuming sulfuric acid dissolved with chlorosulfonic acid, wherein the mass ratio of the fuming sulfuric acid to the chlorosulfonic acid to the halogenated white balls is 6-10: 1-3: 1, stirring to fully mix the resin balls with a sulfonating agent, heating to 100-120 ℃, reacting for 8-20 h, and cooling.

6. The general temperature-resistant acid-reinforced resin catalyst according to claim 1, wherein the active group stabilization modification process comprises: the sulfonated resin balls are soaked in pressurized water at 120 ℃ for 120 hours, and finally, the resin with the water content of 50% +/-5% is separated out and is used as a catalyst.

7. The universal temperature-resistant acid-strengthening resin catalyst according to claim 6, wherein the water pressurization value is 0.2MPa to 0.3 MPa.

8. A method for preparing the general temperature-resistant acidic-reinforced resin catalyst as claimed in any one of claims 1 to 7.

Technical Field

The application relates to a catalyst for preparing high molecular polymer resin and a preparation method thereof, in particular to a polystyrene strong acid temperature-resistant catalyst and a preparation method thereof.

Background

The strong acid type cation exchange resin catalyst overcomes the problem of strong corrosivity of homogeneous acid catalysis, has the advantage of convenient separation from products, and is widely applied to various manufacturing fields of petrochemical industry, fine chemical industry, pharmaceutical industry and the like. However, the strong acid type cation exchange resin catalyst generally has the technical problem of poor heat resistance stability, and particularly in the organic reaction catalysis application such as etherification, esterification and hydration, the sulfonic acid group of the resin catalyst can be seriously peeled off due to the rise of the reaction temperature, so that the catalytic activity is lost.

Patent document CN111111791A discloses a methanesulfonic acid type cation exchange resin and a method for producing the same. Concretely, chloromethylation macroporous crosslinked polystyrene chloride spheres react with a sulfhydrylation reagent to obtain sulfhydrylation resin, and then the methanesulfonic acid type cation exchange resin is obtained under the action of an oxidant, and the record shows that the heat resistance stability of the prepared resin is improved by 30% compared with that of the conventional cation exchange resin. However, the technical method for oxidizing the chloromethylation reagent and the sulfhydrylation reagent of the chlorine ball disclosed in the document has high toxicity, potential safety production hazards and great environmental protection pressure.

Another technical means for improving the temperature resistance of the cationic resin catalyst is to perform halogenation and sulfonation. For example, patent document CN107537570A discloses a strong acid type high temperature resistant cationic resin catalyst and a preparation method thereof, wherein styrene and divinyl benzene are subjected to suspension polymerization to obtain a resin, the structure of the resin is stabilized, and then halogenation, sulfonation and active group stabilization are carried out to stabilize sulfonate. However, the temperature resistance of the method is not ideal, the stable temperature is limited to 90 ℃, the temperature resistance is limited, the method has no general applicability and universality, and the method is only used for catalytic synthesis of sec-butyl acetate.

Disclosure of Invention

The invention aims to further improve the temperature resistance of the resin catalyst, maintain the temperature-resistant catalytic activity and stability and have wider temperature-resistant catalytic reaction application range, and provides a general temperature-resistant acidic reinforced resin catalyst and a preparation method thereof.

The invention provides a technical scheme of a general temperature-resistant acid-reinforced resin catalyst, which mainly comprises the following technical contents: a general temperature-resistant acidic reinforced resin catalyst is prepared by suspension copolymerization of styrene and divinylbenzene monomer systems coexisting with a pore-forming agent and a dispersing agent, extracting and drying to obtain resin-based spheres, chlorination, sulfonation, active group stabilization modification and washing, wherein in the suspension system, an initiator is benzoyl peroxide, the pore-forming agent is sec-butyl alcohol, the dispersing agent is polyvinyl alcohol, a halogenating agent is chlorine, and a sulfonating agent is fuming sulfuric acid and chlorosulfonic acid, wherein the weight part ratio of the styrene to the divinylbenzene monomer is 60: (6-7.2).

One of the preferred options of the whole technical scheme is that the weight ratio of styrene to divinylbenzene monomer to pore-foaming agent to initiator to dispersant to water is 60: (6-7.2): (20-50): (0.3-0.6): (1.0-2.0): (300-500).

One preferred item of the above overall technical scheme is that the chlorination reaction is as follows: soaking the resin-based ball in dichloromethane solvent for 6 hr, taking out, contacting with catalyst iron chloride powder, halogenating at 70 deg.c under 0.2MPa chlorine pressure for 7 hr, and washing to obtain halogenated resin ball.

One preferred item of the whole technical scheme is that clean resin-based balls are extracted, dried until the water content is 5-10 wt%, and screened to have the particle size of 0.3-1.2mm to be used as the resin-based balls.

In one preferred embodiment of the above overall technical solution, the sulfonation process comprises: immersing the halogenated resin balls in fuming sulfuric acid dissolved with chlorosulfonic acid, wherein the mass ratio of the fuming sulfuric acid to the chlorosulfonic acid to the halogenated white balls is 6-10: 1-3: 1, stirring to fully mix the resin balls with a sulfonating agent, heating to 100-120 ℃, reacting for 8-20 h, and cooling.

In one preferred aspect of the above overall technical solution, the active group stabilization modification process comprises: the sulfonated resin balls are soaked in pressurized water at 120 ℃ for 120 hours, and finally, the resin with the water content of 50% +/-5% is separated out and is used as a catalyst.

Long-term research shows that halogen is mainly introduced to para position and ortho position of styrene-CH, and a considerable part of sulfonic acid groups in sulfonation are extruded to divinylbenzene except for introduction of meta position of the halogen, so that the catalyst is a main technical reason for influencing temperature resistance of the catalyst and causing poor temperature resistance of the catalyst. The recombinant monomer system and the suspension system thereof improve the introduction amount of a sulfonate group in styrene, control the cross-linking amount on the premise of ensuring the strength and the halogenation rate of resin, solve the technical problems that the introduction amount of the sulfonate group on the styrene is influenced by the introduction amount of halogen, so that the strength of catalyst acid is insufficient and the temperature resistance is poor, and simultaneously combine with chlorination, sulfonation and stabilization processes to strengthen sulfonation reaction, sulfonation is carried out by fuming sulfuric acid and chlorosulfonic acid, and the chlorosulfonic acid reacts with water to synthesize sulfuric acid and hydrogen chloride, so that the technical problems that the sulfuric acid concentration is reduced and the sulfonation is insufficient due to the generation of water in the fuming sulfuric acid sulfonation are solved, deep sulfonation is realized, and the activity and the stability of the catalyst are comprehensively improved. Compared with the existing temperature-resistant cation exchange resin catalyst, the resin catalyst has more excellent temperature resistance, and through experimental comparison, the temperature resistance of the catalyst is improved by more than 70% compared with the existing temperature-resistant cation exchange resin catalyst, the exchange capacity level of the catalyst is improved to a certain extent, and the catalyst also has the technical advantages of being widely applicable to organic catalytic reactions such as etherification, esterification and hydration, becoming a general resin catalyst and changing the technical current situation that the prior art needs to provide a special cation exchange resin catalyst for organic catalytic reactions such as etherification, esterification and hydration.

Detailed Description

The technical solution of the present invention will be described in detail with reference to the following examples, but the scope of the present invention is not limited by the following specific examples. For convenience of illustration, in each example, the initiator is benzoyl peroxide, the pore-forming agent is sec-butyl alcohol, the dispersant is polyvinyl alcohol, the halogenating agent is chlorine, and the sulfonating agent is fuming sulfuric acid and chlorosulfonic acid.

Example 1-catalyst a:

(1) polymerisation

Adding styrene, divinyl benzene, a pore-forming agent and an initiator into a mixing tank according to the dosage in the table 1, and uniformly stirring and mixing to obtain an oil phase;

adding water and a dispersing agent into a polymerization kettle according to the dosage shown in the table 1, stirring and heating to 40 ℃ to obtain a dissolved water solution; adding an oil phase, regulating the stirring speed to 90 r/min according to the monomer dispersion condition, slowly heating to 80 ℃, carrying out polymerization reaction for 8 hours, cooling, filtering, washing the filtered polymer with hot water and cold water respectively for three times, and separating out a polymerized white ball;

TABLE 1

(2) De-pore-forming agent

Putting the polymerized white ball in the step (1) into an extraction kettle, adding excessive water into a distillation kettle, and heating to ensure that the pore-forming agent of the polymerized white ball in the kettle is distilled out by azeotropy with the water. Repeating the steps for 6 times, and completely extracting the pore-foaming agent of the polymerized white ball.

(3) Drying and sieving

Drying the polymer which is extracted cleanly in a ventilation position until the water content is 5%, and screening white balls with the grain diameter of 0.3mm to serve as a subsequent modified matrix;

(4) chlorination of

Soaking the white ball obtained in the step (3) in a dichloromethane solvent for 6 hours, then uniformly contacting with catalyst iron chloride powder, carrying out halogenation reaction in chlorine gas with the pressure of 0.2Mpa and the temperature of 70 ℃ for 7 hours, and cleaning the halogenated ball after the reaction is finished;

(5) sulfonation of

Immersing a halogenated ball in fuming sulfuric acid for dissolving chlorosulfonic acid, wherein the mass ratio of the halogenated ball to the chlorosulfonic acid to the fuming sulfuric acid is 1:1:6, and stirring for 0.5h until the mixture is fully mixed; the reaction temperature is 100 ℃ for 8 hours, and the reaction is cooled;

(6) reactive group stabilization

Transferring the sulfonated resin into a reaction kettle, adding water with the pressure of 0.2MPa-0.3MPa and the temperature of 120 ℃ into the kettle, soaking for 120 hours, and finally separating out a resin product with the water content of 50% +/-5%, wherein the resin product is used as a catalyst A.

Example 2-catalyst B:

(1) polymerisation

Adding styrene, divinyl benzene, a pore-forming agent and an initiator into a mixing tank according to the dosage shown in the table 2, and uniformly stirring and mixing to obtain an oil phase;

adding water and a dispersing agent into a polymerization kettle according to the dosage shown in the table 2, stirring and heating to 50 ℃ to obtain a dissolved water solution; adding an oil phase, regulating the stirring speed to be 100 revolutions per minute according to the dispersion condition of the monomers, slowly heating to 80 ℃ for polymerization reaction for 18 hours, cooling, filtering, washing the filtered polymer with hot water and cold water respectively for three times, and separating out a polymerized white ball;

TABLE 2

(2) De-pore-forming agent

The same as example 1, wherein the extraction was repeated 20 times.

(3) Drying and sieving

Drying the polymer which is extracted cleanly in a ventilation place until the water content is 10%, and screening white balls with the grain diameter of 0.3-1.2mm to serve as a subsequent modified matrix;

(4) chlorination of

The same as example 1;

(5) sulfonation of

Immersing a halogenated ball in fuming sulfuric acid for dissolving chlorosulfonic acid, wherein the mass ratio of the halogenated ball to the chlorosulfonic acid to the fuming sulfuric acid is 1:3:10, and stirring for 2 hours until the mixture is fully mixed; the reaction temperature is 120 ℃ for 20 hours, and the reaction is cooled;

(6) reactive group stabilization

Catalyst B was obtained in the same manner as in example 1.

Example 3-catalyst C:

(1) polymerisation

Adding styrene, divinyl benzene, a pore-forming agent and an initiator into a mixing tank according to the dosage shown in the table 3, and uniformly stirring and mixing to obtain an oil phase;

adding water and a dispersing agent into a polymerization kettle according to the dosage shown in the table 3, stirring and heating to 45 ℃ to form a dissolved water solution; adding an oil phase, regulating the stirring speed to 95 revolutions per minute according to the dispersion condition of the monomers, slowly heating to 80 ℃ for polymerization reaction for 10 hours, cooling, filtering, washing the filtered polymer with hot water and cold water for three times respectively, and separating out a polymerized white ball;

TABLE 3

Styrene (meth) acrylic acid ester	60
		Divinylbenzene	7.0
Pore-forming agent	30
		Initiator	0.4
Dispersing agent	1.5
		Water (W)	400

(2) De-pore-forming agent

The same as example 1, wherein the extraction was repeated 10 times.

(3) Drying and sieving

Drying the white balls which are completely extracted in a ventilation place until the water content is 8%, and screening the white balls with the grain diameter of 0.3-1.2mm to be used as a subsequent modified matrix;

(4) chlorination of

The same as example 1;

(5) sulfonation of

Immersing a halogenated ball in fuming sulfuric acid for dissolving chlorosulfonic acid, wherein the mass ratio of the halogenated ball to the chlorosulfonic acid to the fuming sulfuric acid is 1:2:8, stirring for 1h until the halogenated ball, the chlorosulfonic acid and the fuming sulfuric acid are fully mixed, reacting for 10 h at the reaction temperature of 110 ℃, and cooling after the reaction;

(6) reactive group stabilization

Catalyst C was obtained as in example 1.

Comparative example 1:

comparative example 1 was synthesized using the technique disclosed in patent CN 111111791A.

Comparative example 2:

comparative example 2 was synthesized using the technique disclosed in patent CN 107537570A.

The above 5 kinds of resin catalysts were transferred to a reaction kettle, respectively, and pressurized in water at 150 ℃ for 120 hours under a pressure ranging from 0.5MPa to 0.6MPa, and their stability test results are shown in the following table:

experiments show that the acid strength of the novel resin catalyst prepared by the invention is obviously improved compared with a comparative example, and particularly, stability tests show that: compared with the conventional resin catalyst, the novel resin catalyst prepared by the invention has the advantages that the exchange capacity of the product with two pairs of proportions is reduced to a small extent, the temperature resistance is greatly improved compared with the two pairs of proportions, and the temperature resistance is higher than that of the conventional resin by more than 70 percent.