CN103122044A - Sulphonic acid type macroporous ion exchange resin and preparation method thereof - Google Patents
Sulphonic acid type macroporous ion exchange resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a sulphonic acid type macroporous ion exchange resin and a preparation method thereof, and mainly aims to solve the technical problem that a silver-bearing resin deiodination agent for preparing the sulphonic acid type macroporous ion exchange resin is poor in deiodination effect in the prior art. The problem is well solved by adopting the technical scheme that the sulphonic acid type macroporous ion exchange resin, a copolymer skeleton containing macroporous styrene-divinylbenzene and -SO3H are adopted, and the -SO3H is connected with a benzene ring in the copolymer skeleton through -CH2-. The technical scheme can be used for industrial production of the sulphonic acid type macroporous ion exchange resin.
Description
Technical field
The present invention relates to a kind of sulfonic acid type macroporous ion exchange resin and preparation method thereof, relate in particular to take vinylbenzene--the divinylbenzene crosslink multipolymer is sulfonic acid type macroporous ion exchange resin of skeleton and preparation method thereof.
Background technology
Ion exchange resin take vinylbenzene-divinylbenzene crosslink multipolymer as skeleton is divided into gel-type and macroporous type with pore structure character, and is divided into anionic and cationic with the charge property of cation exchange groups in ion exchange resin.In order to prepare macroreticular ion exchange resin, usually at first carrying out vinylbenzene and divinylbenzene suspension polymerization under the existence of pore-creating agent prepares macropore vinylbenzene-divinylbenzene crosslink multipolymer (this field is called for short making large-pore white balls used, can buy from a lot of ion exchange resin manufacturers), for example, " containing synthesizing and characterizing of two keys wide aperture styrene-divinylbenzene microballoon " (applied chemistry [J], 1998,15 (2): reported making large-pore white balls used preparation method 103-105).And then as required the making large-pore white balls used chemical modification of carrying out is obtained containing macroporous cation or the anionite-exchange resin that negatively charged ion or positively charged ion etc. have ion exchanging function.
In prior art, take vinylbenzene--the divinylbenzene crosslink multipolymer is the sulfonic group (SO of the sulfonic acid type macroporous ion exchange resin of skeleton
3H) with this resin in phenyl ring directly be connected, can by under the existence of swelling agent, use dense H
2SO
4Perhaps SO
3Making large-pore white balls usedly carry out sulfonation and obtain described Deng sulphonating agent commonly used.For example, " sulfonation of porous vinylbenzene one divinyl benzene copolymer microballoon and to the absorption of bovine serum albumin " (ion-exchange and absorption [J], 2010,26 (4): 334-34) and " sulfonation reaction of high Crosslinked Macroporous styrene-divinylbenzene copolymer " (ion-exchange and absorption [J], 2000,16 (1): the method for sulfonating of having reported making large-pore white balls used resin 1-8).This sulfonic acid type macroporous ion exchange resin all has sale at home and abroad.
In order to obtain take vinylbenzene--the divinylbenzene crosslink multipolymer is the macroporous anion exchange resin of skeleton, the commonly used chloromethylation reagent such as available chlorine methyl ether carries out modification to making large-pore white balls used, obtain connecting on phenyl ring the vinylbenzene of chloromethyl--divinylbenzene crosslink multipolymer (macropore chlorine ball is called for short in this field), for example, " polystyrene chloromethylation Investigation on Technological Conditions " (Yindu Journal (certainly attaining the science version) [J], 1993,3:44-53) reported the preparation technology of chlorine ball, then the chlorine ball can obtain macroporous anion exchange resin with the amine reaction.
In addition, point out in " tensio-active agent and washing composition chemistry and technology " ([M] China Light Industry Press Beijing 1997 May the 1st edition 287 pages), alkyl chloride and sulphite reaction can obtain alkylsulfonate, and this reaction is called the Strecker reaction, and its reaction formula is as follows:
RCH
2Cl+Na
2SO
3→RCH
2SO
3Na+NaCl
US Patent No. 2115192 also disclose adopt the Strecker reaction with in compound-CH
2-Cl groups converted is-CH
2SO
3M, wherein M is K, Na etc.
As a kind of purposes of sulfonic acid type macroporous ion exchange resin, by with Ag ion exchange after obtain containing silver resin and take off idodine, this takes off idodine and can be used for removing iodine in carbonyl process acetic acid.For example, US 4,615, and 806 disclose employing sulfonic acid type macroporous ion exchange resin and AgNO
3, CH
3COOAg carries out ion-exchange and obtains argentiferous and take off idodine, then this is taken off the iodine that idodine is used for removing acetic acid, the sulfonic acid type macroporous ion exchange resin that adopts in embodiment is take Amberlyst 15 as representative, and its sulfonic group directly is connected with phenyl ring in styrene diethylene benzene copoly mer.
But the resin that adopts sulfonic group and phenyl ring in styrene diethylene benzene copoly mer directly to be connected is standby contains silver resin and takes off idodine and take off the iodine weak effect.
Summary of the invention
One of technical problem to be solved by this invention is that the silver resin that contains of the sulfonic acid type macroporous ion exchange resin preparation that exists in prior art takes off the technical problem that idodine is taken off the iodine weak effect, a kind of new sulfonic acid type macroporous ion exchange resin is provided, and the argentiferous that this resin has a preparation takes off idodine and takes off the effective characteristics of iodine.
Two of technical problem to be solved by this invention is to provide a kind of preparation method with solving the problems of the technologies described above corresponding sulfonic acid type macroporous ion exchange resin.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of sulfonic acid type macroporous ion exchange resin, have macropore styrene diethylene benzene copoly mer skeleton and-SO
3H is characterized in that described-SO
3H passes through-CH
2-be connected with phenyl ring in described copolymerization skeleton.
The styrene diethylene benzene copoly mer of macropore described in the technique scheme skeleton content of Vinylstyrene unit by weight percentage is preferably 8～28%; The preferred specific surface of described sulfonic acid type macroporous ion exchange resin is 200～400m
2/ g, pore volume is preferably 0.4～0.6cm
3/ g; The quality complete exchange capacity of described sulfonic acid type macroporous ion exchange resin is preferably 3.4～5.3mmol/g.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of method for preparing sulfonic acid type macroporous ion exchange resin as claimed in claim 1 comprises the steps:
(1) with the macropore styrene diethylene benzene copoly mer that is connected with chloromethyl on phenyl ring in reaction solvent with M
2SO
3React and obtain the ion exchange resin precursor I, wherein M is selected from Na, K, and wherein said reaction solvent is methyl-sulphoxide and/or water;
(2) with described ion exchange resin precursor I with the dilute aqueous soln of strong acid process, the pure water washing obtains described sulfonic acid type macroporous ion exchange resin.
Reaction solvent described in step in technique scheme (1) forms by weight percentage and is preferably: dimethyl sulfoxide (DMSO) 70～90%, water 10～30%; The cl content that is connected with on phenyl ring in the macropore styrene diethylene benzene copoly mer of chloromethyl is preferably 14～20% by weight percentage; Temperature of reaction in step (1) is preferably 150～170 ℃, and the reaction times is preferably 4～8 hours; Be connected with the macropore styrene diethylene benzene copoly mer of chloromethyl in step (1) in chlorine, with M
2SO
3Mol ratio be preferably 1: 1.05～1.2; M in step (1)
2SO
3Be preferably 1: 5 with the weight ratio of described reaction solvent～10.
Sulfonic acid type macroporous ion exchange resin of the present invention, due to-SO
3H passes through-CH
2-indirectly be connected with phenyl ring in described copolymerization skeleton, take off the in use harsh environment for use of tolerance more of idodine with what this resins exchange silver obtained.can find out from the experimental result that table 6 embodiment 10 to 13 and comparative example 1 to 4 provide, take off the idodine evaluation experimental under 45 ℃, resin of the present invention and comparative example are close, but the evaluation temperature of resin of the present invention be increased to 90 ℃ to 115 the time, the iodine effect of taking off of taking off idodine obviously improves along with the raising of temperature, and the iodine effect of taking off of Comparative Examples improves the trend that is deleterious with temperature under condition on year-on-year basis, for example in the embodiment 13 rear acetic acid of processing, iodine content is 1.2ppb, and on year-on-year basis in situation the iodine content of Comparative Examples 4 up to 15.1ppb, obtained technique effect preferably.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
1, making large-pore white balls used preparation
With reference to " containing synthesizing and characterizing of two keys wide aperture styrene-divinylbenzene microballoon " (applied chemistry [J], 1998,15 (2): 103-105) carry out.Under room temperature, add in polymeric kettle 450 grams through the vinylbenzene of underpressure distillation, (content is 49.5% to 590 gram technical grade Vinylstyrenes, all the other are vinyl xylene, ethyl vinyl benzene), 1560 gram pore-creating agents (being the toluene solution of the linear polystyrene (number-average molecular weight Mn=9.8 ten thousand) of 15% (weight)), 8 gram benzoyl peroxides, stirring and dissolving.Add the aqueous solution 2000ml that contains gum arabic 2% (weight) and polyvinyl alcohol (polymerization degree 1750. alcoholysis degrees 88%) 2% (weight), stir lower logical nitrogen 30min.Carried out suspension polymerization 10 hours under 88 ℃ under stirring.Suction filtration, water and toluene wash filter cake each 3 times.Take toluene as solvent extraction 24 hours, 60 ℃ of lower vacuum-dryings 48 hours, get 1019 gram styrene diethylene benzene copoly mer microballoons (namely making large-pore white balls used).Making large-pore white balls used middle Vinylstyrene content is 28% (weight).With technical grade Vinylstyrene consumption, pore-creating agent consumption, and making large-pore white balls used middle Vinylstyrene content is listed in table 1.
2, the preparation of macropore chlorine ball
Reference " polystyrene chloromethylation Investigation on Technological Conditions " (Yindu Journal (certainly attaining the science version) [J], 1993,3:44-53) carry out.Add making large-pore white balls used that 500 gram steps 1 obtain in enamel reaction still, (molecular formula is Cl-CH to add 3000 gram chloromethyl methyl ethers
2-O-CH
3), swelling 6 hours slowly adds Zinc Chloride Anhydrous 195 grams under stirring, be warming up to 40 ℃ of reactions 10 hours, filter, filter cake washing with alcohol 2 times, washing with acetone 2 times, under room temperature, vacuum-drying is 48 hours, obtains chloromethylation macropore styrene diethylene benzene copoly mer (being macropore chlorine ball).Through ultimate analysis, cl content is 19.8% (weight).The cl content of chloromethyl methyl ether consumption, reaction times and macropore chlorine ball is listed in table 2.
3, the preparation of sulfonic acid type macroporous ion exchange resin
(1) ion exchange resin precursor I preparation
With reference to US 2115192.Macropore chlorine ball 500 grams, 387 gram Na that step 2 is obtained
2SO
3(be M
2SO
3Be Na
2SO
3, in chlorine, macropore chlorine ball and M
2SO
3Mol ratio be 1: 1.1), 3100 gram water (be that reaction solvent is water, M
2SO
3With the weight ratio of reaction solvent be 1: 8), add in the magnetic agitation autoclave, under stirring 160 ℃ the reaction 6 hours, be down to room temperature, filter, with deionized water wash to filtrate to the reaction that is negative of 1% silver nitrate aqueous solution, the filter cake that obtains is the ion exchange resin precursor I.With M in the preparation of ion exchange resin precursor I
2SO
3Kind, macropore chlorine ball and M
2SO
3Mol ratio, reaction solvent form, M
2SO
3List in table 3 with weight ratio, temperature of reaction, the reaction times of reaction solvent.
(2) be converted into sulfonic acid type macroporous ion exchange resin of the present invention by the ion exchange resin precursor I
The ion exchange resin precursor I that step (1) is obtained whole soak ten times with the aqueous hydrochloric acid of 5% (weight), use 2000 milliliters of described hydrochloric acid solns at every turn, each 6 hours, stir once in every 30 minutes between soak period.Then filter, with deionized water wash to filtrate, 1% silver nitrate aqueous solution is neutral, obtain sulfonic acid type macroporous ion exchange resin aqueous resins of the present invention, 50 ℃ of vacuum-dryings obtained the dry thing of sulfonic acid type macroporous ion exchange resin of the present invention in 24 hours.Record quality complete exchange capacity (being also the butt complete exchange capacity) according to GB GB8144-87 method and be 3.42mmol/g.
The dry thing of the sulfonic acid type macroporous ion exchange resin that step (2) is obtained, the specific surface that gets dried resin with the low temperature nitrogen determination of adsorption method are 397, pore volume is 0.58; Through ultimate analysis, the sulphur content of dried resin is 11.3% (weight).Suppose that the chlorine in step (1) and (2) precursor I all is converted into sulfonic group, the sulphur theoretical content of the dried resin that calculate this moment is 18.3% (weight).The sulfonic group productive rate that calculates according to the formula of sulfonic group productive rate=(the sulphur theoretical content of the sulphur content/dried resin of dried resin) * 100% is 61.7%.The sulfonic group productive rate is higher, shows that the reaction of step (1) is higher to generating sulfonic selectivity, and is more favourable to preparation sulfonic acid type macroporous ion exchange resin of the present invention.The character of sulfonic acid type macroporous ion exchange resin of the present invention is listed in table 4.
4, take off the preparation of idodine
With reference to US 4,615,806 carry out.Get dry thing 100 grams of sulfonic acid type macroporous ion exchange resin of the present invention that step (2) obtains, add 1000 ml deionized water, add 5.65 gram Silver Nitrates, stirred 12 hours, filtering, is neutral with deionized water washing leaching cake to filtrate, and 50 ℃ of vacuum-dryings obtain taking off the dry thing of idodine.Take the dry thing that takes off idodine as benchmark, through ultimate analysis, silver content is 3.43% by weight percentage.With the silver compound kind, the silver compound consumption that adopt and take off in idodine the character such as silver content and list in table 5.
5, take off the evaluation of idodine
Get and take off dry thing 25 grams of idodine in above-mentioned steps 3, the internal diameter of packing into is that 2.5 centimetres, length are in the chromatographic column of vertical placement of 20 centimetres, with respect to taking off idodine volume 4h
-1Air speed (annotate: air speed refers to the quality of taking off the acetic acid that idodine per hour processes of unit mass.) contain the acetic acid of methyl iodide 200ppb with peristaltic pump in iodine from chromatographic column top injection, controlling the interior acetic acid temperature of chromatographic column is 90 ℃, treated acetic acid is from chromatographic column bottom outflow, when outflow acetic acid reaches 250 gram, from the acetic acid spout sampling of chromatographic column, be 7.1ppb through the gas chromatography determination iodine content.Evaluation temperature, the iodine content that contains iodine acetic acid air speed and acetic acid sample are listed in table 6.
[embodiment 2～13]
1, making large-pore white balls used preparation
Except technical grade Vinylstyrene consumption and the variation of pore-creating agent consumption, all the step 1 with embodiment 1 is identical for other.With technical grade Vinylstyrene consumption, pore-creating agent consumption, and making large-pore white balls used middle Vinylstyrene content is listed in table 1.
2, the preparation of macropore chlorine ball
Except adopting making large-pore white balls used in step 1, beyond chloromethyl methyl ether consumption and reaction times changed, all the step 2 with embodiment 1 was identical for other.The cl content of chloromethyl methyl ether consumption, reaction times and macropore chlorine ball is listed in table 2.
3, the preparation of sulfonic acid type macroporous ion exchange resin
(1) ion exchange resin precursor I preparation
Except the macropore chlorine ball in employing step 2, and M
2SO
3Kind, macropore chlorine ball and M
2SO
3Mol ratio, reaction solvent form, M
2SO
3Outside changing with weight ratio, temperature of reaction, reaction times of reaction solvent, operate identical with step (1) in embodiment 1 step 3.The Main change condition is listed in table 3.
(2) be converted into sulfonic acid type macroporous ion exchange resin of the present invention by the ion exchange resin precursor I
Except the ion exchange resin precursor I that adopts step (1) preparation, operation steps is identical with step (2) in embodiment 1 step 3, and the specific nature of sulfonic acid type macroporous ion exchange resin is listed in table 4.
embodiment 1 to embodiment 6 only changes solvent and the experiment that do not change other condition can be found out from table 3 and table 4, it is that the sulfonic group productive rate of solvent ratio when adopting water to be solvent is high that DMSO is adopted in the reaction of preparation precursor I, the resin quality complete exchange capacity that the present invention makes is corresponding also high, and when mixed solvent that the water that adopts by 70～90% (weight) dimethyl sulfoxide (DMSO) and 10～30% (weight) forms, further when mixed solvent that the water that adopts by 85～90% (weight) dimethyl sulfoxide (DMSO) and 10～15% (weight) forms, the resin quality complete exchange capacity that sulfonic group productive rate and the present invention make is higher, has better technique effect.
4, take off the preparation of idodine
Except adopting the sulfonic acid type macroporous ion exchange resin of step (2) preparation, and outside the silver compound kind, the silver compound consumption that adopt changed, other operation steps was with embodiment 1 step 4.With the silver compound kind, the silver compound consumption that adopt and take off in idodine the character such as silver content and list in table 5.
5, take off the evaluation of idodine
Except adopting the idodine of taking off of step 4 preparation, and evaluation temperature, contain outside iodine acetic acid air speed changes, other operation steps is with the step 5 of embodiment 1.Evaluation temperature, the iodine content that contains iodine acetic acid air speed and acetic acid sample are listed in table 6.
[comparative example 1]
1, making large-pore white balls used preparation
With the step 1 in embodiment 1.
2, the preparation of sulfonic acid type macroporous ion exchange resin
(ion-exchange and absorption [J], 2000,16 (1): method 1-8) is carried out with reference to " sulfonation reaction of high Crosslinked Macroporous styrene-divinylbenzene copolymer ".Be specially: add making large-pore white balls used in 500 gram steps 1 in the enamel sulphonation kettle, add 1000 milliliters of ethylene dichloride, under room temperature standing 24 hours, then add 98% the vitriol oil 1000 grams, under stirring, first 83 ℃ of reactions 3 hours, then reacted again 5 hours at 110 ℃.After reaction finishes, reaction mixture is down to room temperature, filter, with washing with acetone 3 times, each 1000 milliliters, acetone of washing, then deionized water wash to washings is negative to 5% barium chloride solution, obtains sulfonic acid type macroporous ion exchange resin aqueous resins, then obtains the dry thing of sulfonic acid type macroporous ion exchange resin in 24 hours 50 ℃ of vacuum-dryings.
3, take off the preparation of idodine
Except the dry thing of the sulfonic acid type macroporous ion exchange resin that adopts step 2 preparation, and the consumption of Silver Nitrate is beyond 28.43 grams, other operation is all identical with step 4 in embodiment 1, with silver compound kind, the silver compound consumption of employing and take off in idodine the character such as silver content and list in table 5.
4, take off the evaluation of idodine
Except adopting the idodine of taking off of step 3 preparation, evaluation temperature is beyond 45 ℃, and other appreciation condition is identical with embodiment 1 step 5.The iodine content of concrete evaluation temperature, acetic acid air speed and acetic acid sample is listed in table 6.
[comparative example 2～4]
Except the evaluation temperature in step 4 changed, other operation was identical with comparative example 1, and the iodine content of concrete evaluation temperature, acetic acid air speed and acetic acid sample is listed in table 6.
Can find out from table 6 embodiment 10 to 13 and comparative example 1 to 4, take off the idodine evaluation experimental under 45 ℃, resin of the present invention and comparative example are close, but when resin of the present invention is brought up to the evaluation temperature of 90 ℃ to 115 ℃, take off the iodine effect of taking off of idodine and take off the iodine successful and improve along with the raising of temperature, and the iodine effect of taking off of Comparative Examples improves the trend that is deleterious with temperature under condition on year-on-year basis.
The preparation that table 1 is making large-pore white balls used
The preparation of table 2 macropore chlorine ball
| The chloromethyl methyl ether consumption, g | Reaction times, h | The cl content of macropore chlorine ball, % (weight) | |
| Embodiment 1 | 3000 | 10 | 19.8 |
| Embodiment 2 | 3000 | 10 | 19.8 |
| Embodiment 3 | 3000 | 10 | 19.8 |
| Embodiment 4 | 3000 | 10 | 19.8 |
| Embodiment 5 | 3000 | 10 | 19.8 |
| Embodiment 6 | 3000 | 10 | 19.8 |
| Embodiment 7 | 3000 | 10 | 19.8 |
| Embodiment 8 | 2500 | 7 | 18.5 |
| Embodiment 9 | 2100 | 5 | 14.2 |
| Embodiment 10 | 2100 | 5 | 14.2 |
| Embodiment 11 | 2100 | 5 | 14.2 |
| Embodiment 12 | 2100 | 5 | 14.2 |
| Embodiment 13 | 2100 | 5 | 14.2 |
| Comparative example 1 | -- | -- | -- |
| Comparative example 2 | -- | -- | -- |
| Comparative example 3 | -- | -- | -- |
| Comparative example 4 | -- | -- | -- |
The preparation of table 3 ion exchange resin precursor I
★DMSO represents dimethyl sulfoxide (DMSO).
Claims (10)
1. sulfonic acid type macroporous ion exchange resin, have macropore styrene diethylene benzene copoly mer skeleton and-SO
3H is characterized in that described-SO
3H passes through-CH
2-be connected with phenyl ring in described copolymer skeleton.
2. sulfonic acid type macroporous ion exchange resin according to claim 1, it is characterized in that described macropore styrene diethylene benzene copoly mer skeleton by weight percentage the content of Vinylstyrene unit be 8～28%.
3. sulfonic acid type macroporous ion exchange resin according to claim 1, the specific surface that it is characterized in that described sulfonic acid type macroporous ion exchange resin is 200～400m
2/ g, pore volume are 0.4～0.6cm
3/ g.
4. sulfonic acid type macroporous ion exchange resin according to claim 1, the quality complete exchange capacity that it is characterized in that described sulfonic acid type macroporous ion exchange resin is 3.4～5.3mmol/g.
5. the preparation method of sulfonic acid type macroporous ion exchange resin claimed in claim 1, comprise the steps:
(1) with the macropore styrene diethylene benzene copoly mer that is connected with chloromethyl on phenyl ring in reaction solvent with M
2SO
3React and obtain the ion exchange resin precursor I, wherein M is selected from Na, K, and wherein said reaction solvent is methyl-sulphoxide and/or water;
(2) with described ion exchange resin precursor I with the dilute aqueous soln of strong acid process, the pure water washing obtains described sulfonic acid type macroporous ion exchange resin.
6. the preparation method of sulfonic acid type macroporous ion exchange resin according to claim 5 is characterized in that described in step (1), reaction solvent consists of by weight percentage:
Dimethyl sulfoxide (DMSO) 70～90%
Water 10～30%.
7. the preparation method of sulfonic acid type macroporous ion exchange resin according to claim 5, the cl content that it is characterized in that being connected with on phenyl ring in the macropore styrene diethylene benzene copoly mer of chloromethyl is 14～20% by weight percentage.
8. the preparation method of sulfonic acid type macroporous ion exchange resin according to claim 5, is characterized in that the temperature of reaction in step (1) is 150～170 ℃, and the reaction times is 4～8 hours.
9. the preparation method of sulfonic acid type macroporous ion exchange resin according to claim 5, the macropore styrene diethylene benzene copoly mer that it is characterized in that being connected with chloromethyl in step (1) is in chlorine, with M
2SO
3Mol ratio be 1: 1.05～1.2.
10. the preparation method of sulfonic acid type macroporous ion exchange resin according to claim 5, is characterized in that M in step (1)
2SO
3With the weight ratio of described reaction solvent be 1: 5～10.
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Cited By (7)
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| CN104086692A (en) * | 2014-06-26 | 2014-10-08 | 蓝星（成都）新材料有限公司 | Super-macropore strong acid resin used as solid catalyst matrix and preparation method thereof |
| CN104693336A (en) * | 2015-03-09 | 2015-06-10 | 华东理工大学 | Sulfonyl modified strong cationic hypercrosslinked resin and preparation method thereof |
| CN107629167A (en) * | 2017-10-17 | 2018-01-26 | 厦门大学 | A kind of sulfonic acid ion exchange resin microballoon and preparation method thereof |
| CN109180850A (en) * | 2018-09-20 | 2019-01-11 | 扬州金珠树脂有限公司 | A kind of composite pore-forming is preparing the application in macroreticular ion exchange resin |
| CN111111791A (en) * | 2020-01-06 | 2020-05-08 | 凯瑞环保科技股份有限公司 | Methanesulfonic acid type cation exchange resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104086692A (en) * | 2014-06-26 | 2014-10-08 | 蓝星（成都）新材料有限公司 | Super-macropore strong acid resin used as solid catalyst matrix and preparation method thereof |
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| CN109180850A (en) * | 2018-09-20 | 2019-01-11 | 扬州金珠树脂有限公司 | A kind of composite pore-forming is preparing the application in macroreticular ion exchange resin |
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| CN111659335A (en) * | 2020-06-15 | 2020-09-15 | 浙江普尔树脂有限公司 | Cation exchange resin sulfuric acid recovery and reuse equipment and process |
| CN116333204A (en) * | 2023-05-24 | 2023-06-27 | 山东德川化工科技有限责任公司 | Preparation method of nuclear-grade cation exchange resin |
| CN116333204B (en) * | 2023-05-24 | 2023-09-22 | 山东德川化工科技有限责任公司 | Preparation method of nuclear-grade cation exchange resin |
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