CN111909299A - Novel alkalescent styrene ion exchange resin - Google Patents
Novel alkalescent styrene ion exchange resin Download PDFInfo
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- CN111909299A CN111909299A CN202010857270.XA CN202010857270A CN111909299A CN 111909299 A CN111909299 A CN 111909299A CN 202010857270 A CN202010857270 A CN 202010857270A CN 111909299 A CN111909299 A CN 111909299A
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- ion exchange
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/24—Haloalkylation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
Abstract
The invention relates to a weak-base styrene ion exchange resin with large total exchange capacity, a preparation method and application thereof. The invention takes styrene and divinyl benzene as reaction monomers and prepares the intermediate product white ball through suspension polymerization reaction in water. And adding the intermediate product white balls and chloromethyl ether obtained by the suspension polymerization reaction into a reaction kettle, and reacting to obtain the functional group modified intermediate product chlorine balls. Adding chlorine balls and dimethylamine aqueous solution into a reaction kettle, and reacting under normal pressure to prepare the new weak-base styrene ion exchange resin. The weakly basic styrene ion exchange resin prepared by the invention has simple synthesis steps and mild reaction conditions. The resin has the advantages of high regeneration efficiency, large exchange capacity, strong pollution resistance and good mechanical strength.
Description
Technical Field
The invention belongs to the field of ion exchange resin, and particularly relates to weak-alkaline styrene ion exchange resin.
Background
The ion exchange resin is a high molecular polymer, and in the molecular structure of the ion exchange resin, one part is an insoluble three-dimensional space net-shaped matrix skeleton, and the other part is an active group consisting of fixed ions and exchangeable ions. The ion exchange resin has exchange and adsorption functions, and can be divided into cation exchange resin and anion exchange resin according to the property of exchangeable ions carried by the resin, and can be divided into strong acid and weak acid cation exchange resin and strong base and weak base anion exchange resin according to the dissociation capability. The ion exchange resin is widely applied to various industries of national economy, such as water treatment, petrochemical industry, wet metallurgy, medicine and other industries, and plays an indispensable role in the development process of the national economy.
The weakly basic styrene ion exchange resin is widely used in the industries of wet metallurgy, water treatment, medicine, chemical engineering and the like. The D301 ion exchange resin has simple synthesis steps and mild reaction conditions. The resin has the advantages of high regeneration efficiency, large exchange capacity, strong pollution resistance and good mechanical strength. At present, weak-base styrene ion exchange resin in the market of China has the problems of low exchange capacity and low adsorption capacity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a weak-base styrene ion exchange resin with large total exchange capacity, a preparation method and application thereof. The invention takes styrene and divinyl benzene as reaction monomers and prepares the intermediate product white ball through suspension polymerization reaction in water. And adding the intermediate product white balls and chloromethyl ether obtained by the suspension polymerization reaction into a reaction kettle, and reacting to obtain the functional group modified intermediate product chlorine balls. Adding chlorine balls and dimethylamine aqueous solution into a reaction kettle, and reacting under normal pressure to prepare the new weak-base styrene ion exchange resin.
The invention provides the following technical scheme:
a weakly basic styrene ion exchange resin has water content of 48-58%, mass total exchange capacity of 4.8mmol/g or more, and volume total exchange capacity of 1.45mmol/mL or more.
A preparation method of a weakly-alkaline styrene ion exchange resin comprises the following steps:
s1, suspension polymerization: styrene and divinyl benzene are used as reaction monomers, and suspension polymerization is carried out in water to obtain an intermediate product white ball;
s2, chloromethyl reaction: adding the intermediate product white balls and chloromethyl ether obtained by suspension polymerization into a reaction kettle, and reacting to obtain functional group modified intermediate product chlorine balls; the reaction process is carried out under the condition of normal pressure; the reaction temperature is 40-80 ℃, preferably 50-60 ℃, preferably 51 ℃;
s3, amination reaction: adding chlorine balls and dimethylamine aqueous solution into a reaction kettle, and reacting under normal pressure to prepare the weakly alkaline styrene ion exchange resin.
Preferably, S1, using styrene and divinylbenzene as reaction monomers and gelatin as an initiator, carrying out suspension polymerization reaction in water to obtain an intermediate product white ball, washing with water, and drying to obtain an intermediate product white ball; the molar ratio of styrene to divinylbenzene is 1: 0.8 to 2; preferably 1: 1.2-1.5;
preferably, S2, adding the intermediate products of white balls, chloromethyl ether and ferric trichloride into a reaction kettle, and carrying out functional group modification; filtering and separating the product, and washing with water to obtain an intermediate product chlorine ball; wherein, the chloromethyl ether can be recycled;
preferably, S3, adding the chlorine balls and the dimethylamine aqueous solution into a reaction kettle, reacting under the normal pressure condition, filtering and separating a product, and washing with water to obtain the weakly-alkaline styrene ion exchange resin. Wherein the dimethylamine solution can be recycled.
Preferably, sodium chloride is added into the reaction system of step S1, wherein the concentration of the sodium chloride is 400g/L, preferably 300 g/L;
preferably, the reaction time of S3 is 2 to 12h, preferably 10 h.
The weakly alkaline styrene ion exchange resin is applied to water treatment, petrochemical industry, hydrometallurgy, medicine and chemical industry.
The properties of the weakly basic styrene anion exchange resin obtained by the invention are shown in the following table:
compared with the prior art, the invention has the beneficial effects that:
according to the invention, divinylbenzene is selected as the pore-forming agent, and the styrene-divinylbenzene proportion is adjusted, so that the ion exchange capacity is not influenced while the crosslinking degree is improved. In the synthesis process of the styrene-divinylbenzene macroporous white spheres, styrene has certain hydrophilicity, is easy to adhere in suspension polymerization, the white spheres are elliptical, and the water phase becomes milky white after the polymerization and is mixed with white flocculent polymers. This is due to the fact that the water phase is more soluble in the monomer at the polymerization temperature. Sodium chloride is added into the water phase, so that the solubility of styrene in water can be reduced, and white balls can be prevented from being adhered. When the mass concentration of the aqueous phase sodium chloride is more than 300g/L, the yield of the white balls reaches 90%, and the surface is smooth and round; after the polymerization is complete, the aqueous phase is not cloudy. The weakly basic styrene ion exchange resin prepared by the invention has simple synthesis steps and mild reaction conditions. The resin has the advantages of high regeneration efficiency, large exchange capacity, strong pollution resistance and good mechanical strength.
Drawings
FIG. 1: the process route diagram of the invention.
FIG. 2: effect of sodium chloride concentration on white ball yield.
Detailed Description
The present invention will be described in detail with reference to examples, but the practice of the invention is not limited thereto.
Example 1
A weakly basic styrene ion exchange resin and a preparation method thereof are disclosed:
s1, using styrene and divinyl benzene as reaction monomers, using gelatin as an initiator, carrying out suspension polymerization reaction in water to obtain an intermediate product white ball, washing with water, and drying to obtain an intermediate product white ball; the molar ratio of styrene to divinylbenzene is 1: 1;
s2, adding the intermediate product white balls, chloromethyl ether and ferric trichloride into a reaction kettle, and reacting to perform functional group modification; filtering and separating the product, and washing with water to obtain an intermediate product chlorine ball; wherein, the chloromethyl ether can be recycled;
s3, adding chlorine balls and a dimethylamine aqueous solution into a reaction kettle, reacting under the normal pressure condition, filtering and separating a product, and washing to obtain a weakly basic styrene ion exchange resin; wherein the dimethylamine solution can be recycled. The reaction time was 6 h.
Example 2
A weakly basic styrene ion exchange resin is prepared by adding 100g/L NaCl to S1, and the rest is the same as example 1.
Example 3
A weakly basic styrene ion exchange resin is prepared by adding 200g/L NaCl to S1, and the rest is the same as example 1.
Example 4
A weakly basic styrene ion exchange resin is prepared by adding 300g/L NaCl to S1, and the rest is the same as example 1.
Example 5
A weakly basic styrene ion exchange resin is prepared by adding 400g/L NaCl to S1, and the rest is the same as example 1.
The white ball yields of examples 2-5 were measured and the results are shown in FIG. 2. It can be seen that the mass concentration of aqueous sodium chloride has a great influence on the yield of styrene-divinylbenzene white spheres: the yield of the white balls is increased along with the increase of the mass concentration of the sodium chloride; when the mass concentration of the aqueous phase sodium chloride is more than 300g/L, the yield of the white balls reaches 90%, and the surface is smooth and round; after the polymerization is complete, the aqueous phase is not cloudy.
Example 6
A weakly basic styrene ion exchange resin and a preparation method thereof are disclosed, wherein in S1, the molar ratio of styrene to divinylbenzene is 1: 1.4.
example 7
A weakly basic styrene ion exchange resin and a preparation method thereof are disclosed, wherein in S1, the molar ratio of styrene to divinylbenzene is 1: 1.8.
comparative example 1
A weakly basic styrene ion exchange resin and a preparation method thereof are disclosed, wherein in S1, the molar ratio of styrene to divinylbenzene is 1: 1.4.
comparative example 2
A weakly basic styrene ion exchange resin and a preparation method thereof are disclosed, wherein in S1, the molar ratio of styrene to divinylbenzene is 1: 2.5.
the products of examples 1, 6, 7 and comparative examples 1-2 were tested for their ion exchange capacity and the results are given in the following table:
Claims (10)
1. a weakly basic styrene ion exchange resin is characterized in that the water content is 48-58%, the mass total exchange capacity is more than or equal to 4.8mmol/g, and the volume total exchange capacity is more than or equal to 1.45 mmol/mL.
2. A preparation method of a weakly basic styrene ion exchange resin is characterized by comprising the following steps:
s1, suspension polymerization: styrene and divinyl benzene are used as reaction monomers, and suspension polymerization is carried out in water to obtain an intermediate product white ball;
s2, chloromethyl reaction: adding the intermediate product white balls and chloromethyl ether obtained by suspension polymerization into a reaction kettle, and reacting to obtain functional group modified intermediate product chlorine balls; the reaction process is carried out under the condition of normal pressure; the reaction temperature is 40-80 ℃, preferably 50-60 ℃, preferably 51 ℃;
s3, amination reaction: adding chlorine balls and dimethylamine aqueous solution into a reaction kettle, and reacting under normal pressure to prepare the weakly alkaline styrene ion exchange resin.
3. The method for preparing a weakly basic styrenic ion exchange resin as claimed in claim 2, comprising the steps of: s1, using styrene and divinyl benzene as reaction monomers, using gelatin as an initiator, carrying out suspension polymerization reaction in water to obtain an intermediate product white ball, washing with water, and drying to obtain an intermediate product white ball; the molar ratio of styrene to divinylbenzene is 1: 0.8 to 2; s2, adding the intermediate product white balls, chloromethyl ether and ferric trichloride into a reaction kettle, and reacting to perform functional group modification; filtering and separating the product, and washing with water to obtain an intermediate product chlorine ball; wherein, the chloromethyl ether can be recycled; and S3, adding the chlorine balls and the dimethylamine aqueous solution into a reaction kettle, reacting under the normal pressure condition, filtering and separating a product, and washing to obtain the weakly basic styrene ion exchange resin. Wherein the dimethylamine solution can be recycled.
4. The method for preparing a weakly basic styrenic ion exchange resin according to claim 2 or 3, wherein the molar ratio of styrene to divinylbenzene in S1 is preferably 1: 1.2-1.5.
5. The method for preparing a weakly basic styrenic ion exchange resin according to claim 2 or 3, wherein sodium chloride is added to the reaction system of step S1.
6. The method as claimed in claim 5, wherein the concentration of NaCl is 100-400 g/L.
7. The method for preparing a weakly basic styrenic ion exchange resin of claim 6, wherein the concentration of sodium chloride is 300 g/L.
8. The method for preparing a weakly basic styrenic ion exchange resin according to claim 2 or 3, wherein the reaction time of S3 is 2-12h, preferably 10 h.
9. A weakly basic styrenic ion exchange resin prepared by the preparation process according to any one of claims 2 to 8.
10. The weakly basic styrenic ion exchange resin of claim 9 for use in water treatment, petrochemical, hydrometallurgical, pharmaceutical, chemical industries.
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| CN202010857270.XA CN111909299A (en) | 2020-08-24 | 2020-08-24 | Novel alkalescent styrene ion exchange resin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112471485A (en) * | 2020-12-03 | 2021-03-12 | 山东均智生物科技有限公司 | Decolouring refining process for producing gourmet powder |
| CN115785515A (en) * | 2021-09-09 | 2023-03-14 | 佛山市云米电器科技有限公司 | Weak acid resin and preparation method thereof |
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2020
- 2020-08-24 CN CN202010857270.XA patent/CN111909299A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112471485A (en) * | 2020-12-03 | 2021-03-12 | 山东均智生物科技有限公司 | Decolouring refining process for producing gourmet powder |
| CN115785515A (en) * | 2021-09-09 | 2023-03-14 | 佛山市云米电器科技有限公司 | Weak acid resin and preparation method thereof |
| CN115785515B (en) * | 2021-09-09 | 2024-01-26 | 佛山市云米电器科技有限公司 | Weak acid resin and preparation method thereof |
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Application publication date: 20201110 |