CN104774284A - Preparation method of porous perfluorinated sulfonic acid resin for catalysts - Google Patents
Preparation method of porous perfluorinated sulfonic acid resin for catalysts Download PDFInfo
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Abstract
The invention relates to a preparation method of porous perfluorinated sulfonic acid resin for catalysts, wherein the preparation method comprises that perfluoro(sulfonyl vinyl)ether and tetrafluoroethylene are polymerized under the condition of co-existence of a solvent, a pore-forming agent and an initiating agent to obtain the product, the perfluorinated sulfonic acid resin having low equivalent weight and low molecular weight is used as the pore-forming agent, the solvent is recycled by a way of adding deionized water and a dispersant and carrying out distillation, at the same time, the resin is molded, after further drying, a granular material is obtained, and moreover, a mixture of one or more of perfluorinated hydrocarbon/perfluorinated cyclic ether/chlorofluorocarbon are used as an extraction agent for extracting the pore-forming agent so as to form a porous structure. The method has simple operating conditions, has no need for high temperature and high pressure, and solves the problem in the prior art that effective catalytic component loss is difficult to overcome during a using process, and the service life of the catalyst is increased; and at the same time, due to the existence of the porous structure, the specific surface area is increased, and the active component utilization rate is improved.
Description
Technical field
The present invention relates to a kind of preparation method of catalyzer porous perfluorinated sulfonic resin, relate to a kind of method taking low-molecular(weight)polymer as pore-creating agent and synthesize perfluorinated sulfonic resin class porous strongly acidic cation-exchange catalyzer specifically.
Background technology
After nineteen sixties du pont company scientist Connolly etc. prepares perfluorinated sulfonic resin, it is as fuel cell membranes, and chlorine industry electrolytic experiment barrier film, solid polymer electrolyte etc. are widely used.Find it as solid super acid catalyst in organic synthesis, as alkylation, acidylate, nitrated, sulfonation, phosphorylated, polymerization, condensation, etherificate, esterification, aquation and rearrangement reaction all have good katalysis simultaneously.Perfluorinated sulfonic resin is compared with liquid acid catalysis, there is non-corrosiveness, do not produce spent acid solution, product is easily separated, selectivity is high and can the repeatedly advantage such as Reusability, with general solid acid ratio, there is productive rate high, reaction conditions relaxes, and the advantages such as speed of response is fast, compared with other acidic cation-exchange resin, having stronger acidity, use temperature high, is very desirable a kind of solid acid catalyst.Increasing specific surface area as a kind of catalyzer and improving to utilize the ratio in acid site to be the important measures improving catalysis potentiality.
The main method preparing azochlorosulfonate acid resin catalyst at present have following several 1, perfluorinated sulfonic resin is carried out fine segmentation, this kind of method can increase its surface-area.But can be clogged by the polymkeric substance of fine segmentation in catalyzer continuous processing and hinder flowing.2, Selwyn Lloyd etc. propose sulfonate resin and high pressure fluid as CO in CN1337891
2or SO
2contact, carries out swelling, then this polymkeric substance is heated to more than softening temperature, explosive decompression, makes gas from " escape " swelling polymkeric substance out thus make swelling polymer be vesicular structure.This kind of preparation method needs higher working pressure.3, loading type perfluorinated sulfonic resin, in patent US4038213, patent US4661411, describe conventional inorganic carrier has Al
2o
3, AlF
3, ZrO
2, SiO
2deng, Butt have employed carrier such as tetrafluoroethylene, tetrafluoroethylene and the hexafluoropropylene copolymer, polyethylene, polypropylene, refinery coke etc. with hydrophobic surface and prepares perfluorinated sulfonic resin catalyzer as carrier in patent US5094995.The main preparation methods of supported catalyst has pickling process, dipping circumfluence method, dipping steam seasoning, and obtained specific surface area of catalyst significantly increases, and acidic site is easily close by reactant institute, but active principle easily runs off in reaction process.4, sol-gel method loading type perfluorinated sulfonic resin, contacts sulfonate resin solution with silicate solutions, makes silicate form SiO
2network structure, obtains porous nano mixture, and this kind of preparation method decreases the loss of active principle to a certain extent, adds catalytic activity simultaneously.Sol-gel method is the same with load method needs the water-alcohol solution preparing sulfonate resin, with regard to the perfluorinated sulfonic resin of the very poor high molecular of solvability, this process increases the preparation difficulty of catalyzer undoubtedly, these two kinds of preparation methods also fundamentally cannot solve the problem that active principle runs off, and cause the decline in catalyzer work-ing life.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of preparation method of catalyzer porous perfluorinated sulfonic resin is provided.
Term explanation
EW value: also referred to as molal weight, to the corresponding ion of 1mol in extraneous solution carry out equivalent exchange time, required dried resin weight.Unit is g/mol, is: EW=1000/IEC with the pass of exchange capacity.
Summary of the invention
The present invention adopts low molal weight, lower molecular weight perfluorinated sulfonic resin as pore-creating agent, and perfluor sulfonyl vinyl ether and tetrafluoroethylene are carried out copolymerization, obtains the perfluor sulfonyl fluoro-resin meeting service requirements.Product resin EW value is between 900 ~ 1300, can obtain the particulate state perfluorinated sulfonic acid catalyzer of porous through aftertreatment.
Detailed Description Of The Invention
A preparation method for catalyzer porous perfluorinated sulfonic resin, comprises the steps:
(1) mixed with dispersion medium by pore-creating agent, the mass ratio of pore-creating agent and dispersion medium is 1:(2 ~ 32), temperature be 80 ~ 150 DEG C, constant temperature 2 ~ 8 hours under the condition of pressure 0.1 ~ 1.0MPa, obtained pore-creating agent dispersion liquid;
(2) mixed with perfluor sulfonyl vinyl ether, solvent, initiator by the pore-creating agent dispersion liquid that step (1) is obtained, the mass ratio of pore-creating agent dispersion liquid, perfluor sulfonyl vinyl ether, solvent, initiator is (1 ~ 20): (3 ~ 19): (0 ~ 14): (2 × 10
-5~ 2 × 10
-4), passing into tetrafluoroethylene maintenance reaction pressure is 200 ~ 2000kpa, is under the condition of 10 ~ 80 DEG C in temperature of reaction, polyreaction 1 ~ 8 hour, obtained polymkeric substance feed liquid;
(3) in the obtained polymkeric substance feed liquid of step (2), add deionized water and dispersion agent, be heated to 90 ~ 100 DEG C, stir distillation 1 ~ 4 hour, after filtration, obtained resin particle;
(4) resin particle step (3) obtained, after vacuum-drying, immerses in extraction agent, under the condition of 80 ~ 90 DEG C, extracts 7 ~ 9 hours, then drying, transition, obtained catalyzer porous perfluorinated sulfonic resin.
Perforating agent in described step (1) is EW value 700 ~ 950g/mol, molecular weight be not more than 150,000 perfluorinated sulfonic resin, structural formula is:
Wherein, m=0 ~ 2, n=1 ~ 4, x, y are positive integer.
Dispersion medium in described step (1) is one or more the mixture in perfluoro alkane, fluorochlorohydrocarbon, perfluoro-cyclicether, perfluor ethers, perfluorinated esters class; Be preferably: perfluoro-2-methyl cyclobutane, perflexane, Freon 113 and/or difluoro tetrachloroethane.
The solution solid content of the pore-creating agent dispersion liquid in described step (1) is 1 ~ 50wt%.
Solvent in described step (2) is one or more the mixture in perfluoro alkane, perfluoro-cyclicether and/or fluorochlorohydrocarbon; Preferably, the boiling point of described solvent is 10 ~ 200 DEG C; Preferred further, the boiling point of described solvent is 30 ~ 80 DEG C; Preferably, described solvent is one or more the mixture in Freon 113, C2Cl4F2, perfluoro-2-methyl cyclobutane, PF 5070, perflexane.
Initiator in described step (2) is perfluoroalkyl superoxide, organo-peroxide or azo-initiator; Preferably, initiator is two (perfluor-2-propoxy-propionyl) superoxide, dibenzoyl peroxide, Diisopropyl azodicarboxylate.
Perfluor sulfonyl vinyl ether structure formula in described step (2) is:
Wherein: a=0 ~ 3, b=1 ~ 4.
Deionized water consumption in described step (3) is 1 ~ 10 times of polymkeric substance feed liquid weight.
Dispersion agent in described step (3) is the polyvinyl alcohol of viscosity 44 ~ 52 centipoise, Walocel MT 20.000PV, magnesiumcarbonate, calcium carbonate, talcum powder, Perfluorocaprylic Acid or Sodium dodecylbenzene sulfonate.The consumption of dispersion agent is 0 ~ 5wt% of polymkeric substance feed liquid weight.
Stirring velocity in described step (3) is 30 ~ 300r/min.
The extraction agent of described step (4) is one or more the mixture in perfluoro alkane, fluorochlorohydrocarbon or perfluoro-cyclicether; Preferably, one or more the mixture in Freon 113, C2Cl4F2, perfluoro-2-methyl cyclobutane, PF 5070 or perflexane.
Obtained catalyzer through transition, can obtain catalyzer strong acid type porous ion-exchange resin with porous perfluorinated sulfonic resin.
Above-mentioned processing condition if no special instructions, all can adopt this area routine techniques, and mentioned reagent all can adopt this area common method synthesis or market to buy if no special instructions and obtain.
Beneficial effect
1, the present invention adopts low molal weight, low-molecular-weight perfluorinated sulfonic resin as pore-creating agent, it can be dispersed in polymerization liquid well, and have good consistency between pore-creating agent and product resin, the hole obtained after can making extraction is evenly distributed on resin particle inside.Simultaneously because perforating agent is the linear macromolecule of perfluor, free radical in polymerization process can not be caused to cause to macromolecular chain tra nsfer polymericular weight to decline, distribute the phenomenon such as wide.
2, adopt method of the present invention to obtain uniform particle sizes, sizeable polymer globules, a small amount of dispersion agent of introducing can not pollute and reclaim solution and unreacted perfluor sulfonyl fluorine monomer.The a small amount of dispersion agent carried secretly in the polymer can be removed by follow-up transition and water washing process, can not impact the use of resin.
3, the method for the invention operational condition is simple, do not need High Temperature High Pressure, the problem of the loss of effective catalyst component in the use procedure overcome is difficult in technology before solving, add the work-ing life of catalyzer, simultaneously because the existence of vesicular structure makes specific surface area increase, active ingredient utilization ratio improves.
4, the pore-creating agent used in the present invention can recycle, and can not cause the raising of preparation cost.
Embodiment
Now, in conjunction with following embodiment, the present invention is described in further detail, but the present invention is not limited to these embodiments.
In the following embodiments, except as otherwise noted, all percentage ratio is weight percentage.Adopt the EW value of determination of acid-basetitration product in the present invention, adopt fusion index instrument to measure the melting index of product, adopt scanning electron microscope to measure pore size, adopt method of sieving determination size.Adopt the heat decomposition temperature of thermal weight loss methods analyst product.
Raw material sources
The A of pore-creating agent described in embodiment, Ew are 870, and molecular weight is 100,000, and structural formula is as follows:
The preparation method of pore-creating agent A:
In the reactor of 1L, at room temperature add the perfluor sulfonyl vinyl ether (LSPSVE) of 150g, 650g water (wherein containing ammonium perfluorocaprylate 2g), 50g buffer reagent is (wherein containing 1g potassium hydrogen phosphate, 0.5g potassium primary phosphate) find time to replace until oxygen level is less than 10ppm in reactor, be warming up to 65 DEG C, in reactor, pass into TFE(tetrafluoroethylene) to pressure be 0.15MPa, ammonium persulfate aqueous solution 50g (ammonium persulphate mass percentage is 3%) is added in reactor, maintain constant reaction pressure, react 2 hours, cooling, releases material.High-speed stirring makes material breakdown of emulsion, with deionized water wash 3 ~ 5 times, dries and obtains pore-creating agent.This pore-creating agent after tested, Ew is 870, and molecular weight is 100,000.
Described perfluor sulfonyl vinyl ether LSPSVE structural formula is:
E.I.Du Pont Company, Shandong Huaxia Shenzhou New Material Co., Ltd. are all on sale.
The B of pore-creating agent described in embodiment, Ew are 660, and molecular weight is 130,000, and structural formula is as follows:
The preparation method of pore-creating agent B:
In the reactor of 1L, at room temperature add the perfluor sulfonyl vinyl ether (SSPSVE) of 130g, 650g water (wherein containing ammonium perfluorocaprylate 2g), 50g buffer reagent is (wherein containing 1g potassium hydrogen phosphate, 0.5g potassium primary phosphate), find time to replace until oxygen level is less than 10ppm in reactor, be warming up to 65 DEG C, in reactor, pass into TFE(tetrafluoroethylene) to pressure be 0.35MPa, ammonium persulfate aqueous solution 50g (ammonium persulphate mass percentage is 3%) is added in reactor, maintain constant reaction pressure, react 2 hours, cooling, release material.High-speed stirring makes material breakdown of emulsion, with deionized water wash 3 ~ 5 times, dries and obtains pore-creating agent.This pore-creating agent after tested, Ew is 660, and molecular weight is 130,000.
The structural formula of described perfluor sulfonyl vinyl ether SSPSVE is:
DOW Chemical (Dow) company, Shandong Huaxia Shenzhou New Material Co., Ltd. are all on sale.
Other reagent is common commercially available prod.
Embodiment 1
A preparation method for catalyzer porous perfluorinated sulfonic resin, comprises the steps:
(1) get the PF 5070 of 125g, the pore-creating agent A of 25g adds in 300ml autoclave, is heated with stirring to 120 DEG C in oil bath, and constant temperature 1 hour, is cooled to room temperature, obtains the water white transparency pore-creating agent A dispersion liquid that solid content is 17wt%;
(2) in 2L stainless steel cauldron, add 450g perfluor sulfonyl vinyl ether (LSPSVE) under room temperature, add 150g pore-creating agent A dispersion liquid and 1g peroxy dicarbonate isopropyl ester, add 900g PF 5070.Replace with TFE again with after nitrogen replacement, then pass into TFE(tetrafluoroethylene) pressurization, be warming up to 70 DEG C, pressure regulation, make TFE pressure remain on 650kpa, react after 1.5 hours and cool, exhaust discharging, obtained polymkeric substance feed liquid;
(3) in the polymkeric substance feed liquid obtained, 4000g water is added, 100ml mass percentage is the polyvinyl alcohol solution of 3%, join in the round-bottomed flask of 10L, low whipping speed is under the condition of 60r/min, adds thermal distillation, and temperature is warming up to 100 DEG C from 65 DEG C, solvent in polymkeric substance feed liquid is all steamed, stop stirring, the resin particle obtained swims in water, filters and obtains resin particle;
(4) resin particle obtained is put into Rotary Evaporators, temperature 180 DEG C, under the condition of vacuum tightness-0.098Mpa, the unreacted perfluor sulfonyl vinyl ether of further recovery, then in apparatus,Soxhlet's, perforating agent is extracted as extraction agent using PF 5070, constant temperature 85 DEG C, 8 hours.By the resin that obtains in air dry oven, 100 DEG C of dryings 2 hours.Obtain 143g white globules, be porous perfluorinated sulfonic resin.Particle diameter is 0.3 ~ 1.0mm, and pore size is 10 ~ 3000nm, and resin EW value is 1050g/mol, and melting index is 3g/10min, and (test condition is 250 DEG C, 2.16kg), heat decomposition temperature is 380 DEG C.
Last handling process: the NaOH aqueous solution obtained porous perfluorinated sulfonic resin being placed in 20wt%, 80 DEG C of heating 8 hours, exchange 10 hours with 5wt%HCl, use deionized water wash afterwards, obtaining can as the porous perfluorosulfonic acid ion exchange resin particle of strong solid acid catalyst.
Embodiment 2
Preparation method as described in Example 1; difference is; 8g mass concentration is used to be that two (perfluor-2-propoxy-propionyl) peroxide solutions (solvent is perfluoro-2-methyl cyclobutane) of 10% are as initiator; temperature of reaction is 25 DEG C; reaction pressure is 300kpa; react after 1.5 hours, exhaust, discharging.
Last handling process is as embodiment 1, and by testing the EW value of the product obtained for 900g/mol, melting index is 15g/10min, and heat decomposition temperature is 340 DEG C, and size is 0.5 ~ 1.5mm, and pore size is 5 ~ 2000nm.
Embodiment 3-5
Preparation method as described in Example 1, difference is, the consumption of the pore-creating agent A of use is respectively 10g, 15g, 20g.The results are shown in Table 1 for the analytical test of embodiment 1 and 3-5
The proterties of product under the different perforating agent condition of table 1
| Pore-creating agent (g) | Outward appearance | EW value | Melting index | Decomposition temperature DEG C | |
| Embodiment 1 | 25 | White globules | 998 | 7 | 380 |
| Embodiment 3 | 10 | Transparent beads | 1150 | 2.3 | 394 |
| Embodiment 4 | 15 | Translucent bead | 1110 | 2.7 | 388 |
| Embodiment 5 | 20 | White globules | 1050 | 3 | 380 |
Embodiment 6-8
Select pore-creating agent A dispersion liquid obtained in embodiment 1.
In 2L stainless steel cauldron, 250g perfluor sulfonyl vinyl ether (LSPSVE) is added under room temperature; (wherein solvent is Freon 113 to peroxide solutions to add 150g pore-creating agent A dispersion liquid and 8g bis-(perfluor-2-propoxy-propionyl); peroxide concentrations is 5wt%), add 900g Freon 113.Replace with TFE again with after nitrogen replacement, then pass into TFE pressurization, be warming up to 29 DEG C, pressure regulation, make TFE pressure remain on 320kpa, react after 1.5 hours and cool, exhaust discharging, obtained polymkeric substance feed liquid;
In polymkeric substance feed liquid, add 3000g water, the 6wt% hydroxyethyl cellulose aqueous solution of 20g, be 45 revs/min at mixing speed respectively, 55 revs/min, process under the condition of 65 revs/min, other treatment steps are identical with embodiment 1.The resin particle size obtained has significant difference, and other indexs are identical, melting index 15, EW value 952, decomposition temperature 351 DEG C, and outward appearance is white globules, and in embodiment 6-8, the median size of bead is as shown in table 2.
Table 2
| Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Mixing speed | 45 revs/min | 55 revs/min | 65 revs/min |
| Particle diameter mm | 1.75 | 1.4 | 1.15 |
Embodiment 9
Preparation method as described in Example 8, difference is, adds the water of 2000g in polymkeric substance feed liquid, be 80 revs/min at mixing speed, temperature is warming up to 100 DEG C by 50 DEG C, the solvent in recovered material, when temperature is increased to 100 DEG C, stops stirring, filter and obtain resin particle.
Resin particle is placed in Rotary drying instrument, temperature 180 DEG C, dry further under the condition of vacuum tightness-0.098MPa, until do not have liquid to flow out.Take out resin particle and be placed in 500ml autoclave, add 300ml Freon 113, be heated to 80 DEG C of constant temperature 1 hour, cooling, obtained catalyzer porous perfluorinated sulfonic resin.
Test resin indices is as follows: melting index 11g/10min, resin EW value is 1050g/mol.Obtain the NaOH aqueous solution that resin particle is placed in 20%, 80 DEG C of heating 8 hours, exchange 10 hours with 5%HCl, use deionized water wash afterwards, obtaining can as the porous perfluorosulfonic acid ion exchange resin particle of strong solid acid catalyst.Passing through its size of test is 0.1 ~ 2mm, and resin mesoporous size is 2 ~ 1000nm.
Embodiment 10
Get the perfluoro-2-methyl cyclobutane of 90g, the pore-creating agent B of 60g adds in 300ml autoclave, is heated to 120 DEG C in oil bath, and constant temperature 1 hour, is cooled to room temperature, obtains the water white transparency pore-creating agent B dispersion liquid that solid content is 40wt%.
The preparation of porous catalyst
In 2L stainless steel cauldron, add 450g perfluor sulfonyl vinyl ether (LSPSVE) under room temperature, add 150g pore-creating agent B dispersion liquid and 900g perfluoro-2-methyl cyclobutane.With nitrogen replacement until in reactor oxygen level be less than 10ppm; 40 DEG C are warming up to reactor; then pass into TFE(tetrafluoroethylene) to reacting kettle inner pressure be 0.35MPa; in reactor, add the Freon 113 solution (mass percentage concentration is 3.5%) of 30g bis-(perfluor-2-propoxy-propionyl) superoxide, constantly pass into tetrafluoroethylene monomer in reaction process and maintain constant reaction pressure.React after 1.5 hours and cool, exhaust discharging, obtained polymkeric substance feed liquid.
The polymkeric substance feed liquid that 1750g obtains is added in the round-bottomed flask of 10L, 4000g water, 30g perfluoro ammonium caprylate aqueous solution (mass percentage is 5%), low whipping speed is under the condition of 80r/min, adds thermal distillation, and temperature is warming up to 100 DEG C from 65 DEG C, solvent in polymkeric substance feed liquid is all steamed, stop stirring, the resin particle obtained swims in water, filters and obtains resin particle;
The resin particle obtained is put into Rotary Evaporators, temperature 180 DEG C, under the condition of vacuum tightness-0.098Mpa, reclaims unreacted perfluor sulfonyl vinyl ether (LSPSVE) further and obtain dry polymer beads.This particle 98g is placed in 300ml autoclave and adds 150g perfluoro-2-methyl cyclobutane, be heated to 120 DEG C, constant temperature 1 hour, leaches resin particle, by the resin particle that obtains in air dry oven, and 100 DEG C of dryings 2 hours.The dry resin particle obtained can obtain the porous perfluorosulfonic acid ion exchange resin used as strong solid acid catalyst after transition.Its size is 0.3 ~ 1.1mm, and pore size is 20 ~ 800nm, IEC=0.98mmol/g, and heat decomposition temperature is 320 DEG C.
Embodiment 11
As described in Example 10, difference is, the preparation process of porous catalyst is as follows:
In 2L stainless steel cauldron, add 400g perfluor sulfonyl vinyl ether (SSPSVE) under room temperature, add 150g pore-creating agent B dispersion liquid and 900g Freon 113.With nitrogen replacement until in reactor oxygen level be less than 10ppm; 40 DEG C are warming up to reactor; then TFE(tetrafluoroethylene is passed into) make reacting kettle inner pressure remain 0.65MPa; the Freon 113 solution (mass percentage concentration is 3.5%) of 30g bis-(perfluor-2-propoxy-propionyl) superoxide is added in reactor; start reaction, constantly add tetrafluoroethylene monomer in reaction process and maintain constant reaction pressure at 0.65MPa.React after 1.5 hours and cool, exhaust discharging, obtained polymkeric substance feed liquid.
Obtained porous perfluorosulfonic acid ion exchange resin size is 0.2-1.1mm, and aperture is 2-800nm, IEC=1.35mmol/g, and decomposition temperature is 335 DEG C.
Application examples:
Application perfluorinated sulfonic resin catalyzer carries out esterification.
Reflux exchanger is being housed, in the 250ml there-necked flask of water trap and agitator, add 3g perfluorinated sulfonic resin catalyzer (preparing in embodiment 1), 1mol Glacial acetic acid and 1.04mol alcohol, reflux, treat that point aquifer yield is calculated value, when backflow reaches the boiling point of ester, continuation insulation 1 hour, reaction terminates, filter, filtrate is crude product, analyzes ester content.Isolated catalyst recirculation is reacted next time, and the productive rate of record ester, result is as shown in table 3.
Table 3
| Esterification products | 1 productive rate | 2 productive rates | 3 productive rates | 4 productive rates | 5 productive rates |
| Ritalin | 60.3 | 62.4 | 60.6 | 64.1 | 61.1 |
| Vinyl acetic monomer | 58.2 | 61.2 | 62.1 | 58.1 | 59.3 |
| Propyl acetate | 71.1 | 70.6 | 73.4 | 72.3 | 71.9 |
| N-BUTYL ACETATE | 93 | 92.6 | 93.8 | 91.7 | 92.8 |
| Isobutyl acetate | 99.1 | 98.7 | 97.9 | 96.2 | 97.6 |
Interpretation of result
As can be seen from table 3 data, after adopting perfluorinated sulfonic resin catalyzer of the present invention to reuse through 5 times, catalytic efficiency can not decline, and illustrates that the present invention can overcome the problem of catalyzer active principle loss in prior art and the problem of active principle utilization ratio reduction.
Claims (10)
1. a catalyzer preparation method for porous perfluorinated sulfonic resin, is characterized in that, comprise the steps:
(1) mixed with dispersion medium by pore-creating agent, the mass ratio of pore-creating agent and dispersion medium is 1:(2 ~ 32), temperature be 80 ~ 150 DEG C, constant temperature 2 ~ 8 hours under the condition of pressure 0.1 ~ 1.0MPa, obtained pore-creating agent dispersion liquid;
(2) mixed with perfluor sulfonyl vinyl ether, solvent, initiator by the pore-creating agent dispersion liquid that step (1) is obtained, the mass ratio of pore-creating agent dispersion liquid, perfluor sulfonyl vinyl ether, solvent, initiator is (1 ~ 20): (3 ~ 19): (0 ~ 14): (2 × 10
-5~ 2 × 10
-4), passing into tetrafluoroethylene maintenance reaction pressure is 200 ~ 2000kpa, is under the condition of 10 ~ 80 DEG C in temperature of reaction, polyreaction 1 ~ 8 hour, obtained polymkeric substance feed liquid;
(3) in the obtained polymkeric substance feed liquid of step (2), add deionized water and dispersion agent, be heated to 90 ~ 100 DEG C, stir distillation 1 ~ 4 hour, after filtration, obtained resin particle;
(4) resin particle step (3) obtained, after vacuum-drying, immerses in extraction agent, under the condition of 80 ~ 90 DEG C, extracts 7 ~ 9 hours, then drying, transition, obtained catalyzer porous perfluorinated sulfonic resin;
Perforating agent in described step (1) is EW value 700 ~ 950g/mol, molecular weight be not more than 150,000 perfluorinated sulfonic resin, structural formula is:
Wherein, m=0 ~ 2, n=1 ~ 4, x, y are positive integer.
2. preparation method as claimed in claim 1, it is characterized in that, the dispersion medium in described step (1) is one or more the mixture in perfluoro alkane, fluorochlorohydrocarbon, perfluoro-cyclicether, perfluor ethers, perfluorinated esters class; Be preferably: perfluoro-2-methyl cyclobutane, perflexane, Freon 113 and/or difluoro tetrachloroethane.
3. preparation method as claimed in claim 1, it is characterized in that, the solution solid content of the pore-creating agent dispersion liquid in described step (1) is 1 ~ 50wt%.
4. preparation method as claimed in claim 1, it is characterized in that, the solvent in described step (2) is one or more the mixture in perfluoro alkane, perfluoro-cyclicether and/or fluorochlorohydrocarbon; Preferably, the boiling point of described solvent is 10 ~ 200 DEG C; Preferred further, the boiling point of described solvent is 30 ~ 80 DEG C; Preferably, described solvent is one or more the mixture in Freon 113, C2Cl4F2, perfluoro-2-methyl cyclobutane, PF 5070, perflexane.
5. preparation method as claimed in claim 1, it is characterized in that, the initiator in described step (2) is perfluoroalkyl superoxide, organo-peroxide or azo-initiator; Preferably, initiator is two (perfluor-2-propoxy-propionyl) superoxide, dibenzoyl peroxide, Diisopropyl azodicarboxylate.
6. preparation method as claimed in claim 1, it is characterized in that, the perfluor sulfonyl vinyl ether structure formula in described step (2) is:
Wherein: a=0 ~ 3, b=1 ~ 4.
7. preparation method as claimed in claim 1, it is characterized in that, the deionized water consumption in described step (3) is 1 ~ 10 times of polymkeric substance feed liquid weight.
8. preparation method as claimed in claim 1, is characterized in that, the dispersion agent in described step (3) is the polyvinyl alcohol of viscosity 44 ~ 52 centipoise, Walocel MT 20.000PV, magnesiumcarbonate, calcium carbonate, talcum powder, Perfluorocaprylic Acid or Sodium dodecylbenzene sulfonate.The consumption of dispersion agent is 0 ~ 5wt% of polymkeric substance feed liquid weight.
9. preparation method as claimed in claim 1, it is characterized in that, the stirring velocity in described step (3) is 30 ~ 300r/min.
10. preparation method as claimed in claim 1, it is characterized in that, the extraction agent of described step (4) is one or more the mixture in perfluoro alkane, fluorochlorohydrocarbon or perfluoro-cyclicether; Preferably, one or more the mixture in Freon 113, C2Cl4F2, perfluoro-2-methyl cyclobutane, PF 5070 or perflexane.
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| CN106925347A (en) * | 2015-12-29 | 2017-07-07 | 山东华夏神舟新材料有限公司 | The preparation method of porous perfluorinated sulfonic resin catalyst |
| CN107311868A (en) * | 2017-06-23 | 2017-11-03 | 北京理工大学 | A kind of method for preparing p-tert-butyl benzoic acid methyl esters |
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