CN1082945A - Weak-acid cation-exchange resin - Google Patents
Weak-acid cation-exchange resin Download PDFInfo
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- CN1082945A CN1082945A CN93105858A CN93105858A CN1082945A CN 1082945 A CN1082945 A CN 1082945A CN 93105858 A CN93105858 A CN 93105858A CN 93105858 A CN93105858 A CN 93105858A CN 1082945 A CN1082945 A CN 1082945A
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Abstract
The invention discloses a class weak-acid cation-exchange resin, this resin mainly is to carry out free radical suspension copolymerization greater than the diene of the polymerization activity of acrylonitrile or polyene cross-linking agent and one or more radical polymerization activity less than the crosslinking agent of acrylonitrile polymerization activity by functional group monomer acrylonitrile and one or more radical polymerization activity, and hydrolysis obtains then.Its major advantage is: good performance indexes, cost is low.Wherein leading indicator volume-exchange amount is 4.5-4.8mmol/ml, and soda acid Volume Changes transition is 53%-60%, and intensity is greater than 90%.
Description
The invention belongs to the ion exchange resin field.What specifically, it related to is weak-acid cation-exchange resin.
One of principal item of weak-acid cation-exchange resin is for there being the polyacrylic acid spherical beads body of cross-linked structure.Practical weak-acid cation-exchange resin should have higher weight exchange capacity and volume-exchange amount, less acid, alkali Volume Changes transition and higher mechanical strength.And are uniformities of resin crosslinks structure to the key factor of above-mentioned various performance impacts.Cross-linked structure is even more, and then above-mentioned every index is just good more, and simultaneously, production cost is low, technology simply also is the requirement of practical production technology.At present, weak-acid cation-exchange resin is mostly by methyl acrylate and divinylbenzene copolymerization, and polymer hydrolysis under alkali condition then makes ester group be converted into carboxyl, can obtain, and also can add other crosslinking agent sometimes.Because the free-radical polymerized reactivity ratio of methyl acrylate and divinylbenzene differs bigger, the cross-linked structure of this weak-acid cation-exchange resin copolymer is inhomogeneous, therefore there is volume-exchange amount low (smaller or equal to 4.2mmol/ml) in product, acid, alkali Volume Changes transition big (more than or equal to 72%), intensity low (smaller or equal to 51%) etc. are not enough, and raw material propylene acid methyl esters price height is so that production cost is higher.
Purpose of the present invention is exactly in order to overcome the deficiencies in the prior art, proposes a kind of novel weak-acid cation-exchange resin.It has preferable performance is weight exchange capacity and volume-exchange amount height, and acid, alkali transition, Volume Changes was little, the intensity height, and with low cost.
To achieve these goals, the technical solution used in the present invention is: the acrylonitrile with cheapness is primary raw material-functional group monomer, and the copolymer of synthesizing cross-linked even structure is hydrolyzed into the weak-acid cation-exchange resin of function admirable then.Because, do not find at present a kind of, diene or polyene cross-linking agent that price lower close as yet with the acrylonitrile reactivity ratio, therefore, key problem of the present invention is selected the crosslinking agent problem exactly for use.The present invention adopts the mixed cross-linker of the crosslinked mixing of two classes to constitute crosslinking agent of the present invention, wherein the polymerization activity of the radical polymerization specific activity acrylonitrile of a class crosslinking agent is big, and the polymerization activity of the radical polymerization specific activity acrylonitrile of an other class crosslinking agent is little, and above-mentioned two class crosslinking agents respectively select one or more in mixed cross-linker.
Above-mentioned polymerization activity comprises greater than the crosslinking agent of the polymerization activity of acrylonitrile: divinylbenzene, trivinylbenzene, divinyl toluene, divinyl dimethylbenzene, divinyl naphthalene, methacrylate glycol ester, itaconic acid allyl ester (utilizing wherein active bigger two keys), itaconic acid diallyl ester (utilizing wherein active bigger two keys).
Above-mentioned polymerization activity comprises less than the crosslinking agent of the polymerization activity of acrylonitrile: itaconic acid allyl ester (utilizing wherein active less two keys), itaconic acid diallyl ester (utilizing wherein active less two keys), cyanuric acid triallyl ester, the cyamelide triallyl ester, butene dioic acid diallyl ester.
In polymerization system, also can add a spot of other functional group monomer, as acrylic acid, methyl acrylate, methacrylic acid, methyl methacrylate etc., to adjust some performance of resin, as exchange capacity, soda acid Volume Changes transition etc.
In the above-mentioned copolymerization system, also can add inert organic solvents-pore-foaming agent.Pore-foaming agent is not participated in any chemical reaction in polymerization process, it is distributed in the polymer of formation, make polymer form macroreticular resin, inert organic solvents can be one or more in aliphatic hydrocarbon, aromatic hydrocarbon, water-insoluble alcohols, water-insoluble organic acid, ethers, ester class, the water-insoluble ketone etc.Monomer in polymerization system (functional group monomer and the agent of effect connection) is 2 with the inert organic solvents ratio: 1-1: 0.
Technical process of the present invention is: above-mentioned functional group monomer, crosslinking agent and inert organic solvents are at radical initiator azo-compound (azodiisobutyronitrile, ABVN etc.), peroxide (benzoyl peroxide, acetyl peroxide, lauroyl peroxide) etc. exist down, carry out suspension polymerisation at aqueous phase, obtain spherical resin, the granularity of resin can be by changing the rotating speed of agitating device, the kind of dispersant is (as gelatin, polyvinyl alcohol, carboxymethyl cellulose etc.) and consumption (concentration is 0.01%-2%) adjust, copolymer hydrolysis under strong acid or highly basic condition of obtaining of copolymerization thus can obtain weak-acid cation-exchange resin.The strong acid hydrolysising condition can be: adopt the HCL of 30%-36%, and under 80-110 ℃ of condition, hydrolysis 8-30 hour; The highly basic hydrolysising condition can be: with the NaHO aqueous solution of 5%-40%, at 70-100 ℃ of hydrolysis 8-30 hour.
Major advantage of the present invention is: the performance than traditional product improves a lot, and production cost is low.It is 10.0-11.0mmol/g that leading indicator can reach the weight exchange capacity, and the volume-exchange amount is 4.5-4.8mmol/ml, and acid, alkali Volume Changes transition are 53%-60%, and intensity is＞90%.
The invention will be further described below in conjunction with embodiment:
Embodiment 1:
In the reactor that agitator, logical nitrogen conduit and condenser pipe are housed, drop into the aqueous solution (water) that contains 0.5% polyvinyl alcohol, logical nitrogen adds the oil phase that is equivalent to water weight 25% to drive the air in the reactor away.Consisting of of oil phase: 56% acrylonitrile, 7.2% divinyl polyphenyl (contain pure divinylbenzene and be 42.4% industrial goods, down with), 3.3% itaconic acid diallyl ester, 33% toluene and 0.5% azodiisobutyronitrile.Adjusting mixing speed makes the hanging drop diameter mainly between 0.3-1.0mm, be warmed up to 60 ℃ with 5 ℃/10 minutes speed, kept 2 hours, be warmed up to 70 ℃ and kept 10 hours with same programming rate then, be warmed up to 85 ℃ again and kept 1 hour, obtain sphere polymers.Continue the rising temperature, there is the azeotropic mixture of toluene and water to steam, if liquid phase is very little the time in the reactor, can directly feed steam or add a certain amount of hot water, till distillate is transparent, after the distillate layering, reclaim toluene, gained resin filter, washing back are dried to constant weight at 110 ℃, get the copolymer intermediate.
Above-mentioned copolymer intermediate joins and is equivalent in 50% sulfuric acid copolymer intermediate weight 200%, content, starts agitator and is heated to 100 ℃ with 5 ℃/10 minutes programming rate, keeps 1 hour, is heated to 120 ℃ and kept 20 hours again.Cooling washes neutrality with water, gets the macropore weak-acid cation-exchange resin.Its key technical indexes is: weight exchange capacity 10.0mmol/g, and the volume-exchange amount is 4.7mmol/ml, and soda acid Volume Changes transition is 58%, and intensity (oozing the mill method, down together) is 96%.
Embodiment 2:
Device is with embodiment 1, and water is the aqueous solution that contains 0.5% polyvinyl alcohol and 10% sodium chloride.Oil phase consists of: 53.2% acrylonitrile, 4% methyl acrylate, 6% divinylbenzene, 3.3% cyamelide triallyl ester, 33% toluene, 0.25% azodiisobutyronitrile and 0.25% benzoyl peroxide.The weight ratio of water and oil phase is 4: 1.Except that the concentration of used sulfuric acid is 60%, other operation is identical with embodiment 1.The key technical indexes of gained weak-acid cation-exchange resin is: weight exchange capacity 10.5mmol/g, and the volume-exchange amount is 4.5mmol/ml, and soda acid Volume Changes transition is 60%, and intensity is 96%.
Embodiment 3:
Device, water and water compare with embodiment 2 with oil phase, and oil phase consists of: 87.5% acrylonitrile, 12% itaconic acid diallyl ester, 0.5% azodiisobutyronitrile.Adjusting mixing speed makes the diameter of hanging drop mainly between 0.3-1.0mm, be heated to 60 ℃ with 5 ℃/10 minutes programming rates, kept 2 hours, be heated to 70 ℃ and kept 10 hours with identical programming rate then, be heated to 85 ℃ again and kept 2 hours, cooling, filtration, resin are dried to constant weight under 110 ℃.Get the copolymer intermediate.
Above-mentioned copolymer intermediate adds and is equivalent in 60% sulfuric acid resin 200%, content, start agitator, be heated to 80 ℃ with 5 ℃/10 minutes programming rates, kept 2 hours, be heated to 120 ℃ again, kept 20 hours, cooling, wash neutrality with water, get the gel-type weak-acid cation-exchange resin.Its key technical indexes is: the weight exchange capacity is 10.1mmol/g, and the volume-exchange amount is 4.5mmol/ml, and soda acid Volume Changes transition is 53%, and intensity is 90%.
Embodiment 4:
Device, water and water implement 2 together with the oil phase ratio, and oil phase consists of: 79.5% acrylonitrile, 5% divinylbenzene, 5% cyanuric acid triallyl ester, 10% toluene, 0.25% azodiisobutyronitrile and 0.25% benzoyl peroxide.Other condition and operation are with embodiment 2.Gained resin the key technical indexes is: the weight exchange capacity is 10.5mmol/g, and the volume-exchange amount is 4.8mmol/ml, and soda acid Volume Changes transition is 55%, and intensity is 93%.
Embodiment 5:
Device, water and water implement 2 together with the oil phase ratio, and oil phase consists of 79.5% acrylonitrile, 5% divinylbenzene, 5% maleic acid diallyl methyl esters, 10% toluene, 0.5% azodiisobutyronitrile.Other condition is with embodiment 2, and the key technical indexes of gained resin is: the weight exchange capacity is 10.8mmol/g, and the volume-exchange amount is 4.6mmol/ml, and soda acid Volume Changes transition is 59%, and temperature is 90%.
Embodiment 6-10:
Toluene among the embodiment 4 is replaced with the pore-foaming agent in the following table, then obtain embodiment 6-10.
| The embodiment pore-foaming agent | Weight exchange capacity (mmol/g) | Volume-exchange amount (mmol/ml) | Soda acid body transition becomes (%) | Intensity (%) |
| 6 n-octyl alcohols, 7 n-butyl ethers, 8 ethyl butyrates, 9 200# gasoline, 10 cyclohexanone | 10.3 10.4 10.0 10.2 10.6 | 4.6 4.7 4.5 4.5 4.6 | 57 57 53 60 60 | 98 93 94 90 94 |
Embodiment 11
The pore-foaming agent stearic acid, except that the extraction of the kind of pore-foaming agent and pore-foaming agent and embodiment 4 were different, other condition and operation were fully with embodiment 4.The stearic extraction of pore-foaming agent is to use the Sha Shi extractor in the copolymer intermediate, is solvent with ethanol, extracts 2 hours.The key technical indexes of gained macropore weak-acid cation-exchange resin is: the weight exchange capacity is 10.4mmol/g, and the volume-exchange amount is 4.8mmol/ml, and soda acid Volume Changes transition is 55%, and intensity is 96%.
Embodiment 12:
Combined polymerization prepares the copolymer intermediate with embodiment 4, its copolymer intermediate joins that to be equivalent to copolymer intermediate weight 300%, content be in 20% the sodium hydroxide solution, be heated to 95 ℃ with 5 ℃/10 minutes programming rates, kept 24 hours, cool off, wash neutrality, make resin transfer the H type to and wash neutrality with 2N hydrochloric acid, the macropore weak-acid cation-exchange resin.Its key technical indexes is: weight exchange capacity 10.1mmol/g, and the volume-exchange amount is 4.5mmol/ml, and soda acid Volume Changes transition is 60%, and intensity is 91%.
Claims (10)
1, a kind of weak-acid cation-exchange resin, it is characterized in that: to be functional group monomer acrylonitrile and one or more polymerization activities carry out the free radical suspension copolymerization greater than the diene of the polymerization activity of acrylonitrile or polyene cross-linking agent A and one or more polymerization activities less than the crosslinking agent B of the polymerization activity of acrylonitrile for it, then the resin that hydrolysis obtains under strong acid or highly basic condition;
Wherein, crosslinking agent A comprises: divinylbenzene, trivinylbenzene, divinyl toluene, divinyl dimethylbenzene, divinyl naphthalene, methacrylate glycol ester, itaconic acid allyl ester (utilizing wherein active bigger two keys), itaconic acid diallyl ester (utilizing wherein active bigger two keys);
Wherein: crosslinking agent B comprises: itaconic acid allyl ester (utilizing wherein active less two keys), itaconic acid diene handle base ester (utilizing wherein active less two keys), cyanuric acid triallyl ester, cyamelide triallyl ester, butene dioic acid diallyl ester.
2, a kind of copolymer intermediate of producing weak-acid cation-exchange resin is characterized in that: to be functional group monomer acrylonitrile and one or more polymerization activities carry out the free radical suspension copolymerization greater than the diene of the polymerization activity of acrylonitrile or polyene cross-linking agent and one or more polymerization activities less than the diene of the polymerization activity of acrylonitrile or polyene cross-linking agent obtains for it.
3, according to claim 1 or 2 described weak-acid cation-exchange resin and intermediates, it is characterized in that: can contain one or more of monomers such as acrylic acid, methyl acrylate, methacrylic acid in the functional group monomer acrylonitrile.
4, according to claim 1 or 2 described weak-acid cation-exchange resin and intermediates, it is characterized in that: can add one or more of inert organic solvents such as aliphatic hydrocarbon, aromatic hydrocarbon, alcohol, acid, ether, ester, ketone in its polymerization system, as pore-foaming agent.
5, a kind of technology of producing weak-acid cation-exchange resin, it is characterized in that: with above-mentioned functions base monomer, crosslinking agent and inert organic solvent are in the presence of radical initiator, carry out suspension polymerisation at aqueous phase, obtain the spherical resin copolymer, copolymer hydrolysis under strong acid or highly basic condition with copolymerization obtains obtains weak-acid cation-exchange resin.
6, according to claim 1 or 2 described weak-acid cation-exchange resin and intermediates, it is characterized in that: the ratio of functional group monomer and crosslinking agent is 98: 2-80: the 20(weight ratio).
7, according to described weak-acid cation-exchange resin of claim 4 and intermediate, it is characterized in that: free radical suspending copolymerization oil phase consists of: acrylonitrile, divinylbenzene, itaconic acid, two alkenyl esters, toluene and initator.
8, according to described weak-acid cation-exchange resin of claim 4 and intermediate, it is characterized in that: the oil phase of free radical suspending copolymerization consists of: acrylonitrile, methyl acrylate, divinylbenzene, cyamelide triallyl ester, toluene, initator.
9, according to described weak-acid cation-exchange resin of claim 4 and intermediate, it is characterized in that, the oil phase of free radical suspension copolymerization consists of: acrylonitrile, divinylbenzene, cyanuric acid triallyl ester, initator, pore-foaming agent, wherein pore-foaming agent is one of in n-octyl alcohol, cyclohexanone, n-butyl ether, ethyl butyrate or the 200# gasoline.
10, according to described weak-acid cation-exchange resin of claim 4 and intermediate, it is characterized in that: the oil phase of free radical suspending copolymerization consists of: acrylonitrile, divinylbenzene, cyanuric acid triallyl ester, stearic acid, initator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93105858A CN1043410C (en) | 1993-05-27 | 1993-05-27 | Weak-acidic cationic exchange resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93105858A CN1043410C (en) | 1993-05-27 | 1993-05-27 | Weak-acidic cationic exchange resin |
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| Publication Number | Publication Date |
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| CN1082945A true CN1082945A (en) | 1994-03-02 |
| CN1043410C CN1043410C (en) | 1999-05-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN93105858A Expired - Fee Related CN1043410C (en) | 1993-05-27 | 1993-05-27 | Weak-acidic cationic exchange resin |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326621C (en) * | 2002-09-11 | 2007-07-18 | 昭和电工株式会社 | Production process of film and column for cation chromatography |
| CN102234353A (en) * | 2011-04-20 | 2011-11-09 | 安徽美佳新材料股份有限公司 | Preparation method of D113 dilute acid acrylic cation-exchange resin |
| CN103881016A (en) * | 2012-12-20 | 2014-06-25 | 南开大学 | Porous resin using as solid phase synthesis carrier |
| CN105884967A (en) * | 2015-08-26 | 2016-08-24 | 同济大学 | Contamination-resistant large-capacity macroporous weak-acid resin synthesis method |
| CN106699974A (en) * | 2016-12-16 | 2017-05-24 | 东至绿洲环保化工有限公司 | Macroporous weakly-acidic cation exchange resin used for removing basic salts in wastewater |
| CN114763393A (en) * | 2021-01-13 | 2022-07-19 | 朗盛德国有限责任公司 | Cation exchangers, method for the production thereof, use thereof and polymers |
| CN115785513A (en) * | 2021-09-09 | 2023-03-14 | 佛山市云米电器科技有限公司 | Weak acid base material with high specific surface area and application thereof |
| CN117024654A (en) * | 2023-09-05 | 2023-11-10 | 河北利江生物科技有限公司 | Synthesis method of low-conversion-expansion-rate acrylic weak-acid cation exchange resin |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6050361B2 (en) * | 1981-08-21 | 1985-11-08 | 三菱化学株式会社 | Manufacturing method of cation exchange resin |
| CN86101585A (en) * | 1986-03-10 | 1987-09-23 | 南开大学化工厂 | Synthetic technology of resins used for acrylic weak ion exchange |
| DE3922201A1 (en) * | 1989-07-06 | 1991-01-17 | Bayer Ag | METHOD FOR THE PRODUCTION OF WATER ACID CUBE EXCHANGE RESINS |
| CN1072111A (en) * | 1991-11-06 | 1993-05-19 | 夏新 | J111 equal hole weakly acidic cationic exchanger resin and technology |
-
1993
- 1993-05-27 CN CN93105858A patent/CN1043410C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326621C (en) * | 2002-09-11 | 2007-07-18 | 昭和电工株式会社 | Production process of film and column for cation chromatography |
| CN102234353A (en) * | 2011-04-20 | 2011-11-09 | 安徽美佳新材料股份有限公司 | Preparation method of D113 dilute acid acrylic cation-exchange resin |
| CN103881016B (en) * | 2012-12-20 | 2017-08-25 | 南开大学 | A kind of porous resin as synthesis in solid state carrier |
| CN103881016A (en) * | 2012-12-20 | 2014-06-25 | 南开大学 | Porous resin using as solid phase synthesis carrier |
| CN105884967B (en) * | 2015-08-26 | 2018-08-31 | 同济大学 | A kind of synthetic method of anti-pollution type large capacity Macroporous Weakly-Acid |
| CN105884967A (en) * | 2015-08-26 | 2016-08-24 | 同济大学 | Contamination-resistant large-capacity macroporous weak-acid resin synthesis method |
| CN106699974A (en) * | 2016-12-16 | 2017-05-24 | 东至绿洲环保化工有限公司 | Macroporous weakly-acidic cation exchange resin used for removing basic salts in wastewater |
| CN114763393A (en) * | 2021-01-13 | 2022-07-19 | 朗盛德国有限责任公司 | Cation exchangers, method for the production thereof, use thereof and polymers |
| EP4029604A1 (en) | 2021-01-13 | 2022-07-20 | LANXESS Deutschland GmbH | Acrylonitrile-based cation exchanger |
| CN114763393B (en) * | 2021-01-13 | 2024-03-08 | 朗盛德国有限责任公司 | Cation exchanger, method for producing same, use thereof and polymer |
| CN115785513A (en) * | 2021-09-09 | 2023-03-14 | 佛山市云米电器科技有限公司 | Weak acid base material with high specific surface area and application thereof |
| CN115785513B (en) * | 2021-09-09 | 2023-11-03 | 佛山市云米电器科技有限公司 | Weak acid substrate with high specific surface area and application thereof |
| CN117024654A (en) * | 2023-09-05 | 2023-11-10 | 河北利江生物科技有限公司 | Synthesis method of low-conversion-expansion-rate acrylic weak-acid cation exchange resin |
| CN117024654B (en) * | 2023-09-05 | 2024-05-28 | 河北利江生物科技有限公司 | Synthesis method of low-conversion-expansion-rate acrylic weak-acid cation exchange resin |
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| CN1043410C (en) | 1999-05-19 |
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