CN102746429B - Preparation method for polystyrene sulfonic acid type ion exchange resin - Google Patents
Preparation method for polystyrene sulfonic acid type ion exchange resin Download PDFInfo
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- CN102746429B CN102746429B CN201210230670.3A CN201210230670A CN102746429B CN 102746429 B CN102746429 B CN 102746429B CN 201210230670 A CN201210230670 A CN 201210230670A CN 102746429 B CN102746429 B CN 102746429B
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- polystyrene
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- ethylene dichloride
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Abstract
The invention provides a preparation method for a polystyrene sulfonic acid type ion exchange resin, which belongs to the technical field of preparation of resins. The method is as follows: a heterogeneous reaction of suspending of polystyrene in a dispersant is carried out for 2 to 8 h under the condition of normal pressure with an SO3/alkyl phosphate sulfonation system or acetyl sulfonate used as a sulfonating agent and alkylogen as the dispersant, then the heterogeneous reaction is terminated by using lower alcohol, and then rinsing and drying are carried out. The preparation method provided in the invention has the advantages of high efficiency and mild reaction conditions.
Description
Technical field
The present invention relates to the preparation method of polystyrolsulfon acid, mainly use different sulphonating agent desulfonate polystyrene, obtain polystyrolsulfon acid type ion exchange resin, belong to the preparing technical field of resin.
Background technology
Polystyrene type ion exchange resin is a kind of water soluble polymer, take polystyrene as skeleton, with small molecules function base with chemical bonds, both retained micromolecular premium properties, there is again high molecular performance, the performance of this ion exchange resin is significantly improved, and range of application expands, and is widely used in chemical enterprise, pharmacy corporation, environmental protection industry (epi).
Polystyrene sulfonation technology is the industrialized key of polystyrene type ion exchange resin.Theoretically, polystyrolsulfon acid is mainly synthetic from two aspects, and a kind of is to take polystyrene as raw material, is dispersed in suitable organic solvent, by adding strong sulphonating agent, carries out sulfonation reaction under catalyzer and certain condition; Another kind is first repolymerization after polystyrene monomers sulfonation to be obtained to polystyrolsulfon acid.Traditional chemical technique is with dense H
2sO
4make sulphonating agent, stirring reaction at catalyzer and certain temperature, reaction finishes, with deionized water, washes, alkali neutralization, washing is dry.In its reaction process, there is side reaction: generate sulfone, generate sulphonic acid anhydride, generate many sulfonic acid, oxidation side reaction, generates unsaturated cyclic ketones and quinone, coking.In addition, aftertreatment has spent acid to produce, and especially, after industrialization, spent acid amount is large, and equipment is had to corrosion, and processing cost is high.
In recent years, the sulfonated phenylethylene dense H of sulphonating agent used
2sO
4by novel sulphonating agent, replaced gradually, wherein have the electronics of the sulphur trioxide being connected with Lewis base to supply with body, acyl group sulphonate.
Summary of the invention
The present invention is for fear of using dense H
2sO
4make in spent acid that sulphonating agent produces and last handling process product water content too high, and proposition SO
3/ alkyl phosphate sulfonation system or acetyl sulphonate carry out sulfonated polystyrene as sulphonating agent, and aftertreatment replaces deionized water by low-carbon alcohol, preferably resolve the problem of spent acid and product water content.
Technical problem solved by the invention is to reach by following measure: adopt polystyrene to be suspended in the out-phase reaction in dispersion agent, respectively with SO
3/ alkyl phosphate sulfonation system or acetyl sulphonate are made sulphonating agent, under condition of normal pressure, with haloalkane, make dispersion agent, reaction 2-8 hour.
A kind of preparation method of polystyrolsulfon acid type ion exchange resin, it is characterized in that, comprise the following steps: with oleum air distillation, produce sulphur trioxide, pass through condensing works, liquid sulphur trioxide is dissolved in haloalkane solvent, insulation is at 20 ~ 40 ℃, in the above-mentioned haloalkane solvent that is dissolved with sulphur trioxide, adds alkyl phosphate, obtains SO
3/ alkyl phosphate sulfonation system is as sulphonating agent, standby; Polystyrene joins in dispersion agent haloalkane, adds the above-mentioned sulphonating agent having prepared, and stirs, and synthesis under normal pressure 2 ~ 8 hours, adopts low-carbon alcohol termination reaction, then washs, is dried.
SO in preferred sulphonating agent
3with the mol ratio of polystyrene be (1-4): 1; SO
3with the mol ratio of alkyl phosphate be (3-4): 1, SO
3the temperature of/alkyl phosphate sulfonation system is at 30 ~ 60 ℃.
A preparation method for polystyrolsulfon acid type ion exchange resin, is characterized in that, comprises the following steps: at 0-10 ℃ (preferably 0 ℃), and dense H
2sO
4with diacetyl oxide with mol ratio 1:(1-1.5), preferred 1:(1.1-1.5) in haloalkane solvent reaction make acetyl sulphonate sulphonating agent, standby; Polystyrene is joined in dispersion agent haloalkane and be heated to 40-68 ℃, preferably 60 ℃, add the above-mentioned sulphonating agent having prepared, stir, react 2 ~ 4 hours, adopt low-carbon alcohol termination reaction, then wash, be dried.The temperature of sulfonation reaction is 40-60 ℃, preferably 60 ℃.The mol ratio of sulphonating agent and polystyrene is (1-4): 1.
Haloalkane in the present invention is solvent or dispersion agent, as long as can realize the dissolving of sulphonating agent and the dispersion of polystyrene, all can realize object of the present invention, and even acetone also can be realized object of the present invention.SO
3in/alkyl phosphate, due to SO
3with phosphoric acid ester complexing, thus make sulfonation reaction can be slowly, leniently carry out.The inventive method efficiency is high.
Embodiment
In conjunction with specific embodiments, the present invention will be further described, but the present invention is not limited to following examples:
The usage quantity of following polystyrene is 2g, SO
31, SO in 2-dichloroethane solution
3with the mass ratio of 1,2-ethylene dichloride be 1:3.
Embodiment 1
By 1,2-ethylene dichloride be heated to 40 ℃ stand-by, oleum air distillation, steams SO
3and become liquid by condensing tube condensation, with 1,2-ethylene dichloride, accept SO
3, get 13ml SO
31,2-dichloroethane solution adds 2.6g triethyl phosphate, obtains lurid sulphonating agent standby.
Polystyrene is joined to dispersion agent 1, in 2-ethylene dichloride, under mechanical stirring, sulphonating agent is added drop-wise to wherein, room temperature mechanical stirring reaction 2 hours, finishes reaction, with deionized water wash, filters, dry, obtains yellowish brown particle, and its sulfonation degree is more than 60%.
Embodiment 2
By 1,2-ethylene dichloride be heated to 40 ℃ stand-by, oleum air distillation, steams SO
3and become liquid by condensing tube condensation, with 1,2-ethylene dichloride, accept SO
3, get 18ml SO
31,2-dichloroethane solution adds 3.5g triethyl phosphate, obtains lurid sulphonating agent standby.
Polystyrene is joined to dispersion agent 1, in 2-ethylene dichloride, under mechanical stirring, sulphonating agent is added drop-wise to wherein, room temperature mechanical stirring reaction 2 hours, finishes reaction, with deionized water wash, filters, dry, obtains yellowish brown particle, and its sulfonation degree is more than 60%.
Embodiment 3
By 1,2-ethylene dichloride be heated to 40 ℃ stand-by, oleum air distillation, steams SO
3and become liquid by condensing tube condensation, with 1,2-ethylene dichloride, accept SO
3, get 13ml SO
31,2-dichloroethane solution adds 3.5g triethyl phosphate, obtains lurid sulphonating agent standby.
Polystyrene is joined to dispersion agent 1, in 2-ethylene dichloride, under mechanical stirring, sulphonating agent is added drop-wise to wherein, room temperature mechanical stirring reaction 2 hours, reaction finishes, and with deionized water wash, filters, dry, obtains yellowish brown particle, and its sulfonation degree is more than 60%.
Embodiment 4
At 0 ℃, get 4.4ml diacetyl oxide and add a certain amount ofly 1,2-ethylene dichloride, mixes, by the dense H of 2.0ml
2sO
4add in mixed solution, shake up, be cooled to 0 ℃, obtain acetyl sulphonate standby.
Polystyrene is distributed in 1,2-ethylene dichloride, is stirred and heated to 60 ℃, acetyl sulphonate is added drop-wise to wherein; isothermal reaction 2 hours, reaction finishes, and uses dehydrated alcohol termination reaction, and washing; filter, cryodrying, obtains yellow translucent particulate product, and sulfonation efficiency reaches more than 70%.
Embodiment 5
At 0 ℃, get 6.6ml diacetyl oxide and add a certain amount ofly 1,2-ethylene dichloride, mixes, by the dense H of 3.1ml
2sO
4add in mixed solution, shake up, be cooled to 0 ℃, obtain acetyl sulphonate standby.
Polystyrene is distributed in 1,2-ethylene dichloride, is stirred and heated to 60 ℃, acetyl sulphonate is added drop-wise to wherein; isothermal reaction 3 hours, reaction finishes, and uses dehydrated alcohol termination reaction, and washing; filter, cryodrying, obtains yellow translucent particulate product, and sulfonation efficiency reaches more than 90%.
Embodiment 6
At 0 ℃, get 8.8ml diacetyl oxide and add a certain amount ofly 1,2-ethylene dichloride, mixes, by the dense H of 4.1ml
2sO
4add in mixed solution, shake up, be cooled to 0 ℃, obtain acetyl sulphonate standby.
Polystyrene is distributed in 1,2-ethylene dichloride, is stirred and heated to 60 ℃, acetyl sulphonate is added drop-wise to wherein; isothermal reaction 3 hours, reaction finishes, and uses dehydrated alcohol termination reaction, and washing; filter, cryodrying, obtains yellow translucent particulate product, and sulfonation efficiency reaches more than 90%.
Embodiment 7
At 0 ℃, get 10.9ml diacetyl oxide and add 1,2-ethylene dichloride, mix, by the dense H of 5.1ml
2sO
4add in mixed solution, shake up, be cooled to 0 ℃, obtain acetyl sulphonate standby.
Polystyrene is distributed in 1,2-ethylene dichloride, is stirred and heated to 60 ℃, acetyl sulphonate is added drop-wise to wherein; isothermal reaction 3 hours, reaction finishes, and uses dehydrated alcohol termination reaction, and washing; filter, cryodrying, obtains yellow translucent particulate product, and sulfonation efficiency reaches more than 90%.
Embodiment 8
At 0 ℃, get 2.2ml diacetyl oxide and add a certain amount ofly 1,2-ethylene dichloride, mixes, by the dense H of 1.0ml
2sO
4add in mixed solution, shake up, be cooled to 0 ℃, obtain acetyl sulphonate standby.
Polystyrene is distributed in 1,2-ethylene dichloride, is stirred and heated to 60 ℃, acetyl sulphonate is added drop-wise to wherein; isothermal reaction 3 hours, reaction finishes, and uses dehydrated alcohol termination reaction, and washing; filter, cryodrying, obtains yellow translucent particulate product, and sulfonation efficiency reaches more than 70%.
Embodiment 9
Polystyrene is joined to dispersion agent 1, in 2-ethylene dichloride, under mechanical stirring, the sulphonating agent in embodiment (1) is added drop-wise to wherein, room temperature mechanical stirring reaction 2 hours, with dehydrated alcohol termination reaction washing, filters, dry, obtain yellowish brown particle, its sulfonation degree is more than 60%.
Embodiment 10
Polystyrene is joined to dispersion agent 1, in 2-ethylene dichloride, under mechanical stirring, the sulphonating agent in embodiment (2) is added drop-wise to wherein, room temperature mechanical stirring reaction 2 hours, with dehydrated alcohol termination reaction washing, filters, dry, obtain yellowish brown particle, its sulfonation degree is more than 60%.
Embodiment 11
Polystyrene is joined to dispersion agent 1, in 2-ethylene dichloride, under mechanical stirring, the sulphonating agent in embodiment (3) is added drop-wise to wherein, room temperature mechanical stirring reaction 2 hours, with dehydrated alcohol termination reaction washing, filters, dry, obtain yellowish brown particle, its sulfonation degree is more than 60%.
Embodiment 12
Polystyrene is distributed to 1; in 2-ethylene dichloride, be stirred and heated to 60 ℃, acetyl sulphonate in embodiment (4) is added drop-wise to wherein; isothermal reaction 3 hours; reaction finishes, and uses dehydrated alcohol termination reaction, and washing; filter; cryodrying, obtains yellow translucent particulate product, and sulfonation efficiency reaches more than 80%.
Claims (3)
1. a preparation method for polystyrolsulfon acid type ion exchange resin, is characterized in that, the usage quantity of polystyrene is 2g, at 0 ℃, gets 6.6ml diacetyl oxide and adds a certain amount ofly 1, and 2-ethylene dichloride, mixes, by the dense H of 3.1ml
2sO
4add in mixed solution, shake up, be cooled to 0 ℃, obtain acetyl sulphonate standby;
Polystyrene is distributed in 1,2-ethylene dichloride, is stirred and heated to 60 ℃, acetyl sulphonate is added drop-wise to wherein; isothermal reaction 3 hours, reaction finishes, and uses dehydrated alcohol termination reaction, and washing; filter, cryodrying, obtains yellow translucent particulate product, and sulfonation efficiency reaches more than 90%.
2. a preparation method for polystyrolsulfon acid type ion exchange resin, is characterized in that, the usage quantity of polystyrene is 2g, at 0 ℃, gets 8.8ml diacetyl oxide and adds a certain amount ofly 1, and 2-ethylene dichloride, mixes, by the dense H of 4.1ml
2sO
4add in mixed solution, shake up, be cooled to 0 ℃, obtain acetyl sulphonate standby;
Polystyrene is distributed in 1,2-ethylene dichloride, is stirred and heated to 60 ℃, acetyl sulphonate is added drop-wise to wherein; isothermal reaction 3 hours, reaction finishes, and uses dehydrated alcohol termination reaction, and washing; filter, cryodrying, obtains yellow translucent particulate product, and sulfonation efficiency reaches more than 90%.
3. a preparation method for polystyrolsulfon acid type ion exchange resin, is characterized in that, the usage quantity of polystyrene is 2g, at 0 ℃, gets 10.9ml diacetyl oxide and adds 1,2-ethylene dichloride, mixes, by the dense H of 5.1ml
2sO
4add in mixed solution, shake up, be cooled to 0 ℃, obtain acetyl sulphonate standby;
Polystyrene is distributed in 1,2-ethylene dichloride, is stirred and heated to 60 ℃, acetyl sulphonate is added drop-wise to wherein; isothermal reaction 3 hours, reaction finishes, and uses dehydrated alcohol termination reaction, and washing; filter, cryodrying, obtains yellow translucent particulate product, and sulfonation efficiency reaches more than 90%.
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| CN105061655A (en) * | 2015-07-09 | 2015-11-18 | 安徽皖东化工有限公司 | Preparation method of polystyrene sulfonic acid type ion exchange resin |
| CN113430022A (en) * | 2021-05-18 | 2021-09-24 | 南京大学 | Method for preparing sodium polystyrene sulfonate by sulfonating waste polystyrene and application of sodium polystyrene sulfonate in coal water slurry |
| CN115947974B (en) * | 2022-12-29 | 2024-03-19 | 旬阳领盛新材料科技有限公司 | Adsorbent for separating and purifying calcium and magnesium ions in phosphoric acid and preparation method thereof |
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