CN114011465B - Granular porous perfluorinated sulfonic acid resin catalyst and preparation method and application thereof - Google Patents

Granular porous perfluorinated sulfonic acid resin catalyst and preparation method and application thereof Download PDF

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CN114011465B
CN114011465B CN202111357681.3A CN202111357681A CN114011465B CN 114011465 B CN114011465 B CN 114011465B CN 202111357681 A CN202111357681 A CN 202111357681A CN 114011465 B CN114011465 B CN 114011465B
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acid resin
resin catalyst
perfluorinated sulfonic
sulfonic acid
porous
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CN114011465A (en
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裴素朋
徐康伟
张维
韩志越
张英格
马佳璐
刘贵鹏
徐晓钧
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Shanghai Institute of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—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
    • 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
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0063—Granulating
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a granular porous perfluorinated sulfonic acid resin catalyst, a preparation method and application thereof, wherein powdery perfluorinated sulfonic acid resin powder is used as an active component, and the catalyst is prepared by blending calcium carbonate powder and perfluorinated sulfonic acid resin powder, and then carrying out melt extrusion and stretch granulation. The method is simple and easy for large-scale production, and the prepared catalyst has obvious porous characteristics, larger specific surface area and more accessible acid sites, can be used for catalyzing the addition reaction of the 1, 3-dicarbonyl compound and the olefin compound, has good catalytic performance, can be recycled for multiple times and does not obviously reduce the yield.

Description

Granular porous perfluorinated sulfonic acid resin catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic chemical industry, and particularly relates to a granular porous perfluorinated sulfonic acid resin catalyst and a preparation method and application thereof.
Background
In organic chemistry, complex molecular compounds are synthesized from simple small molecules by a reaction efficient, atom economical and environment friendly method, and are one of the most active parts in chemical synthesis today. Among them, the formation of C-C bonds is an important means for achieving this.
As one of the most common modes of C-C bond formation, the addition reaction of a 1, 3-dicarbonyl compound with an olefin compound is a very useful method of forming a C-C bond. The various effective catalysts used in such reactions include essentially: solid acid catalysts such as Lewis acid, molecular sieve, montmorillonite, etc. Meanwhile, new environment-friendly green catalyst-heteropolyacid and its salt development and research are attracting attention. Although these strategies are viable, there are drawbacks, such as the volatile solvents required for most processes, and the corrosiveness of some catalysts. In addition, the recovery frequency of the catalyst is still limited. Clearly, the addition reaction of 1, 3-dicarbonyl compounds with olefin compounds remains a challenge. Thus, there remains a need to find a milder, more reusable, more environmentally friendly solid catalyst for the addition reaction of 1, 3-dicarbonyl compounds with olefin compounds.
Perfluorosulfonic acid resins (PFSA) are the strongest known solid superacids with significant thermal and chemical stability. It has been used as an environmentally friendly green solid acid catalyst for catalyzing many organic reactions such as hydrolysis, esterification, and isomerization, which has been demonstrated to have good catalytic effects. In addition, perfluorinated sulfonic acid resins are superior to other acid catalysts in many respects, have stronger acidity, are non-corrosive, are easy to separate products, and can be reused. Patent CN106925347B discloses a preparation method of a porous perfluorosulfonic acid resin catalyst, wherein the perfluorosulfonic acid resin is hydrolyzed into metal ion type perfluorosulfonic acid resin in alkaline solution; ion exchange is carried out on the metal ion type perfluorinated sulfonic acid resin in acid liquor to obtain acidic hydrogen ion type perfluorinated sulfonic acid resin; swelling the hydrogen ion type perfluorinated sulfonic acid resin in a solvent system; freezing the swelled hydrogen ion type perfluorinated sulfonic acid resin in a freeze drying device, sublimating to remove the solvent and drying to obtain the product. However, it has the disadvantage that its acidic center is not easily contacted with the reactant due to its low specific surface area.
Disclosure of Invention
The invention aims to solve the problems and provide a granular porous perfluorosulfonic acid resin catalyst, a preparation method and application thereof, and the granular porous perfluorosulfonic acid resin catalyst developed by the invention overcomes the defect of low specific surface area of perfluorosulfonic acid resin, remarkably increases the proportion of available acid sites, is easier to contact with reactants, has high usability and efficiency for catalyzing the addition reaction of 1, 3-dicarbonyl compounds and olefin compounds, and can be recycled for multiple times.
The aim of the invention is achieved by the following technical scheme:
a granular porous perfluorinated sulfonic acid resin catalyst is prepared from powdered perfluorinated sulfonic acid resin as active component through mixing perfluorinated sulfonic acid resin powder with calcium carbonate powder, fusing, extruding out, cooling, stretching, granulating, acid treating, washing with water to neutrality, and high-specific-surface-area preparing granular porous solid super acidic catalyst.
Preferably, the granular porous perfluorinated sulfonic acid resin catalyst comprises the following raw materials in percentage by mass: 30-50% of calcium carbonate powder and 50-70% of perfluorosulfonic acid resin powder.
Preferably, the particle size of the calcium carbonate powder is 300 mesh or more, and the ion exchange capacity of the perfluorosulfonic acid resin powder is between 0.7 and 2.2 mmol/g.
A preparation method of a granular porous perfluorinated sulfonic acid resin catalyst comprises the steps of blending perfluorinated sulfonic acid resin powder with calcium carbonate powder, carrying out melt extrusion, water cooling and stretching granulation treatment, and carrying out acid treatment and water washing to neutrality on a granulated sample to obtain a porous solid super acidic catalyst with high specific surface area.
Preferably, the melt extrusion is performed by a twin screw extruder, in which the temperature at which the melt extrusion is performed is 200 to 260 ℃.
Preferably, the acid used in the acid treatment operation is at least one acid selected from hydrochloric acid and nitric acid, and the acid treatment time is 4 to 20 hours.
The granular porous perfluorosulfonic acid resin catalyst is used for catalyzing the addition reaction of 1, 3-dicarbonyl compounds and olefin compounds.
Preferably, the molar ratio of the olefin compound to the 1, 3-dicarbonyl compound is 1:1-1:2; the dosage of the granular porous perfluorinated sulfonic acid resin catalyst is 10-30% of the total mass of the reactants, and the dosage of the catalyst is 20-30% of the total mass of the reactants.
Preferably, the reaction temperature of the addition reaction is 50-90 ℃ and the reaction time is 4-7 h. The reaction time of the series of reactions is accelerated with the rise of the reaction temperature in a suitable temperature range, and too short a reaction time leads to too low a conversion rate, so that the suitable reaction time is 4 to 7 hours.
Preferably, the 1, 3-dicarbonyl compound comprises one of 2, 4-pentanedione, 1, 3-diphenylpropanediol and ethyl trifluoroacetoacetate, and the olefin compound comprises one of styrene and 4-chlorostyrene; after the reaction is finished, the granular porous perfluorinated sulfonic acid resin catalyst is separated, dried and reused, and the drying temperature is 70-130 ℃; the drying time is 30-60 min, the reaction can be carried out under the condition of no solvent, the fluorocarbon main chain structure of the granular porous perfluorinated sulfonic acid resin catalyst has hydrophobicity, the influence of the product water on the hydration of an acid center can be avoided to a certain extent, and further, the cost increase and the environmental pollution caused by adding water-carrying agents such as toluene and the like can be avoided.
Compared with the prior art, the invention has the advantages that:
the invention prepares a brand new granular porous perfluorinated sulfonic acid resin catalyst, takes perfluorinated sulfonic acid resin powder as an active component, and adopts a melt extrusion, stretching and granulating method to prepare the granular porous perfluorinated sulfonic acid resin catalyst. The catalyst has good catalytic performance in the addition reaction of the 1, 3-dicarbonyl compound and the olefin compound under the condition of no solvent, is easy to separate from the product, and can be repeatedly recycled. The granular porous perfluorinated sulfonic acid resin catalyst developed by the invention has relatively large specific surface area, more accessible acid sites and good catalytic performance.
Drawings
FIG. 1 is an SEM characterization of a particulate porous perfluorosulfonic acid resin;
fig. 2 is an SEM characterization of the powdered perfluorosulfonic acid resin.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
The 2, 4-pentanedione used in the invention is a chemical pure REAGENT, GENERAL-REAGENT company; styrene is reagent grade, shanghai Meilin Biochemical technology Co., ltd; the perfluorosulfonic acid resin powder original manufacturer is the eastern mountain group of Shandong.
Example 1: preparation of granular porous perfluorosulfonic acid resin catalyst
The preparation method comprises the steps of mixing perfluorosulfonic acid resin powder and calcium carbonate powder in a mass ratio of 1:1, adding the mixture into a double-screw extruder, setting the melting temperature of the double-screw extruder to be 240 ℃, setting the traction speed to be 5M/min, carrying out water cooling on the melt-extruded perfluorosulfonic acid resin and calcium carbonate, carrying out cutter treatment to obtain granular perfluorosulfonic acid/calcium carbonate, transferring the granular perfluorosulfonic acid/calcium carbonate into 2M hydrochloric acid, carrying out normal-temperature treatment for 6h, and washing with distilled water until the pH value of filtrate is neutral, thereby obtaining the granular porous solid super-acidic catalyst with high specific surface area. BET analysis porous perfluorosulfonic acid resin catalyst having a specific surface area of 2.4322m 2 Per gram, the number of acid centers per unit mass is 0.9mmol/g as determined by titration. FIG. 1 is an SEM characterization of a particulate porous perfluorosulfonic acid resin; fig. 2 is an SEM characterization of the powdered perfluorosulfonic acid resin.
Example 2
25wt% of a particulate porous perfluorosulfonic acid resin catalyst was added to a mixture of 2, 4-pentanedione (1 mmol) and styrene (1 mmol). The mixture was stirred and heated at a reaction temperature of 60℃for a reaction time of 6h. The whole reaction was monitored by TLC until the end of the reaction. When the mixture was cooled to room temperature, the product was stirred with ethyl acetate to dissolve, and then the solution was removed with a syringe. The porous perfluorosulfonic acid resin catalyst was dried at 90℃for 1 hour for reuse. The solution containing the product was concentrated in a rotary evaporator and then dissolved in methanol, and the yield of the product was determined to be 70% by liquid chromatography.
Comparative example
In comparison with example 2, the present comparative example was carried out by replacing the particulate porous perfluorosulfonic acid resin catalyst with a conventional perfluorosulfonic acid resin powder, and the remaining components were the same, and as a result, the yield of the product was measured by liquid chromatography and found to be 51%. This shows that the use of perfluorosulfonic acid resin powder as a catalyst is far less effective than a particulate porous perfluorosulfonic acid resin catalyst.
Example 3
25wt% of a particulate porous perfluorosulfonic acid resin catalyst was added to a mixture of 2, 4-pentanedione (1.5 mmol) and styrene (1 mmol). The mixture was stirred and heated at a reaction temperature of 60℃for a reaction time of 6h. The whole reaction was monitored by TLC until the end of the reaction. When the mixture was cooled to room temperature, the product was stirred with ethyl acetate to dissolve, and then the solution was removed with a syringe. The porous perfluorosulfonic acid resin catalyst was dried at 90℃for 1 hour for reuse. The solution containing the product was concentrated in a rotary evaporator and then dissolved in methanol, and the yield of the product was 73% as determined by liquid chromatography.
Example 4
25wt% of a particulate porous perfluorosulfonic acid resin catalyst was added to a mixture of 2, 4-pentanedione (2 mmol) and styrene (1 mmol). The mixture was stirred and heated at a reaction temperature of 60℃for a reaction time of 6h. The whole reaction was monitored by TLC until the end of the reaction. When the mixture was cooled to room temperature, the product was stirred with ethyl acetate to dissolve, and then the solution was removed with a syringe. The porous perfluorosulfonic acid resin catalyst was dried at 90℃for 1 hour for reuse. The product-containing solution was concentrated in a rotary evaporator and then dissolved in methanol, and the yield of the product was 76% as determined by liquid chromatography.
Example 5
20wt% of a particulate porous perfluorosulfonic acid resin catalyst was added to a mixture of 2, 4-pentanedione (2 mmol) and styrene (1 mmol). The mixture was stirred and heated at a reaction temperature of 60℃for a reaction time of 6h. The whole reaction was monitored by TLC until the end of the reaction. When the mixture was cooled to room temperature, the product was stirred with ethyl acetate to dissolve, and then the solution was removed with a syringe. The porous perfluorosulfonic acid resin catalyst was dried at 90℃for 1 hour for reuse. The solution containing the product was concentrated in a rotary evaporator and then dissolved in methanol, and the yield of the product was 69% as determined by liquid chromatography.
Example 6
15wt% of a particulate porous perfluorosulfonic acid resin catalyst was added to a mixture of 2, 4-pentanedione (2 mmol) and styrene (1 mmol). The mixture was stirred and heated at a reaction temperature of 60℃for a reaction time of 6h. The whole reaction was monitored by TLC until the end of the reaction. When the mixture was cooled to room temperature, the product was stirred with ethyl acetate to dissolve, and then the solution was removed with a syringe. The porous perfluorosulfonic acid resin catalyst was dried at 90℃for 1 hour for reuse. The solution containing the product was concentrated in a rotary evaporator and then dissolved in methanol, and the yield of the product was determined to be 65% by liquid chromatography.
Example 7
25wt% of a particulate porous perfluorosulfonic acid resin catalyst was added to a mixture of 2, 4-pentanedione (2 mmol) and styrene (1 mmol). The mixture was stirred and heated at a reaction temperature of 70℃for a reaction time of 5h. The whole reaction was monitored by TLC until the end of the reaction. When the mixture was cooled to room temperature, the product was stirred with ethyl acetate to dissolve, and then the solution was removed with a syringe. The porous perfluorosulfonic acid resin catalyst was dried at 90℃for 1 hour for reuse. The product-containing solution was concentrated in a rotary evaporator and then dissolved in methanol, and the yield of the product was 78% as determined by liquid chromatography.
Example 8
25wt% of a particulate porous perfluorosulfonic acid resin catalyst was added to a mixture of 2, 4-pentanedione (2 mmol) and styrene (1 mmol). The mixture was stirred and heated at a reaction temperature of 80℃for a reaction time of 4h. The whole reaction was monitored by TLC until the end of the reaction. When the mixture was cooled to room temperature, the product was stirred with ethyl acetate to dissolve, and then the solution was removed with a syringe. The porous perfluorosulfonic acid resin catalyst was dried at 90℃for 1 hour for reuse. The solution containing the product was concentrated in a rotary evaporator and then dissolved in methanol, and the yield of the product was determined to be 72% by liquid chromatography.
Example 9
After the porous perfluorosulfonic acid resin catalyst in the form of granules used in example 7 was circulated 8 times, it was dried again at 90℃for 1 hour and then added to a mixture of 2, 4-pentanedione (2 mmol) and styrene (1 mmol). The mixture was stirred and heated at a reaction temperature of 70℃for a reaction time of 5h. The whole reaction was monitored by TLC until the end of the reaction. When the mixture was cooled to room temperature, the product was stirred with ethyl acetate to dissolve, and then the solution was removed with a syringe. The solution containing the product was concentrated in a rotary evaporator and then dissolved in methanol, and the yield of the product was 69% as determined by liquid chromatography.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.

Claims (8)

1. The application of the granular porous perfluorinated sulfonic acid resin catalyst is characterized in that powdery perfluorinated sulfonic acid resin is used as an active component, perfluorinated sulfonic acid resin powder and calcium carbonate powder are blended, and a granulated sample is subjected to acid treatment and water washing to be neutral after melt extrusion, cooling and stretching granulation treatment, so that the granular porous solid super acid catalyst with high specific surface area is obtained;
the granular porous perfluorosulfonic acid resin catalyst is used for catalyzing the addition reaction of 1, 3-dicarbonyl compounds and olefin compounds.
2. The application of the granular porous perfluorosulfonic acid resin catalyst according to claim 1, which is characterized in that the granular porous perfluorosulfonic acid resin catalyst comprises the following raw materials in percentage by mass: 30-50% of calcium carbonate powder and 50-70% of perfluorosulfonic acid resin powder.
3. The use of a particulate porous perfluorosulfonic acid resin catalyst according to claim 1, wherein the calcium carbonate powder has a particle size of 300 mesh or more and the perfluorosulfonic acid resin powder has an ion exchange capacity of 0.7 to 2.2 mmol/g.
4. The use of a particulate porous perfluorosulfonic acid resin catalyst according to claim 1, wherein the melt extrusion is carried out by a twin screw extruder at a temperature of 200 to 260 ℃.
5. The use of a particulate porous perfluorosulfonic acid resin catalyst according to claim 1, wherein the acid used in the acid treatment operation is at least one acid selected from the group consisting of hydrochloric acid and nitric acid, and the acid treatment time is 4 to 20 hours.
6. The use of a particulate porous perfluorosulfonic acid resin catalyst according to claim 1, wherein the molar ratio of the olefin compound to the 1, 3-dicarbonyl compound is 1:1 to 1:2; the dosage of the granular porous perfluorinated sulfonic acid resin catalyst accounts for 10-30% of the total mass of reactants.
7. The application of the granular porous perfluorinated sulfonic acid resin catalyst according to claim 1, wherein the reaction temperature of the addition reaction is 50-90 ℃ and the reaction time is 4-7 h.
8. The use of a particulate porous perfluorosulfonic acid resin catalyst according to claim 1, wherein the 1, 3-dicarbonyl compound comprises one of 2, 4-pentanedione, 1, 3-diphenylpropanediol, ethyl trifluoroacetoacetate, and the olefin compound comprises one of styrene, 4-chlorostyrene;
after the reaction is finished, the granular porous perfluorinated sulfonic acid resin catalyst is separated, dried and reused, and the drying temperature is 70-130 ℃; the drying time ranges from 30 min to 60min, and the reaction can be carried out under the condition of no solvent.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103554464A (en) * 2013-11-14 2014-02-05 国电新能源技术研究院 Catalytic system for catalyzing ring opening polymerization of tetrahydrofuran
CN106750746A (en) * 2016-11-29 2017-05-31 陕西环珂生物科技有限公司 A kind of preparation method of HDPE microvesicles plastics
CN111359661A (en) * 2020-03-19 2020-07-03 辽宁科京新材料科技有限公司 Preparation method of perfluorosulfonic acid resin super acidic catalyst with porous structure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103554464A (en) * 2013-11-14 2014-02-05 国电新能源技术研究院 Catalytic system for catalyzing ring opening polymerization of tetrahydrofuran
CN106750746A (en) * 2016-11-29 2017-05-31 陕西环珂生物科技有限公司 A kind of preparation method of HDPE microvesicles plastics
CN111359661A (en) * 2020-03-19 2020-07-03 辽宁科京新材料科技有限公司 Preparation method of perfluorosulfonic acid resin super acidic catalyst with porous structure

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