CN107629167B - A kind of sulfonic acid ion exchange resin microballoon and preparation method thereof - Google Patents
A kind of sulfonic acid ion exchange resin microballoon and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of sulfonic acid ion exchange resin microballoons and preparation method thereof, styrene/divinylbenzene/2- acrylamido-2- methyl-1-propane sulfonic acid/the N-N prepared in emulsifier-free emulsion polymerization method, methylene-bisacrylamide cross-linked polymer microsphere is skeleton, it is swollen using solvent, sulfonation is carried out to it with chlorosulfonic acid later, synthesizes the cation exchange resin microballoon containing a large amount of sulfonate radicals.The advantages that sulfonic acid ion exchange resin microballoon of the invention and preparation method thereof has method simple, and mild condition, raw material is cheap, and post-processing is simple, and ion exchange capacity is big.
Description
Technical field
The invention belongs to ion exchange material technical fields, and in particular to a kind of ion exchange material that exchange capacity is big,
It is specifically related to a kind of sulfonic acid ion exchange resin microballoon and preparation method thereof.
Background technique
Ion exchange resin is a kind of reticular polymer compound for having active group, it have exchange, selection,
The functions such as absorption and catalysis, in many necks such as proton exchange membrane, catalyst, separating-purifying, industrial high purity water preparation, medical and health
Domain has major application.Sulfonic polystyrene type ion exchange resin is most widely used, it is the small molecule using polystyrene as skeleton
Function base polystyrene phenyl ring is modified in the form of chemical bond, so both having remained original low molecular various excellent
Performance, and since polymer effect can increase new function, this increases substantially the performance of ion exchange resin.Crosslinking is poly-
Styrene sulfonic acid type ion exchange resin has great role for water softening, as boiler feedwater, drinking water and electronics are used
The purity requirement that water etc. is discharged ion exchange increasingly improves, and the production of ion exchange resin and application technology is promoted constantly to mention
It is high.
In order to make the more efficient of water softening, it is necessary to introduce more commutative groups, accelerate ion exchange.Traditional
Method is with styrene (St), and the copolymer microsphere that diethylbenzene (DVB) is prepared through suspension polymerization is skeleton, is then directly dripped
Enriching sulfuric acid carries out sulfonating reaction, so that phenyl ring be made to modify upper sulfonic group, achievees the purpose that ion exchange, but polymer microballoon
In some granularity it is undesirable, will increase production cost in this way, increase energy consumption, waste of resource, and its ion exchange
Effect is also not especially desirable.
Therefore, a kind of ion exchange resin that exchange efficiency is high is researched and developed to be of great significance.
Summary of the invention
The present invention is intended to provide a kind of sulfonic acid ion exchange resin microballoon and preparation method thereof, using 2- acrylamide
Base-2- methyl-1-propane sulfonic acid (AMPS) is water-soluble monomer, the polystyrene microsphere appearance mask obtained after polymerization
Have hydrophilic nmature, can modify upper sulfonic group in polymer microballoon surfaces externally and internally after swelling sulfonation, thus reach raising from
The purpose of sub- exchange rate.
The technical solution adopted by the present invention to solve the technical problems first is that:
A kind of preparation method of sulfonic acid ion exchange resin microballoon, comprising:
1) under nitrogen protection, stirring and counterflow condition, water, 2- acrylamido -2- methyl-are sequentially added into container
1- propane sulfonic acid, N, N'- methylene-bisacrylamide, stir evenly；Then styrene, divinylbenzene are added thereto, adds
Heat is warming up to 70~80 DEG C, and after 8~12min of constant temperature, potassium peroxydisulfate is added, and reacts 20~26h, product centrifugation, washing several times,
Vacuum drying, obtains polystyrene microsphere；Wherein, the 2- acrylamido-2- methyl-1-propane sulfonic acid, N, N'- methylene
Bisacrylamide, styrene, divinylbenzene, potassium peroxydisulfate formula rate be 0.8~4g:0.015~0.075g:3.5~
4.5ml:0.022~0.028ml:0.09~0.11g；
2) 25~35min of swelling, the polyphenyl second are carried out to polystyrene microsphere obtained in step 1) with methylene chloride
The mass volume ratio of alkene microballoon and methylene chloride is 1g:45~55ml；The mixed solution of chlorosulfonic acid and methylene chloride is added dropwise later,
The volume ratio of chlorosulfonic acid and methylene chloride is 1:2.5~3.5 in the mixed solution, described micro- for being swollen the polystyrene
The volume ratio of the methylene chloride of ball and the mixed solution is 1:1.8~2.2；4~16h of sulfonating reaction is carried out at room temperature, be centrifuged,
Washing is several times to get the sulfonic acid ion exchange resin microballoon.
Above-mentioned steps 1) in, obtained polystyrene microsphere, the i.e. chemical structure of polymer microballoon before swelling sulfonation
Formula is shown below:
Wherein styrene (St) is oil-soluble monomer, and divinylbenzene (DVB) is oil-soluble crosslinking agent, 2- acrylamide
Base-2- methyl-1-propane sulfonic acid (AMPS) is water-soluble monomer, and N-N ,-methylene-bisacrylamide (MBA) is water-soluble cross-linked
Agent.
In one embodiment: in the step 1), potassium peroxydisulfate is in the form of 0.45%~0.55% persulfate aqueous solution
It is added.
In one embodiment: in the step 1), the volume ratio of water and persulfate aqueous solution is 3.5~4.5:1.
The technical solution adopted by the present invention to solve the technical problems second is that:
A kind of sulfonic acid ion exchange resin microballoon according to prepared by above-mentioned preparation method.
The technical solution adopted by the present invention to solve the technical problems third is that:
A kind of purposes of above-mentioned sulfonic acid ion exchange resin microballoon in ion exchange.
The technical solution adopted by the present invention to solve the technical problems fourth is that:
A kind of polystyrene microsphere with cationic function of exchange, the chemical structural formula of the polystyrene microsphere are as follows
Shown in formula:
The technical solution adopted by the present invention to solve the technical problems fifth is that:
A kind of preparation method of the above-mentioned polystyrene microsphere with cationic function of exchange, in nitrogen protection, stirring
Under counterflow condition, water, 2- acrylamido-2- methyl-1-propane sulfonic acid, N, N'- di-2-ethylhexylphosphine oxide are sequentially added into container
Acrylamide stirs evenly；Then styrene, divinylbenzene are added thereto, is heated to 70~80 DEG C, constant temperature 8~
After 12min, potassium peroxydisulfate is added, reacts 20~26h, several times, vacuum drying obtains described having for product centrifugation, washing
The polystyrene microsphere of cationic function of exchange；Wherein, the 2- acrylamido-2- methyl-1-propane sulfonic acid, N, N'- are sub-
Bisacrylamide, styrene, divinylbenzene, potassium peroxydisulfate formula rate be 0.8~4g:0.015~0.075g:
3.5~4.5ml:0.022~0.028ml:0.09~0.11g.
In one embodiment: the potassium peroxydisulfate is added in the form of 0.45%~0.55% persulfate aqueous solution.
In one embodiment: the volume ratio of the water and persulfate aqueous solution is 3.5~4.5:1.
Compared with prior art the invention has the characteristics that:
1) because water-soluble monomer AMPS itself has sulfonic group, sulphur is just had in polystyrene microsphere outer surface after copolymerization
Acidic group, so not carrying out the polystyrene microsphere before swelling sulfonation reacts has ion exchanging function.
2) due to the hydrophilic interaction of AMPS, after being swollen with methylene chloride, make polymer microballoon under chlorosulfonic acid effect
Also upper sulfonic group is modified on internal phenyl ring, is thus greatly improved exchange efficiency.
3) preparation method of the polymer microballoon has simple, and mild condition, raw material is cheap, and post-processing is simple, and ion is handed over
The advantages that amount of changing is big.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Gained sulfonic acid ion exchange resin is micro- when Fig. 1 is St:AMPS (molar ratio)=4:1 in the embodiment of the present invention 2
The infrared spectrum of ball.
Sulfonic acid ion exchange resin microballoon when Fig. 2 is St:AMPS (molar ratio)=4:1 in the embodiment of the present invention 2
Scanning electron microscope (SEM) photograph.
Sulfonic acid ion exchange resin microballoon when Fig. 3 is St:AMPS (molar ratio)=4:1 in the embodiment of the present invention 2
Transmission electron microscope picture.
Specific embodiment
The contents of the present invention are illustrated below by embodiment:
Embodiment 1:
1) it under nitrogen protection, is sequentially added into the 250ml three-necked flask equipped with stirring magneton and condensation reflux unit
80mL deionized water, 3.62g AMPS, 0.067g MBA, stir evenly, and then continue to that 4mL St, 25 μ L DVB, heating is added
It is warming up to 75 DEG C, after constant temperature 10min, the aqueous solution of 0.1g potassium peroxydisulfate (KPS) is added, and (0.1g potassium peroxydisulfate is dissolved in deionized water
In 20mL), for 24 hours, with dehydrated alcohol and deionized water to the multiple centrifuge washing of product, vacuum drying obtains Off-white solid for reaction
Powder, as polystyrene microsphere；
2) swelling 30min, last constant pressure dropping are carried out to above-mentioned Off-white solid powder (0.2g) with 10mL methylene chloride
The mixed solution (chlorosulfonic acid 5mL, methylene chloride 15mL) of chlorosulfonic acid and methylene chloride carries out sulfonating reaction 8h, then at room temperature
After deionized water centrifuge washing, as required sulfonic acid ion exchange resin microballoon.
Embodiment 2:
1) it under nitrogen protection, is sequentially added into the 250ml three-necked flask equipped with stirring magneton and condensation reflux unit
80mL deionized water, 1.81g AMPS, 0.034g MBA, stir evenly, and then continue to that 4mL St, 25 μ L DVB, heating is added
It is warming up to 75 DEG C, after constant temperature 10min, the aqueous solution of 0.1g potassium peroxydisulfate (KPS) is added, and (0.1g potassium peroxydisulfate is dissolved in deionized water
In 20mL), for 24 hours, with dehydrated alcohol and deionized water to the multiple centrifuge washing of product, vacuum drying obtains Off-white solid for reaction
Powder, as polystyrene microsphere；
2) swelling 30min, last constant pressure dropping are carried out to above-mentioned Off-white solid powder (0.2g) with 10mL methylene chloride
The mixed solution (chlorosulfonic acid 5mL, methylene chloride 15mL) of chlorosulfonic acid and methylene chloride carries out sulfonating reaction 12h, then at room temperature
After deionized water centrifuge washing, as required sulfonic acid ion exchange resin microballoon.
The FT-IR infrared spectrum of Fig. 1 is visible in 1228.11cm-1There is the characteristic peak of S-O key in place；The scanning electron microscope of Fig. 2
The transmission electron microscope picture of figure and Fig. 3 can be seen that microballoon has the pattern of similar gear, make ion exchange process faster.
Embodiment 3:
1) it under nitrogen protection, is sequentially added into the 150ml three-necked flask equipped with stirring magneton and condensation reflux unit
80mL deionized water, 0.904g AMPS, 0.017g MBA, stir evenly, and then continue to that 4mL St, 25 μ L DVB, heating is added
It is warming up to 75 DEG C, after constant temperature 10min, the aqueous solution of 0.1g potassium peroxydisulfate (KPS) is added, and (0.1g potassium peroxydisulfate is dissolved in deionized water
In 20mL), for 24 hours, with dehydrated alcohol and deionized water to the multiple centrifuge washing of product, vacuum drying obtains Off-white solid for reaction
Powder, as polystyrene microsphere；
2) swelling 30min, last constant pressure dropping are carried out to above-mentioned Off-white solid powder (0.2g) with 10mL methylene chloride
The mixed solution (chlorosulfonic acid 5mL, methylene chloride 15mL) of chlorosulfonic acid and methylene chloride carries out sulfonating reaction 16h, then at room temperature
After deionized water centrifuge washing, as required sulfonic acid ion exchange resin microballoon.
Table 1 be St:AMPS in different mol ratio obtained by elemental analysis figure, illustrate that sulfonic acid ion exchange resin is micro-
Ball (PSt-SO3H-PAMPS successful synthesis).
Table 1
The above is only the preferred embodiment of the present invention, the range implemented of the present invention that therefore, it cannot be limited according to, i.e., according to
Equivalent changes and modifications made by the invention patent range and description, should still be within the scope of the present invention.
Claims (10)
1. a kind of preparation method of sulfonic acid ion exchange resin microballoon, it is characterised in that: include:
1) under nitrogen protection, stirring and counterflow condition, water, 2- acrylamido-2- methyl-1-the third are sequentially added into container
Alkyl sulfonic acid, N, N'- methylene-bisacrylamide, stir evenly；Then styrene, divinylbenzene are added thereto, heating rises
Temperature is to 70~80 DEG C, and after 8~12min of constant temperature, potassium peroxydisulfate is added, and reacts 20~26h, product centrifugation, washing several times, vacuum
It is dry, obtain polystyrene microsphere；Wherein, the 2- acrylamido-2- methyl-1-propane sulfonic acid, N, N'- di-2-ethylhexylphosphine oxide third
Acrylamide, styrene, divinylbenzene, potassium peroxydisulfate formula rate be 0.8~4g:0.015~0.075g:3.5~
4.5ml:0.022~0.028ml:0.09~0.11g；
2) 25~35min of swelling is carried out to polystyrene microsphere obtained in step 1) with methylene chloride, the polystyrene is micro-
The mass volume ratio of ball and methylene chloride is 1g:45~55ml；The mixed solution of chlorosulfonic acid and methylene chloride is added dropwise later, it is described
The volume ratio of chlorosulfonic acid and methylene chloride is 1:2.5~3.5 in mixed solution, for being swollen the dichloro of the polystyrene microsphere
The volume ratio of methane and the mixed solution is 1:1.8~2.2；At room temperature carry out 4~16h of sulfonating reaction, be centrifuged, wash it is several
It is secondary to get the sulfonic acid ion exchange resin microballoon.
2. the preparation method of sulfonic acid ion exchange resin microballoon according to claim 1, it is characterised in that: the step
1) in, the chemical structural formula of obtained polystyrene microsphere is shown below:
3. the preparation method of sulfonic acid ion exchange resin microballoon according to claim 1, it is characterised in that: the step
1) in, potassium peroxydisulfate is added in the form of 0.45%~0.55% persulfate aqueous solution.
4. the preparation method of sulfonic acid ion exchange resin microballoon according to claim 3, it is characterised in that: the step
1) in, the volume ratio of water and persulfate aqueous solution is 3.5~4.5:1.
5. sulfonic acid ion exchange resin prepared by a kind of preparation method according to any one of claim 1 to 4
Microballoon.
6. purposes of the sulfonic acid ion exchange resin microballoon in ion exchange described in a kind of claim 5.
7. a kind of polystyrene microsphere with cationic function of exchange, it is characterised in that: the chemistry of the polystyrene microsphere
Structural formula is shown below:
8. a kind of preparation method of the polystyrene microsphere with cationic function of exchange as claimed in claim 7, feature exist
In: under nitrogen protection, stirring and counterflow condition, water, 2- acrylamido-2- methyl-1-propane are sequentially added into container
Sulfonic acid, N, N'- methylene-bisacrylamide, stir evenly；Then styrene, divinylbenzene, heat temperature raising are added thereto
To 70~80 DEG C, after 8~12min of constant temperature, potassium peroxydisulfate is added, reacts 20~26h, several times, vacuum is dry for product centrifugation, washing
It is dry, obtain the polystyrene microsphere with cationic function of exchange；Wherein, the 2- acrylamido-2- methyl-1-
Propane sulfonic acid, N, N'- methylene-bisacrylamide, styrene, divinylbenzene, potassium peroxydisulfate formula rate be 0.8~4g:
0.015~0.075g:3.5~4.5ml:0.022~0.028ml:0.09~0.11g.
9. having the preparation method of the polystyrene microsphere of cationic function of exchange according to claim 8, it is characterised in that:
The potassium peroxydisulfate is added in the form of 0.45%~0.55% persulfate aqueous solution.
10. having the preparation method of the polystyrene microsphere of cationic function of exchange according to claim 9, feature exists
In: the volume ratio of the water and persulfate aqueous solution is 3.5~4.5:1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0009395A1 (en) * | 1978-09-19 | 1980-04-02 | Rohm And Haas Company | Cation exchange process, certain cation exchange resins and materials useful therein and processes for their preparation |
| CN103122044A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Sulphonic acid type macroporous ion exchange resin and preparation method thereof |
| KR20140060527A (en) * | 2011-09-13 | 2014-05-20 | 제너럴 일렉트릭 캄파니 | Cation exchange materials prepared in aqueous media |
| CN104119467A (en) * | 2014-07-10 | 2014-10-29 | 上海应用技术学院 | Strong-acid cation exchange resin and preparing method thereof |
| 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 |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0009395A1 (en) * | 1978-09-19 | 1980-04-02 | Rohm And Haas Company | Cation exchange process, certain cation exchange resins and materials useful therein and processes for their preparation |
| KR20140060527A (en) * | 2011-09-13 | 2014-05-20 | 제너럴 일렉트릭 캄파니 | Cation exchange materials prepared in aqueous media |
| CN103122044A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Sulphonic acid type macroporous ion exchange resin and preparation method thereof |
| CN104119467A (en) * | 2014-07-10 | 2014-10-29 | 上海应用技术学院 | Strong-acid cation exchange resin and preparing method thereof |
| 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 |
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