CN104774284B - 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 catalyst preparation method of porous perfluorinated sulfonic resin, particularly relate to a kind of with
The method that low polymer synthesizes perfluorinated sulfonic resin class porous strongly acidic cation-exchange catalyst for pore-foaming agent.
Background technology
Prepare after perfluorinated sulfonic resin from nineteen sixties du pont company scientist connolly etc., its work
For fuel cell membranes, chlorine industry electrolytic experiment barrier film, solid polymer electrolyte etc. are widely used.Find simultaneously
Its as solid super acid catalyst in organic synthesis, such as alkylation, acylation, nitrification, sulfonation, phosphorylated, polymerization, condensation,
Etherificate, esterification, aquation and rearrangement reaction all have good catalytic action.Perfluorinated sulfonic resin and liquid acid catalytic phase ratio, tool
Have the advantages that non-corrosiveness, do not produce that acid pickle, product be easily separated, selectivity is high and can multiple Reusability, and typically solid
Body acid ratio, has that yield is high, and reaction condition relaxes, the advantage such as reaction speed is fast, compared with other acid cation exchange resins,
The features such as have stronger acidity, use temperature high, is a kind of highly desirable solid acid catalyst.Increase as a kind of catalyst
Plus specific surface area and raising can be to improve important measures of catalysis potentiality using the ratio in acid site.
The main method preparing azochlorosulfonate acid resin catalyst at present has following several 1, is finely divided perfluorinated sulfonic resin
Cut, this kind of method can increase its surface area.But can be clogged simultaneously by the polymer of fine segmentation in catalyst continuous processing
Hinder flowing.2nd, Selwyn Lloyd etc. proposes sulfonate resin and high-pressure fluid such as co in cn13378912Or so2Contact, carries out molten
Swollen, then this polymer is heated to more than softening point, explosive decompression, make gas " escape " from swelling polymer out thus
Polymer is made to be expanded to loose structure.This kind of preparation method needs higher operating pressure.3rd, support type perfluorinated sulfonic resin,
Describing conventional inorganic carrier in patent us4038213, patent us4661411 has al2o3、alf3、zro2、sio2Deng,
Butt employs the carrier such as polytetrafluoroethylene (PTFE), polytetrafluoroethylene (PTFE) and hexafluoro third with hydrophobic surface in patent us5094995
Alkene copolymer, polyethylene, polypropylene, petroleum coke etc. prepare perfluorinated sulfonic resin catalyst as carrier.The master of supported catalyst
Preparation method is wanted to have infusion process, dipping circumfluence method, dipping steam seasoning, prepared specific surface area of catalyst significantly increases, acidic site
Easily close by reactant institute, but active principle is easy to run off during the course of the reaction.4th, sol-gal process support type perfluorinated sulfonic resin,
Sulfonate resin solution is contacted with silicate solutions, makes silicate form sio2Network structure, obtains porous nano compound, should
Plant the loss that preparation method decreases active principle to a certain extent, increased catalysis activity simultaneously.Sol-gal process and negative
Load method equally needs to prepare the water-alcohol solution of sulfonate resin, for the perfluorinated sulfonic resin of the very poor HMW of dissolubility,
This process undoubtedly increases the preparation difficulty of catalyst, and both preparation methods also cannot fundamentally solve active principle and run off
Problem, cause the decline of catalyst service life.
Content of the invention
The present invention is directed to the deficiencies in the prior art, provides a kind of preparation method of catalyst porous perfluorinated sulfonic resin.
Term explanation
Ew value: also referred to as molal weight, when carrying out equivalent exchange to the corresponding ion of 1mol in extraneous solution, required is dry
Weight resin.Unit is g/mol, and the relation with exchange capacity is: ew=1000/iec.
Summary of the invention
The present invention adopts low molal weight, low-molecular-weight perfluorinated sulfonic resin as pore-foaming agent, by perfluor sulfonyl vinyl
Ether and tetrafluoroethene carry out combined polymerization, obtain the perfluor sulfonyl fluororesin meeting use requirement.Product resin ew value for 900～
The graininess perfluorinated sulfonic acid catalyst of porous between 1300, can be obtained through post processing.
Detailed Description Of The Invention
A kind of catalyst preparation method of porous perfluorinated sulfonic resin, comprises the steps:
(1) pore-foaming agent is mixed with decentralized medium, pore-foaming agent is 1:(2～32 with the mass ratio of decentralized medium), in temperature
For constant temperature under conditions of 80～150 DEG C, pressure 0.1～1.0mpa 2～8 hours, prepared pore agent dispersing liquid；
(2) the pore agent dispersing liquid that step (1) is obtained is mixed with perfluor sulfonyl vinyl ethers, solvent, initiator, pore
Agent dispersing liquid, perfluor sulfonyl vinyl ethers, solvent, the mass ratio of initiator are (1～20): (3～19): (0～14): (2 ×
10-5～2 × 10-4), being passed through tetrafluoroethene and maintaining reaction pressure is 200～2000kpa, the bar being 10～80 DEG C in reaction temperature
Under part, polymerisation 1～8 hour, prepared polymer feed liquid；
(3) add deionized water and dispersant in the polymer feed liquid being obtained to step (2), be heated to 90～100 DEG C, stir
Mix distillation 1～4 hour, through filtering, prepared resin particle；
(4) after will be vacuum dried for the prepared resin particle of step (3), in immersion extractant, in 80～90 DEG C of condition
Lower extraction 7～9 hours, then drying, transition, prepared catalyst porous perfluorinated sulfonic resin.
Perforating agent in described step (1) is ew value 700～950g/mol, the perfluorinated sulfonic acid tree of molecular weight no more than 150,000
Fat, structural formula is:
Wherein, m=0～2, n=1～4, x, y are positive integer.
Decentralized medium in described step (1) is perfluoro alkane, fluorochlorohydrocarbon, perfluoro-cyclicether, perfluor ethers, in perfluor esters
One or more mixture；It is preferably: perfluoro-2-methyl cyclobutane, perflexane, trifluorotrichloroethane and/or two
Fluorine tetrachloroethanes.
The solution solid content of the pore agent dispersing liquid in described step (1) is 1～50wt%.
Solvent in described step (2) is one of perfluoro alkane, perfluoro-cyclicether and/or fluorochlorohydrocarbon or two or more
Mixture；Preferably, the boiling point of described solvent is 10～200 DEG C；It is further preferred that the boiling point of described solvent is 30～80
℃；Preferably, described solvent is trifluorotrichloroethane, tetrachlorodifluoroethane, perfluoro-2-methyl cyclobutane, PF 5070, perfluor
One of hexane or two or more mixtures.
Initiator in described step (2) is perfluoroalkyl peroxide, organic peroxide or azo-initiator；Excellent
Choosing, initiator is two (perfluor -2- propoxyl group propiono) peroxide, dibenzoyl peroxide, azodiisobutyronitrile.
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 polymer feed liquid weight.
Dispersant in described step (3) is the polyvinyl alcohol of viscosity 44～52 centipoise, hydroxymethyl cellulose, magnesium carbonate,
Calcium carbonate, talcum powder, perfluoro caprylic acid or neopelex.The consumption of dispersant be polymer feed liquid weight 0～
5wt%.
Mixing speed in described step (3) is 30～300r/min.
The extractant of described step (4) is one of perfluoro alkane, fluorochlorohydrocarbon or perfluoro-cyclicether or two or more mixing
Compound；Preferably, in trifluorotrichloroethane, tetrachlorodifluoroethane, perfluoro-2-methyl cyclobutane, PF 5070 or perflexane
One or more mixture.
Prepared catalyst porous perfluorinated sulfonic resin is through transition, you can obtain catalyst strong-acid type porous ion
Exchanger resin.
Above-mentioned process conditions if no special instructions, all can adopt this area routine techniques, mentioned reagent is if no special instructions
All can buy and obtain using method synthesis commonly used in the art or market.
Beneficial effect
1st, the present invention adopts low molal weight, the perfluorinated sulfonic resin of low-molecular-weight as pore-foaming agent, and it can be well
It is dispersed in polymerization liquid, and there is between pore-foaming agent and product resin good compatibility, obtain after extraction can be made
Hole be evenly distributed on inside resin particle.Simultaneously because perforating agent is the linear macromolecule of perfluor, do not result in polymerization process
The chain tra nsfer of middle free basal orientation macromolecular and lead to polymer molecular weight to decline, the distribution phenomenon such as wide.
2nd, uniform particle sizes can be obtained using method of the present invention, sizeable polymer globules, the lacking of introducing
Amount dispersant will not pollute recovery solution and unreacted perfluor sulfonyl fluorine monomer.The a small amount of dispersant carried secretly in the polymer is permissible
Removed by follow-up transition and water-washing process, the use of resin will not be impacted.
3rd, the method for the invention operating condition, simply it is not necessary to HTHP, is difficult in technology before solving overcome
Use during the effective loss of catalyst component problem, increased the service life of catalyst, simultaneously because loose structure
Presence make specific surface area increase, active component utilization rate improve.
4th, used in the present invention, pore-foaming agent can recycle, and does not result in the raising of preparation cost.
Specific embodiment
Now, in conjunction with following embodiments, the present invention is described in further detail, but the present invention is not limited to these enforcements
Example.
In the following embodiments, outer unless otherwise stated, all of percentage is percetage by weight.Adopt in the present invention
With the ew value of determination of acid-basetitration product, measure the melt index of product using fusion index instrument, measured using ESEM
Pore size, determines particle size using sieve method.Heat decomposition temperature using thermal weight loss method assay products.
Raw material sources
Pore-foaming agent a described in embodiment, ew are 870, and molecular weight is 100,000, and structural formula is as follows:
The preparation method of pore-foaming agent a:
Add the perfluor sulfonyl vinyl ethers (lspsve) of 150g at room temperature in the reactor of 1l, 650g water is (wherein
Containing perfluorooctanoic acid 2g), 50g buffer (wherein containing 1g potassium hydrogen phosphate, 0.5g potassium dihydrogen phosphate) evacuates displacement up to instead
Answer in kettle oxygen content to be less than 10ppm, be warming up to 65 DEG C, be passed through tfe(tetrafluoroethene into reactor) to pressure be 0.15mpa,
Add ammonium persulfate aqueous solution 50g (ammonium persulfate weight/mass percentage composition is 3%) into reactor, maintain constant reaction pressure, instead
Answer 2 hours, cooling, release material.High-speed stirred makes material breakdown of emulsion, is washed with deionized 3～5 times, dries and obtains pore-foaming agent.
This pore-foaming agent after tested, ew is 870, and molecular weight is 100,000.
Described perfluor sulfonyl vinyl ethers lspsve structural formula is:
E.I.Du Pont Company, Shandong Huaxia Shenzhou New Material Co., Ltd. are all on sale.
Pore-foaming agent b described in embodiment, ew are 660, and molecular weight is 130,000, and structural formula is as follows:
The preparation method of pore-foaming agent b:
Add the perfluor sulfonyl vinyl ethers (sspsve) of 130g at room temperature in the reactor of 1l, 650g water is (wherein
Containing perfluorooctanoic acid 2g), 50g buffer (wherein contains 1g potassium hydrogen phosphate, 0.5g potassium dihydrogen phosphate), evacuates displacement up to instead
Answer in kettle oxygen content to be less than 10ppm, be warming up to 65 DEG C, be passed through tfe(tetrafluoroethene into reactor) to pressure be 0.35mpa,
Add ammonium persulfate aqueous solution 50g (ammonium persulfate weight/mass percentage composition is 3%) into reactor, maintain constant reaction pressure, instead
Answer 2 hours, cooling, release material.High-speed stirred makes material breakdown of emulsion, is washed with deionized 3～5 times, dries and obtains pore-foaming agent.
This pore-foaming agent after tested, ew is 660, and molecular weight is 130,000.
The structural formula of described perfluor sulfonyl vinyl ethers sspsve is:
DOW Chemical (dow) company, Shandong Huaxia Shenzhou New Material Co., Ltd. are all on sale.
Other reagent are ordinary commercial products.
Embodiment 1
A kind of catalyst preparation method of porous perfluorinated sulfonic resin, comprises the steps:
(1) take the PF 5070 of 125g, the pore-foaming agent a of 25g adds in 300ml autoclave, and stirring in oil bath adds
Heat to 120 DEG C, constant temperature 1 hour, be cooled to room temperature, obtain solid content be 17wt% water white transparency pore-foaming agent a dispersion liquid；
(2) add 450g perfluor sulfonyl vinyl ethers (lspsve) in 2l stainless steel cauldron under room temperature, add 150g
Pore-foaming agent a dispersion liquid and 1g peroxy dicarbonate isopropyl ester, add 900g PF 5070.With being replaced with tfe again after nitrogen displacement,
Then pass to tfe(tetrafluoroethene) pressurization, it is warming up to 70 DEG C, pressure regulation, make tfe pressure be maintained at 650kpa, after reacting 1.5 hours
Cooling, is vented discharging, prepared polymer feed liquid；
(3) in the polymer feed liquid obtaining add 4000g water, 100ml weight/mass percentage composition be 3% polyvinyl alcohol molten
Liquid, is added in the round-bottomed flask of 10l, under conditions of low whipping speed is 60r/min, heating distillation, and temperature heats up from 65 DEG C
To 100 DEG C, so that solvent in polymer feed liquid is all steamed, stop stirring, the resin particle obtaining swims in water, is filtrated to get
Resin particle；
(4) resin particle obtaining is put in Rotary Evaporators, in 180 DEG C of temperature, the condition of vacuum -0.098mpa
Under, reclaim unreacted perfluor sulfonyl vinyl ethers further, then using PF 5070 as extractant in apparatus,Soxhlet's
Extraction perforating agent, 85 DEG C of constant temperature, 8 hours.By the resin obtaining in air dry oven, 100 DEG C of dryings 2 hours.Obtain 143g
White globules, as porous perfluorinated sulfonic resin.Particle diameter is 0.3～1.0mm, and pore size is 10～3000nm, resin ew value
For 1050g/mol, melt index is 3g/10min, (test condition is 250 DEG C, 2.16kg), and heat decomposition temperature is 380 DEG C.
Last handling process: the porous perfluorinated sulfonic resin being obtained is placed in the naoh aqueous solution of 20wt%, heats at 80 DEG C
8 hours, exchanged 10 hours with 5wt%hcl, be washed with deionized afterwards, obtaining can be used as the porous of strong solid acid catalyst
Perfluorosulfonic acid ion exchanger resin particle.
Embodiment 2
Preparation method as described in Example 1, difference is, the two (perfluor -2- the use of 8g mass concentration being 10%
Propoxyl group propiono) as initiator, reaction temperature is 25 DEG C, instead to peroxide solutions (solvent is perfluoro-2-methyl cyclobutane)
Pressure is answered to be 300kpa, after reacting 1.5 hours, exhaust, discharging.
Last handling process such as embodiment 1, the ew value by the product obtained by test is 900g/mol, and melt index is
15g/10min, heat decomposition temperature is 340 DEG C, and particle 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 respectively 10g of the pore-foaming agent a of use,
15g、20g.The analysis test result of embodiment 1 and 3-5 is listed in Table 1 below
The proterties of product under the conditions of the different perforating agent of table 1
| Pore-foaming agent (g) | Outward appearance | Ew value | Melt 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
From the pore-foaming agent a dispersion liquid being obtained in embodiment 1.
Add 250g perfluor sulfonyl vinyl ethers (lspsve) in 2l stainless steel cauldron under room temperature, add 150g pore
(wherein solvent is trifluorotrichloroethane, peroxide for agent a dispersion liquid and 8g bis- (perfluor -2- propoxyl group propiono) peroxide solutions
Compound concentration is 5wt%), add 900g trifluorotrichloroethane.With being replaced with tfe again after nitrogen displacement, then pass to tfe pressurization,
It is warming up to 29 DEG C, pressure regulation, make tfe pressure be maintained at 320kpa, reaction cooled down after 1.5 hours, was vented discharging, prepared polymer material
Liquid；
Add 3000g water in polymer feed liquid, the 6wt% hydroxyethyl cellulose aqueous solution of 20g, respectively in speed of agitator
For 45 revs/min, 55 revs/min, process under conditions of 65 revs/min, other process steps are same as Example 1.Obtained
Resin particle size have significant difference, other indexs are identical, melt index 15, ew value 952,351 DEG C of decomposition temperature, and outward appearance is
White globules, in embodiment 6-8, the average grain diameter of bead is as shown in table 2.
Table 2
| Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Speed of agitator | 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, stirring in polymer feed liquid
Mix rotating speed is 80 revs/min, and 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,
Stop stirring, be filtrated to get resin particle.
Resin particle is placed in Rotary drying instrument, in 180 DEG C of temperature, under conditions of vacuum -0.098mpa further
It is dried, until not having liquid to flow out.Take out resin particle to be placed in 500ml autoclave, add 300ml trifluorotrichloroethane, plus
Heat is to 80 DEG C of constant temperature 1 hour, cooling, prepared catalyst porous perfluorinated sulfonic resin.
Test resin indices are as follows: melt index 11g/10min, resin ew value is 1050g/mol.Obtain resin
Grain is placed in the 20% naoh aqueous solution, heats 8 hours at 80 DEG C, is exchanged 10 hours with 5%hcl, is washed with deionized afterwards,
Obtaining can be used as the porous perfluorosulfonic acid ion exchanger resin particle of strong solid acid catalyst.Through testing its particle size it is
0.1～2mm, in resin, pore size is 2～1000nm.
Embodiment 10
Take the perfluoro-2-methyl cyclobutane of 90g, the pore-foaming agent b of 60g adds in 300ml autoclave, adds in oil bath
Heat to 120 DEG C, constant temperature 1 hour, be cooled to room temperature, obtain solid content be 40wt% water white transparency pore-foaming agent b dispersion liquid.
The preparation of porous catalyst
Add 450g perfluor sulfonyl vinyl ethers (lspsve) in 2l stainless steel cauldron under room temperature, add 150g pore
Agent b dispersion liquid and 900g perfluoro-2-methyl cyclobutane.It is less than 10ppm with nitrogen displacement up to oxygen content in reactor, to reaction
Kettle is warming up to 40 DEG C, then passes to tfe(tetrafluoroethene) to reacting kettle inner pressure be 0.35mpa, into reactor add 30g bis-
The trifluorotrichloroethane solution (mass percentage concentration is 3.5%) of (perfluor -2- propoxyl group propiono) peroxide, course of reaction
In be constantly passed through tetrafluoroethylene monomer maintain constant reaction pressure.Reaction cooled down after 1.5 hours, was vented discharging, prepared polymer
Feed liquid.
Add the polymer feed liquid that 1750g obtains, 4000g water in the round-bottomed flask of 10l, 30g perfluorooctanoic acid is water-soluble
Liquid (weight/mass percentage composition is 5%), under conditions of low whipping speed is 80r/min, heating distillation, temperature is warming up to 100 from 65 DEG C
DEG C, so that solvent in polymer feed liquid is all steamed, stop stirring, the resin particle obtaining swims in water, is filtrated to get resin
Particle；
The resin particle obtaining is put in Rotary Evaporators, in 180 DEG C of temperature, under conditions of vacuum -0.098mpa,
Reclaim the polymer beads that unreacted perfluor sulfonyl vinyl ethers (lspsve) obtains drying further.This particle 98g is put
Add 150g perfluoro-2-methyl cyclobutane in 300ml autoclave, be heated to 120 DEG C, constant temperature 1 hour, leach resin particle, will
The resin particle obtaining in air dry oven, 100 DEG C of dryings 2 hours.The dry resin particle obtaining can obtain after transition
To the porous perfluorosulfonic acid ion exchanger resin using as strong solid acid catalyst.Its particle size is 0.3～1.1mm, hole
Footpath 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:
Add 400g perfluor sulfonyl vinyl ethers (sspsve) in 2l stainless steel cauldron under room temperature, add 150g pore
Agent b dispersion liquid and 900g trifluorotrichloroethane.It is less than 10ppm with nitrogen displacement up to oxygen content in reactor, to reactor liter
Temperature, to 40 DEG C, then passes to tfe(tetrafluoroethene) make reacting kettle inner pressure remain 0.65mpa, add 30g bis- into reactor
The trifluorotrichloroethane solution (mass percentage concentration is 3.5%) of (perfluor -2- propoxyl group propiono) peroxide, starts to react,
It is continuously added tetrafluoroethylene monomer in course of reaction and maintain constant reaction pressure in 0.65mpa.Reaction cooled down after 1.5 hours, row
Gas discharging, prepared polymer feed liquid.
Prepared porous perfluorosulfonic acid ion exchanger resin particle size is 0.2-1.1mm, and aperture is 2-800nm, iec=
1.35mmol/g, decomposition temperature is 335 DEG C.
Application examples:
Application perfluorinated sulfonic resin catalyst carries out esterification.
Equipped with reflux condenser, in the 250ml there-necked flask of water knockout drum and agitator, add the catalysis of 3g perfluorinated sulfonic resin
Agent (preparation in embodiment 1), 1mol glacial acetic acid and 1.04mol alcohol, are heated to reflux, the water yield to be separated is calculated value, backflow
Reach ester boiling point when, continue insulation 1 hour, reaction terminates, filter, filtrate be crude product, analyze ester content.Isolate
Catalyst circulation carries out next secondary response, the yield of record ester, and result is as shown in table 3.
Table 3
| Esterification products | 1 yield | 2 yields | 3 yields | 4 yields | 5 yields |
| Methyl acetate | 60.3 | 62.4 | 60.6 | 64.1 | 61.1 |
| Ethyl acetate | 58.2 | 61.2 | 62.1 | 58.1 | 59.3 |
| Propyl acetate | 71.1 | 70.6 | 73.4 | 72.3 | 71.9 |
| 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
Be can be seen that after being reused through 5 times using perfluorinated sulfonic resin catalyst of the present invention by table 3 data,
Catalytic efficiency will not decline, and illustrates that the present invention can overcome the problem that in prior art, catalyst active principle runs off and active principle
The problem that utilization rate reduces.
Claims (16)
1. a kind of preparation method of catalyst porous perfluorinated sulfonic resin is it is characterised in that comprise the steps:
(1) pore-foaming agent is mixed with decentralized medium, pore-foaming agent is 1:(2～32 with the mass ratio of decentralized medium), it is 80 in temperature
～150 DEG C, constant temperature 2～8 hours, prepared pore agent dispersing liquid under conditions of pressure 0.1～1.0mpa；
(2) the pore agent dispersing liquid that step (1) is obtained is mixed with perfluor sulfonyl vinyl ethers, solvent, initiator, and pore-foaming agent divides
Dispersion liquid, perfluor sulfonyl vinyl ethers, solvent, the mass ratio of initiator are (1～20): (3～19): (0～14): (2 × 10-5~
2×10-4), being passed through tetrafluoroethene and maintaining reaction pressure is 200～2000kpa, under conditions of reaction temperature is 10～80 DEG C,
Polymerisation 1～8 hour, prepared polymer feed liquid；
(3) add deionized water and dispersant in the polymer feed liquid being obtained to step (2), be heated to 90～100 DEG C, stirring is steamed
Evaporate 1～4 hour, through filtering, prepared resin particle；
The consumption of dispersant is 0～5wt% of polymer feed liquid weight；
(4), after will be vacuum dried for the prepared resin particle of step (3), in immersion extractant, extract under conditions of 80～90 DEG C
Take 7～9 hours, then drying, transition, prepared catalyst porous perfluorinated sulfonic resin；
Perforating agent in described step (1) is ew value 700～950 g/mol, the perfluorinated sulfonic resin of molecular weight no more than 150,000,
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 characterised in that decentralized medium in described step (1) be perfluoro alkane,
One of fluorochlorohydrocarbon, perfluor ethers, perfluor esters or two or more mixtures.
3. preparation method as claimed in claim 2 is it is characterised in that the decentralized medium in described step (1) is perfluor diformazan
Basic ring butane, perflexane, trifluorotrichloroethane and/or difluoro tetrachloroethanes.
4. preparation method as claimed in claim 1 is it is characterised in that the solution of pore agent dispersing liquid in described step (1)
Solid content is 1～50wt%.
5. preparation method as claimed in claim 1 is it is characterised in that the solvent in described step (2) is perfluoro alkane, perfluor
One of cyclic ethers and/or fluorochlorohydrocarbon or two or more mixtures.
6. preparation method as claimed in claim 5 it is characterised in that solvent in described step (2) be trifluorotrichloroethane,
One of tetrachlorodifluoroethane, perfluoro-2-methyl cyclobutane, PF 5070, perflexane or two or more mixtures.
7. preparation method as claimed in claim 1 is it is characterised in that the boiling point of solvent in described step (2) is 10～200
℃.
8. preparation method as claimed in claim 7 is it is characterised in that the boiling point of solvent in described step (2) is 30～80
℃.
9. preparation method as claimed in claim 1 is it is characterised in that the initiator in described step (2) is perfluoroalkyl mistake
Oxide, organic peroxide or azo-initiator.
10. preparation method as claimed in claim 9 is it is characterised in that the initiator in described step (2) is two (perfluor -2-
Propoxyl group propiono) peroxide, dibenzoyl peroxide, azodiisobutyronitrile.
11. preparation methods as claimed in claim 1 are it is characterised in that the perfluor sulfonyl vinyl ethers in described step (2) is tied
Structure formula is:
Wherein: a=0～3, b=1～4.
12. preparation methods as claimed in claim 1 are it is characterised in that the deionized water consumption in described step (3) is polymerization
1～10 times of material liquid weight.
13. preparation methods as claimed in claim 1 are it is characterised in that the dispersant in described step (3) is viscosity 44～52
The polyvinyl alcohol of centipoise, hydroxymethyl cellulose, magnesium carbonate, calcium carbonate, talcum powder, perfluoro caprylic acid or neopelex.
14. preparation methods as claimed in claim 1 it is characterised in that mixing speed in described step (3) be 30～
300r/min.
15. preparation methods as claimed in claim 1 are it is characterised in that the extractant of described step (4) is perfluoro alkane, fluorine
One of chlorocarbon or perfluoro-cyclicether or two or more mixtures.
16. preparation methods as claimed in claim 15 are it is characterised in that the extractant of described step (4) is trifluoro three chloroethene
One of alkane, tetrachlorodifluoroethane, perfluoro-2-methyl cyclobutane, PF 5070 or perflexane or two or more mixing
Thing.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410017118.5A CN104774284B (en) | 2014-01-14 | 2014-01-14 | Preparation method of porous perfluorinated sulfonic acid resin for catalysts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410017118.5A CN104774284B (en) | 2014-01-14 | 2014-01-14 | Preparation method of porous perfluorinated sulfonic acid resin for catalysts |
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| CN105618136B (en) * | 2014-10-27 | 2017-12-19 | 中国科学院大连化学物理研究所 | A kind of rhodium base catalyst of the Polymer-supported containing iodine for methanol carbonyl |
| CN106925347B (en) * | 2015-12-29 | 2019-10-29 | 山东东岳未来氢能材料有限公司 | The preparation method of porous perfluorinated sulfonic resin catalyst |
| CN107311896A (en) * | 2017-06-13 | 2017-11-03 | 河北科技大学 | A kind of method of utilization sulfur dioxide synthesizing aryl sulfinic acid |
| CN107311868B (en) * | 2017-06-23 | 2020-05-22 | 北京理工大学 | Method for preparing p-tert-butyl methyl benzoate |
| CN111097540B (en) * | 2018-10-25 | 2023-03-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing methyl glycolate and preparation method thereof |
| CN111097553B (en) * | 2019-11-26 | 2022-07-26 | 南京源泉环保科技股份有限公司 | Solid material for treating cyanided cadmium plating wastewater and preparation method and application thereof |
| CN113999337A (en) * | 2020-07-27 | 2022-02-01 | 上海漫关越水处理有限公司 | Super-macroporous fluorine-containing super-strong acid catalytic resin and synthetic method thereof |
| CN115093792B (en) * | 2020-08-04 | 2023-10-13 | 吴江南玻玻璃有限公司 | Anti-reflection coating liquid and preparation method thereof |
| CN114618585B (en) * | 2020-12-10 | 2023-06-20 | 中国科学院大连化学物理研究所 | Platinum-based catalyst and preparation method and application thereof |
| CN117225476B (en) * | 2023-11-15 | 2024-02-20 | 山东华夏神舟新材料有限公司 | Supported metal catalyst and preparation and regeneration methods and application thereof |
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