CN100443179C - Method for preparing fluorin-containing composite strong acid ion exchange resin - Google Patents
Method for preparing fluorin-containing composite strong acid ion exchange resin Download PDFInfo
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- CN100443179C CN100443179C CNB2004100862298A CN200410086229A CN100443179C CN 100443179 C CN100443179 C CN 100443179C CN B2004100862298 A CNB2004100862298 A CN B2004100862298A CN 200410086229 A CN200410086229 A CN 200410086229A CN 100443179 C CN100443179 C CN 100443179C
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Abstract
The present invention discloses a preparation method of fluorine-containing composite strong acid ion exchange resin, which is characterized in that a tetrafluoroethylene monomer are added to the polymerization process of a styrene monomer and divinylbenzene monomer by the method to form a resin framework with styrene and divinylbenzene, and then, the ion exchange resin is obtained by a sulfonation process. The resin prepared by method maintains a structural pore passage framework of styryl macroporous resin, has fluorine elements in the framework and is capable of improving sulfonic stability and activity.
Description
Technical field
The invention relates to a kind of preparation method of composite strong acid ion exchange resin, more specifically say so about a kind of preparation method of fluorine-containing composite strong acid ion exchange resin.
Background technology
Polystyrene-divinylbenzene macropore sulfonic acid ion exchange resin, be also referred to as the strong-acid type macroporous ion exchange resin, it is as solid acid catalyst, be widely used in various organic synthesis, especially the resistance to water of this class catalyst also is that oxide or molecular sieve catalysts are incomparable; But its functional group's sulfonic group with activated centre effect influences the expansion of its range of application being heated, can coming off when using in the acid medium.Sulfonic acid catalysis effect is not subjected to the influence of process for preparing resins substantially, but sulfonic group all can come off when being subjected to heat or use under acid condition.Therefore, sulfonic stability is to influence the strong-acid type ion exchange resin catalysis key factor in service life, and the heat endurance that improves the strong-acid type macroporous ion exchange resin is the important factor in order that influences its usability.
The production process of strong-acid type macroporous ion exchange resin is a two-step method, promptly synthesize the skeleton macromolecule earlier after, carry out again sulfonation make it with on have acid functional group.Studies show that the principal element that influences the sulfonic group heat endurance of macroporous ion exchange resin is a temperature, under service condition, if 10 ℃ of every risings of temperature, then its sulfonic loss late increases about 10%; Even serviceability temperature is constant, if equivalent of acid every raising of working medium, then sulfonic loss late also can corresponding increase about 10%.Certainly, sulfonic loss takes place gradually, so group quantity on the raising resin, the ion-exchange degree that promptly improves resin also is effective, but the exchange degree that in fact increases ion exchange resin is the comparison difficulty, because but the position of sulfonation is on original styrene monomer on the ion exchange resin, be to increase ion-exchange degree by adjustment cross-linkage of resin, the cinnamic ratio of change in principle, but some research reports show, even the degree of cross linking reduces to 1, ion-exchange degree can obviously not increase yet.
Use HCl and FeCl have been reported in " Yao Fanglian, Zhang Xia, Meng Jihong, Sun Jingwu, functional polymer journal, V9, No.2,247,1996 "
3Styrene-the macropore sulfuric acid resin of divinyl phenyl is carried out the result of study of modification, show that the heat endurance of the resin after the modification has improved.This article author thinks that the p-sulfonic acid base has played stabilization owing to the introducing of electron withdraw group, has therefore improved its stability, and can also improve its activity as acid catalyst simultaneously; But this method of modifying will use HCl to be halogenating agent, will cause the pollution to environment inevitably.
Based on above-mentioned identical principle, the sulfonic heat endurance of the perfluorinate ion exchange resin Nafion that the sixties, du pont company synthesized is just apparently higher than the styryl sulfonate resin, and has an obviously high acid strength, but the Nafion resin but has an outstanding defective, the very low (＜0.02m of its specific area as catalyst
2/ g).Disclosed a kind of sol-gel construction from part in " Harmer M A, Farneth W E, Sun Q; J.Am.Chem.Soc., 1996,118 (33): 7708～7715 ", this method is that the alkaline solution of the Nafion colloidal sol with the preparation silica is mixed under certain condition, makes Nafion/SiO
2, can expand specific area to 200m like this
2About/g.But this preparation process is comparatively complicated, and especially the required condition of Nafion resin dissolves is comparatively harsh.
Summary of the invention
The purpose of this invention is to provide a kind of low in the pollution of the environment, the preparation method of the simple relatively fluorine-containing composite strong acid ion exchange resin of process.
The preparation method of fluorine-containing composite strong acid ion exchange resin provided by the invention is characterized in that this method comprises the following steps:
1) water is made up of water and dispersant, and wherein the part by weight of water and styrene monomer and divinylbenzene monomer is 1: 3～5, and dispersant is gelatin or polyvinyl alcohol, accounts for 1～5% of the volume that always feeds intake;
2) organic monomer is made up of styrene monomer, divinylbenzene monomer and the tetrafluoroethylene monomer that is present in the organic solvent, the divinylbenzene monomer accounts for 1～50 heavy % of styrene monomer and divinylbenzene monomer total amount, and the part by weight of tetrafluoroethylene monomer and styrene monomer is 1: 5～20;
3) water is mixed mutually with organic monomer, the initator benzoyl peroxide that adds 0.1～1 heavy % that accounts for styrene monomer again, descended 2～10 hours at 70～80 ℃, add initator peroxysulphate again in tetrafluoroethylene monomer 0.1～1 heavy %, be incubated after 0.5～4 hour, kept 6～8 hours at 90～95 ℃, obtain copolymer;
4) copolymer carries out sulfonating reaction with the concentrated sulfuric acid again through hot water wash, oven dry, reclaims to obtain finished product.
Preparation method provided by the invention, suspension method commonly used is adopted in the polymerization of styrene and divinylbenzene, be about to the monomer suspended dispersed and carry out in water, the dispersant of use is selected from polyvinyl alcohol or gelatin, and the initator that styrene and divinylbenzene polymerization are used is benzoyl peroxide; The used initator of tetrafluoroethylene polymerization is a peroxysulphate, wherein preferred peroxosulphuric sodium.
Among the preparation method provided by the invention, said styrene and divinylbenzene are preferably sloughed polymerization inhibitor with the NaOH aqueous solution earlier.
Among the preparation method provided by the invention, said tetrafluoroethylene monomer is stored in the organic solvent, and its effect is to avoid it that polymerization at room temperature takes place.It is 1～6 chloralkane that said organic solvent is selected from various carbon numbers, comprises chloroform, dichloroethanes, dichloro hexane etc., benzene and have the aromatic that carbon number is 1～4 alkyl substituent, carbon number is 5～12 various branched paraffins, and the mixture of above-mentioned organic solvent.
Among the preparation method provided by the invention, the operating process of sulfonating reaction is familiar with by those skilled in the art.Said sulfonating reaction is to make sweller with an amount of dichloroethanes, nitrobenzene or many chloroethenes etc., in the concentrated sulfuric acid, carry out, general process is with polymer and the concentrated sulfuric acid (90～95 heavy %) and dichloroethanes, mix with 1: 5: 0.5 ratio, being warmed up to 80～90 ℃ kept 2～6 hours, then copolymer is washed till neutrality with dilution heat of sulfuric acid, oven dry obtains.
Preparation method provided by the invention, it is characterized in that this method adds tetrafluoroethylene monomer in the polymerization process of styrene and divinylbenzene monomer, make it to form resin matrix jointly with styrene and divinylbenzene, both kept the styryl macroreticular resin to have the skeleton of structure pore, make it to have fluorine element again in skeleton, its content is at 0.1～50 heavy %.
Preparation method provided by the invention has low in the pollution of the environment, the relative characteristic of simple of process.In addition, the fluorine-containing composite strong acid ion exchange resin that this method is prepared, sulfonic stability is significantly improved, and can reach 140～150 ℃; Its acid strength is significantly improved than common storng-acid cation exchange resin, and can make acid strength is-12 Hammett indicator discoloration, ordinary resin then can not, illustrate that its acid catalysis activity will be better than ordinary resin.We know that for the acidic catalyst material, high acid strength indicates that it has high catalytic activity, as can the catalysis polyetherization than under the low reaction temperatures, reactions such as esterification, superimposed, alkylation take place.
The specific embodiment
The present invention is further illustrated by the following examples, but content not thereby limiting the invention.
Among the embodiment, the content of fluorine adopts X-fluorescence diffraction approach to analyze in the ion exchange resin.
Among the embodiment, the specific area of ion exchange resin, aperture are measured with BET gas absorption instrument; Adopt thermogravimetric analyzer to measure sulfonic stability.
Among the embodiment, the assay method of acid strength is that resin material is ground is 100 purpose fine powders, when 80 ℃ of vacuum dehydration 4 after, with acid strength H
0Hammett indicator for-12 is measured, and whether range estimation judges variable color, and variable color then illustrates its acid strength H
0Be higher than-12.
Comparative Examples
On three mouthfuls of reaction bulbs of one 1 liter, a side mouth is equipped with condenser pipe, and another side mouth is equipped with the temperature agent, and middle port is a stirring arm.Pack in the bottle earlier water of 500 grams, addition are that 1% gelatin of cumulative volume is a dispersant; 100 gram styrene and divinylbenzene are sloughed polymerization inhibitor with strong-base anion-exchange resin earlier, wherein contain divinylbenzene 7 heavy %, and promptly crosslinked is 7; Add in the entry and disperse, the proportion control of monomer and water was at 1: 5.Weigh the ratio adding initator benzoyl peroxide of % again in monomer total amount 0.5, the control mixing speed keeps constant, begins to heat up, and to 80 ℃ of maintenances 2 hours, is warmed up to 90～95 ℃ again, keeps 6～8 hours.Copolymer is dried through hot water wash, and its fluorinated volume is zero.
Carry out sulfonating reaction again: in 1 liter there-necked flask, add 10 gram copolymers, the concentrated sulfuric acid (90～95 heavy %) and dichloroethanes, ratio is 1: 5: 0.5, is warmed up to 80～90 ℃ and keeps 4 hours.Copolymer is washed till neutrality with dilution heat of sulfuric acid, oven dry, the specific area of measuring with BET gas absorption instrument is 8m
2/ g, aperture are 30nm, make sulfonic stability with thermogravimetric analyzer and measure, and be index with first weightless platform, be 120 ℃.
The acid strength measurement result shows that it is-12 Hammett indicator discoloration that this material can not make acid strength.
Embodiment 1
On three mouthfuls of reaction bulbs of one 1 liter, a side mouth is equipped with condenser pipe, and another side mouth is equipped with the temperature agent, and middle port is a stirring arm.Pack in the bottle earlier water of 500 grams, addition are that 1% gelatin of cumulative volume is a dispersant; 90 gram styrene and divinylbenzene are sloughed polymerization inhibitor with strong-base anion-exchange resin earlier, wherein contain divinylbenzene 28 heavy %, and promptly the degree of cross linking is 28; Adding 10 gram tetrafluoroethene again is the dichloroethane solution of 50 heavy %, adds in the entry and disperses, and the proportion control of monomer and water was at 1: 5.Ratio in monomer total amount 0.5 heavy % adds the initator benzoyl peroxide again, and the control mixing speed keeps constant, begins to be warming up to 80 ℃, adds sodium peroxydisulfate again, keeps 2 hours, is warmed up to 90～95 ℃ again, keeps 6～8 hours.Copolymer is dried through hot water wash, and its fluorinated volume is 3 heavy %.
Sulfonating reaction: in 1 liter there-necked flask, add 10 gram copolymers, the concentrated sulfuric acid (90～95 heavy %) and dichloroethanes, ratio is 1: 5: 0.5, is warmed up to 80～90 ℃ and keeps 4 hours.Copolymer is washed till neutrality with dilution heat of sulfuric acid, oven dry, the specific area of measuring with BET gas absorption instrument is 8m
2/ g, aperture are 30nm, make sulfonic stability with thermogravimetric analyzer and measure, and be index with first weightless platform, be 140 ℃.
The acid strength measurement result shows that it is-12 Hammett indicator discoloration that this material can make acid strength.
Embodiment 2
On three mouthfuls of reaction bulbs of one 1 liter, a side mouth is equipped with condenser pipe, and another side mouth is equipped with the temperature agent, and middle port is a stirring arm.Pack in the bottle earlier water of 500 grams, addition are that 1% gelatin of cumulative volume is a dispersant; 85 gram styrene and divinylbenzene are sloughed polymerization inhibitor with strong-base anion-exchange resin earlier, wherein contain divinylbenzene 7 heavy %, and promptly the degree of cross linking is 7; Adding 15 gram tetrafluoroethene again is the dichloroethane solution of 50 heavy %, adds in the entry and disperses, and the proportion control of monomer and water was at 1: 5.Ratio in monomer total amount 0.5 heavy % adds the initator benzoyl peroxide again, and the control mixing speed keeps constant, begins to be warming up to 75 ℃, adds sodium peroxydisulfate again, keeps 2 hours, is warmed up to 90～95 ℃ again, keeps 6～8 hours.Copolymer is dried through hot water wash.Its fluorinated volume is 0.5 heavy %.
Carry out sulfonating reaction: in 1 liter there-necked flask, add 10 gram copolymers, the concentrated sulfuric acid (90～95 heavy %) and dichloroethanes, ratio is 1: 5: 0.5, is warmed up to 80～90 ℃ and keeps 4 hours.Copolymer is washed till neutrality with dilution heat of sulfuric acid, oven dry, the specific area of measuring with BET gas absorption instrument is 8m
2/ g, aperture are 30nm, make sulfonic stability with thermogravimetric analyzer and measure, and be index with first weightless platform, be 150 ℃.
The acid strength measurement result shows that it is-12 Hammett indicator discoloration that this material can make acid strength.
Embodiment 3
On three mouthfuls of reaction bulbs of one 1 liter, a side mouth is equipped with condenser pipe, and another side mouth is equipped with the temperature agent, and middle port is a stirring arm.Pack in the bottle earlier water of 500 grams, addition are that 1% gelatin of cumulative volume is a dispersant; 80 gram styrene and divinylbenzene are sloughed polymerization inhibitor with strong-base anion-exchange resin earlier, wherein contain divinylbenzene 3 heavy %, and promptly the degree of cross linking is 3; Adding 20 gram tetrafluoroethene again is the hexane solution of 43 heavy %, adds in the entry and disperses, and the proportion control of monomer and water was at 1: 5.Ratio in monomer total amount 0.5 heavy % adds the initator benzoyl peroxide again, and the control mixing speed keeps constant, begins to be warming up to 75 ℃, adds sodium peroxydisulfate again, keeps 2 hours, is warmed up to 85～90 ℃ again, keeps 6～8 hours.Copolymer is dried through hot water wash, and its fluorinated volume is 9.6 heavy %.
Carry out sulfonating reaction: in 1 liter there-necked flask, add 10 gram copolymers, the concentrated sulfuric acid (90～95 heavy %) and dichloroethanes, ratio is 1: 5: 0.5, is warmed up to 80～90 ℃ and keeps 4 hours.Copolymer is washed till neutrality with dilution heat of sulfuric acid, oven dry, the specific area of measuring with BET gas absorption instrument is 8m
2/ g, aperture are 30nm, make sulfonic stability with thermogravimetric analyzer and measure, and be index with first weightless platform, be 155 ℃.
The acid strength measurement result shows that it is-12 Hammett indicator discoloration that this material can make acid strength.
Embodiment 4
On three mouthfuls of reaction bulbs of one 1 liter, a side mouth is equipped with condenser pipe, and another side mouth is equipped with the temperature agent, and middle port is a stirring arm.Pack in the bottle earlier water of 500 grams, addition are that 1% gelatin of cumulative volume is a dispersant; 90 gram styrene and divinylbenzene are sloughed polymerization inhibitor with strong-base anion-exchange resin earlier, wherein contain divinylbenzene 12 heavy %, and promptly the degree of cross linking is 12; Adding 10 gram tetrafluoroethene again is the chloroformic solution of 50 heavy %, adds in the entry and disperses, and the proportion control of monomer and water was at 1: 5.Ratio in monomer total amount 0.5 heavy % adds the initator benzoyl peroxide again, and the control mixing speed keeps constant, begins to be warming up to 80 ℃, adds sodium peroxydisulfate again, keeps 2 hours, is warmed up to 90～95 ℃ again, keeps 6～8 hours.Copolymer is dried through hot water wash, and its fluorinated volume is 3 heavy %.
Carry out sulfonating reaction: in 1 liter there-necked flask, add 10 gram copolymers, the concentrated sulfuric acid (90～95 heavy %) and dichloroethanes, ratio is 1: 5: 0.5, is warmed up to 80～90 ℃ and keeps 4 hours.Copolymer is washed till neutrality with dilution heat of sulfuric acid, oven dry, the specific area of measuring with BET gas absorption instrument is 8m
2/ g, aperture are 30nm, make sulfonic stability with thermogravimetric analyzer and measure, and be index with first weightless platform, be 145 ℃.
The acid strength measurement result shows that it is-12 Hammett indicator discoloration that this material can make acid strength.
Embodiment 5
On three mouthfuls of reaction bulbs of one 1 liter, a side mouth is equipped with condenser pipe, and another side mouth is equipped with the temperature agent, and middle port is a stirring arm.Pack in the bottle earlier water of 500 grams, addition are that 1% gelatin of cumulative volume is a dispersant; 72 gram styrene and divinylbenzene are sloughed polymerization inhibitor with strong-base anion-exchange resin earlier, wherein contain divinylbenzene 7 heavy %, and adding 28 gram tetrafluoroethene again is the benzole soln of 50 heavy %, adds in the entry and disperses, and the proportion control of monomer and water was at 1: 5.Ratio in monomer total amount 0.5 heavy % adds the initator benzoyl peroxide again, and the control mixing speed keeps constant, begins to be warming up to 80 ℃, adds sodium peroxydisulfate again, keeps 2 hours, is warmed up to 90～95 ℃ again, keeps 6～8 hours.Copolymer is dried through hot water wash, and its fluorinated volume is 10 heavy %.
Carry out sulfonating reaction: in 1 liter there-necked flask, add 10 gram copolymers, the concentrated sulfuric acid (90～95 heavy %) and dichloroethanes, ratio is 1: 5: 0.5, is warmed up to 80～90 ℃ and keeps 4 hours.Copolymer is washed till neutrality with dilution heat of sulfuric acid, oven dry, the specific area of measuring with BET gas absorption instrument is 8m
2/ g, aperture are 30nm, make sulfonic stability with thermogravimetric analyzer and measure, and be index with first weightless platform, be 160 ℃.
The acid strength measurement result shows that it is-12 Hammett indicator discoloration that this material can make acid strength.
Embodiment 6
Synthesize in one 1 liter autoclave and carry out.Pack in the still earlier water of 500 grams, addition are that 1% gelatin of cumulative volume is a dispersant; 72 gram styrene and divinylbenzene are sloughed polymerization inhibitor with strong-base anion-exchange resin earlier, wherein contain divinylbenzene 15 heavy %, and promptly the degree of cross linking is 15; Adding 28 gram tetrafluoroethene again is the benzole soln of 50 heavy %, adds in the entry and disperses, and the proportion control of monomer and water was at 1: 5.Ratio in the heavy % of monomer total amount 0.5 adds the initator benzoyl peroxide again, with still airtight after, open and control mixing speed and keep constant, begin to be warming up to 80 ℃, kept 2 hours, this moment, reaction pressure was 0.5MPa, be warmed up to 90～95 ℃ again, kept 6～8 hours.Copolymer is dried through hot water wash, and its fluorinated volume is 10 heavy %.
Sulfonating reaction: in 1 liter there-necked flask, add 10 gram copolymers, the concentrated sulfuric acid (90～95 heavy %) and dichloroethanes, ratio is 1: 5: 0.5, is warmed up to 80～90 ℃ and keeps 4 hours.Copolymer is washed till neutrality with dilution heat of sulfuric acid, oven dry, the specific area of measuring with BET gas absorption instrument is 8m
2/ g, aperture are 30nm, make sulfonic stability with thermogravimetric analyzer and measure, and be index with first weightless platform, be 160 ℃.
The acid strength measurement result shows that it is-12 Hammett indicator discoloration that this material can make acid strength.
Embodiment 7
Synthesize in one 1 liter autoclave and carry out.Pack in the still earlier water of 500 grams, addition are that 1% gelatin of cumulative volume is a dispersant; 72 gram styrene and divinylbenzene are sloughed polymerization inhibitor with strong-base anion-exchange resin earlier, wherein contain divinylbenzene 20 heavy %, and promptly the degree of cross linking is 20; Adding 28 gram tetrafluoroethene again is the benzole soln of 50 heavy %, adds in the entry and disperses, and the proportion control of monomer and water was at 1: 5.Ratio in the heavy % of monomer total amount 0.5 adds the initator benzoyl peroxide again, with still airtight after, open and control mixing speed and keep constant, charge into nitrogen to 6MPa, begin to be warming up to 80 ℃, kept 2 hours, this moment, reaction pressure was 6.4MPa, was warmed up to 90～95 ℃ again, kept 6～8 hours.Copolymer is dried through hot water wash, and its fluorinated volume is 10 heavy %.
Carry out sulfonating reaction: in 1 liter there-necked flask, add 10 gram copolymers, the concentrated sulfuric acid (90～95 heavy %) and dichloroethanes, ratio is 1: 5: 0.5, is warmed up to 80～90 ℃ and keeps 4 hours.Copolymer is washed till neutrality with dilution heat of sulfuric acid, oven dry, the specific area of measuring with BET gas absorption instrument is 8m
2/ g, aperture are 30nm, make sulfonic stability with thermogravimetric analyzer and measure, and be index with first weightless platform, be 160 ℃.
The acid strength measurement result shows that it is-12 Hammett indicator discoloration that this material can make acid strength.
Claims (4)
1, a kind of preparation method of fluorine-containing composite strong acid ion exchange resin is characterized in that this method comprises the following steps:
1) water is made up of water and dispersant, and wherein the part by weight of water and styrene monomer and divinylbenzene monomer is 1: 3～5, and dispersant is gelatin or polyvinyl alcohol, accounts for 1～5% of the volume that always feeds intake;
2) organic monomer is made up of styrene monomer, divinylbenzene monomer and the tetrafluoroethylene monomer that is present in the organic solvent, wherein the divinylbenzene monomer accounts for 1～50 heavy % of styrene monomer and divinylbenzene monomer total amount, and the part by weight of tetrafluoroethylene monomer and styrene monomer is 1: 5～20;
3) water is mixed mutually with organic monomer, the initator benzoyl peroxide that adds 0.1～1 heavy % that accounts for styrene monomer again, descended 2～10 hours at 70～80 ℃, add initator peroxysulphate again in tetrafluoroethylene monomer 0.1～1 heavy %, be incubated after 0.5～4 hour, kept 6～8 hours at 90～95 ℃, obtain copolymer;
4) with copolymer through washing, oven dry, carry out sulfonating reaction with the concentrated sulfuric acid again, reclaim and to obtain finished product.
2, according to the method for claim 1, step 2) to be selected from carbon number be 1～6 chloralkane, benzene to said organic solvent, have carbon number is that aromatic, the carbon number of 1～4 alkyl substituent is 5～12 various branched paraffins in, and the mixture of above-mentioned organic solvent.
3, according to the method for claim 2, said chloralkane is chloroform, dichloroethanes or dichloro hexane.
4, according to the method for claim 1, said peroxysulphate is a peroxosulphuric sodium in the step 3).
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| CN101245113B (en) * | 2007-11-26 | 2010-12-22 | 天津科技大学 | Hemicellulose group ion exchange resin and preparation method thereof |
| CN102234347B (en) * | 2011-04-20 | 2014-01-01 | 安徽美佳新材料股份有限公司 | Preparation method for WA-2 amino acid speciality resin |
| CN102228841B (en) * | 2011-05-11 | 2013-04-10 | 凯瑞化工股份有限公司 | High-temperature-resistant fluorine-containing resin catalyst and preparation method thereof |
| CN104530388A (en) * | 2014-12-10 | 2015-04-22 | 上海大学 | Method for preparing polymeric chromogenic reagent from epoxy resin |
| CN115010842B (en) * | 2022-05-20 | 2024-02-02 | 万华化学集团股份有限公司 | Fluorine-containing strong-alkaline anion resin catalyst, preparation method thereof and preparation method of hydroxyethyl (meth) acrylate |
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| US3282875A (en) * | 1964-07-22 | 1966-11-01 | Du Pont | Fluorocarbon vinyl ether polymers |
| JPH0776644A (en) * | 1993-09-08 | 1995-03-20 | Asahi Glass Co Ltd | Solution composition of fluorine-containing ion-exchange resin and dissolution method thereof |
| CN1119129A (en) * | 1994-04-08 | 1996-03-27 | 三菱化学株式会社 | Modified ion exchange resins and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3282875A (en) * | 1964-07-22 | 1966-11-01 | Du Pont | Fluorocarbon vinyl ether polymers |
| JPH0776644A (en) * | 1993-09-08 | 1995-03-20 | Asahi Glass Co Ltd | Solution composition of fluorine-containing ion-exchange resin and dissolution method thereof |
| CN1119129A (en) * | 1994-04-08 | 1996-03-27 | 三菱化学株式会社 | Modified ion exchange resins and use thereof |
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| Title |
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| Nafion树脂超强酸催化剂在有机合成中的应用. 罗家忠等.离子交换与吸附，第8卷第3期. 1992 |
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| 改性强酸性阳离子交换树脂的合成及性能研究. 姚芳莲等.功能高分子学报，第9卷第2期. 1996 |
| 改性强酸性阳离子交换树脂的合成及性能研究. 姚芳莲等.功能高分子学报，第9卷第2期. 1996 * |
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