CN103122043A - Preparation method of deiodination agent - Google Patents
Preparation method of deiodination agent Download PDFInfo
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- CN103122043A CN103122043A CN2011103690556A CN201110369055A CN103122043A CN 103122043 A CN103122043 A CN 103122043A CN 2011103690556 A CN2011103690556 A CN 2011103690556A CN 201110369055 A CN201110369055 A CN 201110369055A CN 103122043 A CN103122043 A CN 103122043A
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Abstract
The invention relates to a preparation method of deiodination agent, which is mainly used for solving the technical problem that the silver-containing resin deiodination agent prepared by sulfonic acid type macroporous ion exchange resin in the prior art is poor in deiodination effect. The preparation method of the deiodination agent comprises the following steps of: carrying out ion exchange reaction on the sulfonic acid type macroporous ion exchange resin and the silver compound, wherein the sulfonic acid type macroporous ion exchange resin has a macroporous styrene-divinyl benzene copolymer framework and-SO3H. The preparation method is characterized in that the technical problem is solved well by connecting the-SO3H with a benzene ring in the copolymer framework by the-CH2-, so that the preparation method can be used for the industrial production of the deiodination agent.
Description
Technical field
The present invention relates to a kind of preparation method who takes off idodine, relate in particular to take vinylbenzene--the divinylbenzene crosslink multipolymer is the preparation of taking off idodine of the sulfonic acid type macroporous ion exchange resin exchange silver of skeleton.
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
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 problem that idodine is taken off the iodine weak effect, and a kind of new preparation method who takes off idodine is provided.The argentiferous that the method has a preparation takes off idodine and takes off the effective characteristics of iodine.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method who takes off idodine, comprise sulfonic acid type macroporous ion exchange resin and silver compound carried out ion exchange reaction, described sulfonic acid type macroporous ion exchange resin have macropore styrene diethylene benzene copoly mer skeleton and-SO
3H, described-SO
3H passes through-CH
2-be connected with phenyl ring in described copolymer 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 specific surface of described sulfonic acid type macroporous ion exchange resin is preferably 200～400m
2/ g, pore volume is preferably 0.4～0.6cm
3/ g, the quality complete exchange capacity is preferably 3.4～5.3mmol/g; Described sulfonic acid type macroporous ion exchange resin can adopt the method preparation that 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 (1) forms by weight percentage and is preferably: dimethyl sulfoxide (DMSO) 70～90% and water 10～30%; The cl content that is connected with on described 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; Step (1) is connected with the macropore styrene diethylene benzene copoly mer of chloromethyl 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.
Mention " sulfonic acid type macroporous ion exchange resin and silver compound are carried out ion exchange reaction ", one skilled in the art will appreciate that usually to make described ion exchange resin and AgNO take water as medium
3Perhaps CH
3The COOAg contact; Can also in water medium, make described ion exchange resin and Ag
2O or Ag
2CO
3Mix, and add a small amount of acetic acid or HNO
3Complete ion exchange reaction; Can also adopt non-aqueous media, for example acetic acid carries out ion exchange reaction.These those skilled in the art's general knowledge all can be used for preparation method of the present invention.
The preparation method who takes off idodine 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 ℃, the inventive method preparation take off idodine to take off the iodine effect close with comparative example, but what the inventive method prepared takes off idodine when the evaluation temperature of bringing up to 90 ℃ to 115 ℃, 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.Add in polymeric kettle under room temperature 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 the sulfonic acid type macroporous ion exchange resin 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, 50 ℃ of vacuum-dryings obtained the dry thing of sulfonic acid type macroporous ion exchange resin 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.The character of sulfonic acid type macroporous ion exchange resin 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 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 the sulfonic acid type macroporous ion exchange resin 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 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, sulfonic group productive rate and the resin quality complete exchange capacity that makes are 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 ℃, the inventive method preparation take off idodine to take off the iodine effect close with comparative example, but what the inventive method prepared takes off idodine when the evaluation temperature of bringing up to 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).
The character of the sulfonic acid type macroporous ion exchange resin that table 4 the inventive method adopts
▲The sulphur theoretical content of butt resin, % (weight)=[(cl content * sulfur atomic weight of macropore chlorine ball/chlorine nucleidic mass)/(cl content * sulfur atomic weight of the cl content of 100-macropore chlorine ball+macropore chlorine ball/chlorine nucleidic mass)] * 100%.
Table 5 takes off the preparation of idodine
☆Take off silver content in idodine * 1000/[silver atoms amount (taking off silver content in idodine in 1-table 5) in silver exchange capacity=table 5];
△The silver exchange capacity accounts for complete exchange capacity ratio=(the quality complete exchange capacity in the silver-colored exchange capacity in table 5/table 4) * 100%.
Table 6 takes off the evaluation of idodine
| Evaluation temperature, ℃ | Contain iodine acetic acid air speed ◇，h -1 | The iodine content of acetic acid sample, ppb | |
| Embodiment 1 | 90 | 4 | 7.1 |
| Embodiment 2 | 90 | 4 | 6.9 |
| Embodiment 3 | 90 | 4 | 6.5 |
| Embodiment 4 | 90 | 10 | 7.3 |
| Embodiment 5 | 100 | 8 | 2.1 |
| Embodiment 6 | 100 | 8 | 0.8 |
| Embodiment 7 | 100 | 8 | 0.5 |
| Embodiment 8 | 115 | 8 | 0.5 |
| Embodiment 9 | 115 | 8 | 1.1 |
| Embodiment 10 | 45 | 4 | 3.1 |
| Embodiment 11 | 90 | 4 | 2.4 |
| Embodiment 12 | 100 | 4 | 1.7 |
| Embodiment 13 | 115 | 4 | 1.2 |
| Comparative Examples 1 | 45 | 4 | 3.2 |
| Comparative Examples 2 | 90 | 4 | 5.4 |
| Comparative Examples 3 | 100 | 4 | 12.2 |
| Comparative Examples 4 | 115 | 4 | 15.1 |
◇Refer to the quality of taking off the acetic acid that idodine per hour processes of unit mass.
Claims (9)
1. a preparation method who takes off idodine, comprise sulfonic acid type macroporous ion exchange resin and silver compound carried out ion exchange reaction, described 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. the preparation method who takes off idodine 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. the preparation method who takes off idodine 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, the quality complete exchange capacity is 3.4～5.3mmol/g.
4. the preparation method who takes off idodine according to claim 1 is characterized in that described sulfonic acid type macroporous ion exchange resin adopts the method preparation that 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.
5. the preparation method who takes off idodine according to claim 4 is characterized in that described in step (1), reaction solvent consists of by weight percentage:
Dimethyl sulfoxide (DMSO) 70～90%
Water 10～30%.
6. the preparation method who takes off idodine according to claim 4, the cl content that it is characterized in that being connected with on described phenyl ring in the macropore styrene diethylene benzene copoly mer of chloromethyl is 14～20% by weight percentage.
7. the preparation method who takes off idodine according to claim 4, is characterized in that the temperature of reaction in step (1) is 150～170 ℃, and the reaction times is 4～8 hours.
8. the preparation method who takes off idodine according to claim 4 is characterized in that macropore styrene diethylene benzene copoly mer that step (1) is connected with chloromethyl is in chlorine, with M
2SO
3Mol ratio be 1: 1.05～1.2.
9. the preparation method who takes off idodine according to claim 8, 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106552596A (en) * | 2015-09-24 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of de- iodine resin adsorbent and its preparation method and application |
| CN107583628A (en) * | 2017-10-27 | 2018-01-16 | 王泽山 | A kind of acetic acid takes off the production technology of iodine silver resin adsorbent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106552596A (en) * | 2015-09-24 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of de- iodine resin adsorbent and its preparation method and application |
| CN107583628A (en) * | 2017-10-27 | 2018-01-16 | 王泽山 | A kind of acetic acid takes off the production technology of iodine silver resin adsorbent |
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