CN1247671C - Carbon nanometer tube ion exchange resin preparation method - Google Patents
Carbon nanometer tube ion exchange resin preparation method Download PDFInfo
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- CN1247671C CN1247671C CN 200310109478 CN200310109478A CN1247671C CN 1247671 C CN1247671 C CN 1247671C CN 200310109478 CN200310109478 CN 200310109478 CN 200310109478 A CN200310109478 A CN 200310109478A CN 1247671 C CN1247671 C CN 1247671C
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Abstract
The present invention relates to a preparation method for ion exchange resin of a carbon nanometer tube, which belongs to the technical field of ion exchange resin preparation. By utilizing the heat stability and the special hole structure of a carbon nanometer tube, micro hole type high temperature resistant ion exchange resin of a carbon nanometer tube is prepared. Before the polymerizing reaction is carried out, the carbon nanometer tube, a polymerization monomer and an initiating agent are agitated and mixed at certain temperature for a period of time, the original position reset polymerization is delayed so as to increase the molecular weight of a polymer, and the crosslinking degree is increased so as to improve the mechanical strength of the ion exchange resin. The ion exchange resin of a carbon nanometer tube, which is prepared by the preparation method of the present invention, has the advantages of good performance, high temperature resistant performance, beehive-shaped micro hole structure, high specific surface areas, large hole capability and low swelling degree. The hollow diameter is less than 10 nm. The ion exchange resin of a carbon nanometer tube has wide application to high temperature water treatment, special adsorptive resin, acidic catalysts, alkali catalysts, etc.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nanotube ionic exchange resin, belong to the ion exchange resin preparing technical field.
Background technology
The preparation good thermal stability, the ion exchange resin with reasonable skeleton and pore structure, low thermal expansion is the target that people lay siege to always.Because material and structural reason, common acidic cation-exchange resin can not be in the medium-term and long-term use of the reaction more than 100 ℃, common basic anion exchange resin can not use in the midium or long term of the reaction more than 50 ℃, and the serious use range that has limited resin to a great extent that expands.
The preparation method of fire resistant resin generally adopts two kinds of methods in the world at present: first method adopts the thermostability that improves material itself, NafionR, the NafionXR, Nafion511, the NafionXR-500 etc. that produce as E.I.Du Pont Company adopt perfluorinated sulfonic resin, this resin has good thermostability and chemical stability, 180-190 ℃ of Nafion series maximum operation (service) temperature, the structure atresia, specific surface is low, and can't prepare resin anion(R.A).Another kind method adopts the phenyl ring halogenation, to increase the stability of sulfonic acid group, oh group, Amberlyst35, Amberlyst36 etc. as Rhom and Hass's production, the maximum operation (service) temperature of its acidic cation-exchange resin is 140 ℃, and the maximum operation (service) temperature of basic anion exchange resin is 60 ℃.
As for the pass structure resin, generally adopt pore-creating agent, as ROHM AND HAAS Amberlyst series, the about 30nm in its aperture, the aperture is bigger, and above-mentioned series plastics exists the serious problem of swelling simultaneously.
Summary of the invention
Utilize carbon nanotube to be expected to synthesize high temperature resistant, micropore, low swelling ion exchange resin, but this design yet there are no any report so far.
The technical problem to be solved in the present invention is to release a kind of preparation method of carbon nanotube ionic exchange resin: utilize the thermostability of carbon nanotube and special pore structure, the resistant to elevated temperatures carbon nanotube ionic exchange resin of preparation microporous type.
The technical solution used in the present invention is, before polyreaction, carry out carbon nanotube and polymerization single polymerization monomer, initiator mix for some time at a certain temperature, adopt to postpone the original position polymerization that resets and improve the molecular weight of polymkeric substance, adopt and improve the physical strength that degree of crosslinking improves ion exchange resin.
The operation steps of technical solution of the present invention:
The first step raw material is handled
Vinylbenzene, benzene divinyl are removed stopper with 2N sodium hydroxide or ion exchange resin treatment;
The second step even carbon nanotube participates in polyreaction
With vinylbenzene, benzene divinyl, peroxidation phenyl-diformyl about 1.5 hours of 60 ℃ of following polymerizations, added the carbon nanotube polymerase 10 .5 hour, get monomer solution, vinylbenzene: benzene divinyl: peroxidation phenyl-diformyl: carbon nanotube=(50～90wt%): (5～40wt%): (0.5～5wt%): (0.01～30wt%);
The water preparation of the 3rd step
Gelatin, water and dispersion agent poly amic acid are dissolved water: gelatin: dispersion agent=(97～98.5wt%): (1～2wt%): (0.5～1wt%) down at 40 ℃;
The 4th step polymerization
The monomer solution in second step is poured into the aqueous phase in the 3rd step, and the control stirring velocity is with the particle diameter of control resin, simultaneously progressively be warming up to 78～80 ℃, be incubated 5～6 hours, be warmed up to 85～86 ℃ of insulations 5～6 hours again, last, be warming up to 95-96 ℃, be incubated 5～6 hours, obtain the carbon nanotube compound resin;
The 5th step compound resin is handled
The carbon nanotube compound resin that the 4th step was made takes out, and washing is put into baking oven, 80 ℃ of oven dry;
The 6th step was selected
Plan the 5th carbon nanotube compound resin that make of step and prepare acidic cation-exchange resin,, plan the carbon nanotube compound resin that the step makes and prepare basic anion exchange resin, operate by following the 8th step by following the 7th step operation;
The preparation of the 7th step acidic cation-exchange resin
The 5th carbon nanotube compound resin that make of step added 90～95% sulfuric acid, press carbon nanotube compound resin and vitriolic weight ratio adds at 1: 3, add ethylene dichloride, the weight ratio of pressing carbon nanotube compound resin and ethylene dichloride adds at 2: 1, reacts 12 hours down at 90 ℃, after 10～60% dilute sulphuric acid dilution, after water cleans, get finished product, the acid Zeo-karb of carbon nanotube advanced for the 9th step;
The preparation of the 8th step basic anion exchange resin
The carbon nanotube compound resin that the 5th step was made adds chloromethyl ether, the weight ratio of pressing carbon nanotube compound resin and chloromethyl ether adds at 1: 3, add zinc chloride, the weight ratio of pressing carbon nanotube compound resin and zinc chloride adds at 1: 0.2, add methylal, the weight ratio of pressing carbon nanotube compound resin and methylal adds at 1: 0.2, reacted 10～16 hours down at 30～40 ℃, after the methylal cleaning, add Trimethylamine 99, the weight ratio of pressing carbon nanotube compound resin and Trimethylamine 99 adds at 1: 3, reacted 10～16 hours down at 30～40 ℃, get finished product, the carbon nanotube basic anion exchange resin advanced for the 9th step;
The preparation of the 9th step finishes.
Method of the present invention has following beneficial effect:
The present invention is a kind of novel ion exchange resin preparation method, the product carbon nanotube ionic exchange resin excellent property of preparation, has higher heat resistance, the acidic cation-exchange resin use temperature reaches 200 ℃, the basic anion exchange resin use temperature reaches 100 ℃, and its structure is the honeycomb shape micropore, and the aperture is less than 10nm, has higher specific surface, bigger pore volume and low bulk degree.
Embodiment
All embodiment all operate by the operation steps of technique scheme.
Embodiment 1
The first step is by the first step operation of technique scheme;
Second step, benzene divinyl 14 restrained with vinylbenzene 84 grams, and peroxidation phenyl-diformyl 1 restrains, and carbon nanotube 1 gram was operated by second step of technique scheme, got carbon nanotube compound resin 98 grams;
Third and fourth, five steps respectively by technique scheme third and fourth, five step operations;
The 6th synchronous selector system is equipped with the acid Zeo-karb of carbon nanotube;
The 7th step got acid Zeo-karb 250 grams of carbon nanotube by the 7th step operation of technique scheme;
The preparation of the 9th step finishes.
Embodiment 2
The first step is by the first step operation of technique scheme;
Second step, benzene divinyl 35 restrained with vinylbenzene 60 grams, and peroxidation phenyl-diformyl 2 restrains, and carbon nanotube 3 grams were operated by second step of technique scheme, got carbon nanotube compound resin 98 grams;
Third and fourth, five steps respectively by technique scheme third and fourth, five step operations;
The 6th synchronous selector system is equipped with the carbon nanotube basic anion exchange resin;
The 8th step got carbon nanotube basic anion exchange resin 240 grams by the 8th step operation of technique scheme;
The preparation of the 9th step finishes.
Embodiment 3
The first step is by the first step operation of technique scheme;
Second step, benzene divinyl 15 restrained with vinylbenzene 75 grams, and peroxidation phenyl-diformyl 3 restrains, and carbon nanotube 7 grams were operated by second step of technique scheme, got carbon nanotube compound resin 98 grams;
Third and fourth, five steps respectively by technique scheme third and fourth, five step operations;
The 6th synchronous selector system is equipped with the acid Zeo-karb of carbon nanotube;
The 7th step got acid Zeo-karb 250 grams of carbon nanotube by the 7th step operation of technique scheme;
The preparation of the 9th step finishes.
Embodiment 4
The first step is by the first step operation of technique scheme;
Second step, benzene divinyl 8 restrained with vinylbenzene 55 grams, and peroxidation phenyl-diformyl 4 restrains, and carbon nanotube 23 grams were operated by second step of technique scheme, got carbon nanotube compound resin 98 grams;
Third and fourth, five steps respectively by technique scheme third and fourth, five step operations;
The 6th synchronous selector system is equipped with the carbon nanotube basic anion exchange resin;
The 8th step got carbon nanotube basic anion exchange resin 240 grams by the 8th step operation of technique scheme;
The preparation of the 9th step finishes.
The present invention is particularly suitable for preparing the carbon nanotube ionic exchange resin, that prepared carbon nanotube ionic exchange resin has is high temperature resistant, micropore, low swollen advantage, has a wide range of applications at aspects such as high-temperature water processing, extraordinary polymeric adsorbent, an acidic catalyst, basic catalysts.
Claims (1)
1. the preparation method of a carbon nanotube ionic exchange resin, it is characterized in that, before polyreaction, carry out carbon nanotube and polymerization single polymerization monomer, initiator mix for some time at a certain temperature, adopt to postpone the original position polymerization that resets and improve the molecular weight of polymkeric substance, adopt and improve the physical strength that degree of crosslinking improves ion exchange resin, operation steps:
The first step raw material is handled
Vinylbenzene, benzene divinyl are removed stopper with 2N sodium hydroxide or ion exchange resin treatment;
The second step even carbon nanotube participates in polyreaction
With vinylbenzene, benzene divinyl, peroxidation phenyl-diformyl about 1.5 hours of 60 ℃ of following polymerizations, added the carbon nanotube polymerase 10 .5 hour, get monomer solution, vinylbenzene: benzene divinyl: peroxidation phenyl-diformyl: carbon nanotube=(50～90wt%): (50～40wt%): (0.5～5wt%): (0.01～30wt%);
The water preparation of the 3rd step
Gelatin, water and dispersion agent poly amic acid are dissolved water: gelatin: dispersion agent=(97～98.5wt%): (1～2wt%): (0.5～1wt%) down at 40 ℃;
The 4th step polymerization
The monomer solution in second step is poured into the aqueous phase in the 3rd step, and the control stirring velocity is with the particle diameter of control resin, simultaneously progressively be warming up to 78-80 ℃, be incubated 5～6 hours, be warmed up to 85～86 ℃ of insulations 5～6 hours again, last, be warming up to 95～96 ℃, be incubated 5～6 hours, obtain the carbon nanotube compound resin;
The 5th step compound resin is handled
The carbon nanotube compound resin that the 4th step was made takes out, and washing is put into baking oven, 80 ℃ of oven dry;
The 6th step was selected
Plan the 5th carbon nanotube compound resin that make of step and prepare acidic cation-exchange resin,, plan the carbon nanotube compound resin that the step makes and prepare basic anion exchange resin, operate by following the 8th step by following the 7th step operation;
The preparation of the 7th step acidic cation-exchange resin
The 5th carbon nanotube compound resin that make of step added 90～95% sulfuric acid, press carbon nanotube compound resin and vitriolic weight ratio adds at 1: 3, add ethylene dichloride, the weight ratio of pressing carbon nanotube compound resin and ethylene dichloride adds at 2: 1, reacts 12 hours down at 90 ℃, after 10～60% dilute sulphuric acid dilution, after water cleans, get finished product, the acid Zeo-karb of carbon nanotube advanced for the 9th step;
The preparation of the 8th step basic anion exchange resin
The carbon nanotube compound resin that the 5th step was made adds chloromethyl ether, the weight ratio of pressing carbon nanotube compound resin and chloromethyl ether adds at 1: 3, add zinc chloride, the weight ratio of pressing carbon nanotube compound resin and zinc chloride adds at 1: 0.2, add methylal, the weight ratio of pressing carbon nanotube compound resin and methylal adds at 1: 0.2, reacted 10～16 hours down at 30～40 ℃, after the methylal cleaning, add Trimethylamine 99, the weight ratio of pressing carbon nanotube compound resin and Trimethylamine 99 adds at 1: 3, reacted 10～16 hours down at 30～40 ℃, get finished product, the carbon nanotube basic anion exchange resin advanced for the 9th step;
The preparation of the 9th step finishes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310109478 CN1247671C (en) | 2003-12-17 | 2003-12-17 | Carbon nanometer tube ion exchange resin preparation method |
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|---|---|---|---|
| CN 200310109478 CN1247671C (en) | 2003-12-17 | 2003-12-17 | Carbon nanometer tube ion exchange resin preparation method |
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| CN1546555A CN1546555A (en) | 2004-11-17 |
| CN1247671C true CN1247671C (en) | 2006-03-29 |
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| CN 200310109478 Expired - Fee Related CN1247671C (en) | 2003-12-17 | 2003-12-17 | Carbon nanometer tube ion exchange resin preparation method |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103122045B (en) * | 2011-11-18 | 2015-09-09 | 中国石油化工股份有限公司 | Nano composite quaternary phosphonium salt resin |
| CN107175136A (en) * | 2017-07-11 | 2017-09-19 | 河南省科学院能源研究所有限公司 | A kind of weak-base anion-exchange resin and the method that levulic acid is purified using it |
| CN114656187B (en) * | 2022-04-29 | 2022-08-30 | 武汉大学 | Curing agent resistant to complex harmful ion coupling environment and preparation method and application thereof |
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