CN107556412A - A kind of micron order sulfonated polystyrene microballoon and its preparation method and application - Google Patents
A kind of micron order sulfonated polystyrene microballoon and its preparation method and application Download PDFInfo
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- CN107556412A CN107556412A CN201710656321.0A CN201710656321A CN107556412A CN 107556412 A CN107556412 A CN 107556412A CN 201710656321 A CN201710656321 A CN 201710656321A CN 107556412 A CN107556412 A CN 107556412A
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- micron order
- sulfonated polystyrene
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- polystyrene microballoon
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Abstract
The invention belongs to sorbing material technical field, discloses a kind of micron order sulfonated polystyrene microballoon and its preparation method and application.The preparation method is：Styrene monomer, dispersant and initiator are added in absolute ethyl alcohol, are warming up to 65~78 DEG C of 10~24h of reaction, solid product is scrubbed, dries, and obtains polystyrene microsphere；Then polystyrene microsphere is added in the concentrated sulfuric acid, 30~80 DEG C of 8~24h of sulfonating reaction, reaction product is scrubbed, dries, and obtains micron order sulfonated polystyrene microballoon.Sulfonic group introducing Surfaces of Polystyrene Microparticles is prepared micron order sulfonated polystyrene microballoon by the present invention, and microspherulite diameter is homogeneous, has the characteristics that adsorption capacity is big, processing speed is fast to heavy metal ion in water.
Description
Technical field
The invention belongs to sorbing material technical field, and in particular to a kind of micron order sulfonated polystyrene microballoon and its preparation
Methods and applications.
Background technology
In numerous micro materials, polystyrene microsphere is steady because of its rigid big, high mechanical strength, acid and alkali-resistance, chemical property
The features such as determining and receive much concern.Wherein its Materials Styrene aboundresources, cheap, and polystyrene microsphere has than table
Area is big, particle size is homogeneous and the property such as controllable.The preparation method of polystyrene microsphere is generally divided into dispersion copolymerization method, seed
Polymerization, emulsion polymerization, wherein seeded polymerization prepare polystyrene microsphere complex steps, it is necessary to carry out secondary swelling system
It is standby, but polystyrene microsphere particle diameter distribution prepared by the method is extensive；Dispersion copolymerization method preparation process is simple, the polyphenyl second of preparation
Alkene microspherulite diameter also can reach micron order, and functional modification is also relatively easy.Polystyrene microsphere grain prepared by emulsion polymerization
Footpath is smaller, generally micron order, has the advantages that particle diameter is small, easily scattered after functional modification.
Because Surfaces of Polystyrene Microparticles does not have functional groups, hydrophobicity is too strong, it is difficult to, limitation compatible with other materials
The application of polystyrene microsphere in other respects.The functionalization of polystyrene microsphere mainly has three kinds of methods at present：First, profit
With the phenyl ring of styrene；Second, utilize the remaining suspension ethylene double bond of phenylethylene micro ball；Third, utilize with particular functional group
Monomer copolymerization.By the functional modification to polystyrene microsphere, its consolidating with bioactive substance such as enzyme, protein can be strengthened
The adsorption capacity of fixedization or heavy metal ion.
At present, the heavy metal in drinking water, mainly carried out by the methods of other activated carbon of grade, ion exchange resin
, the problems such as adsorption rate is slow, and exchange capacity is small, and effect is limited be present in processing.
The content of the invention
In place of shortcoming and defect existing for above prior art, primary and foremost purpose of the invention is to provide a kind of micron
The preparation method of level sulfonated polystyrene microballoon.
Another object of the present invention is to provide a kind of micron order sulfonated polystyrene being prepared by the above method
Microballoon.
It is still another object of the present invention to provide above-mentioned micron order sulfonated polystyrene microballoon in water at heavy metal pollution
Application in reason.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of micron order sulfonated polystyrene microballoon, including following preparation process：
(1) styrene monomer, dispersant and initiator are added in absolute ethyl alcohol, be warming up to 65~78 DEG C reaction 10~
24h, solid product is scrubbed, dries, and obtains polystyrene microsphere；
(2) polystyrene microsphere obtained by step (1) is added in the concentrated sulfuric acid, 30~80 DEG C of 8~24h of sulfonating reaction, instead
Answer product scrubbed, dry, obtain micron order sulfonated polystyrene microballoon.
Dispersant described in step (1) is preferably polyvinylpyrrolidone, and the addition of dispersant is styrene monomer matter
The 1.0~6.0% of amount.
The initiator is preferably azodiisobutyronitrile, the addition of initiator for styrene monomer quality 0.3~
1.0%.
Preferably, the washing described in step (1) refers to wash using absolute ethyl alcohol；Described drying refers to 50~60
24h is dried in vacuo at DEG C.
Preferably, the ratio that polystyrene microsphere described in step (2) and the concentrated sulfuric acid add is 1:(10~40) g/mL.
Preferably, the washing described in step (2) refers to alternately wash using water and absolute ethyl alcohol；Described drying refers to
12h is dried in vacuo at 60 DEG C.
Preferably, the temperature of sulfonating reaction described in step (2) is 30~60 DEG C, and the time is 10~24h.
A kind of micron order sulfonated polystyrene microballoon, is prepared by the above method.
Application of the above-mentioned micron order sulfonated polystyrene microballoon in water in heavy metal pollution processing.
The present invention principle be：Using styrene as monomer, use dispersion copolymerization method to prepare polystyrene microsphere as matrix, lead to
Cross concentrated acid sulfonation modification and sulfonic group is introduced to Surfaces of Polystyrene Microparticles, it is carried electronegativity in aqueous, not only
Solve the problems, such as its hydrophobicity strong and and the spy of polystyrene microsphere Liquidity limit can not be improved with other substances compatibles
Property, and can heavy metal in quick adsorption water, realize the quick and emergency processing of heavy metal pollution water quality.
The present invention preparation method and resulting product has the following advantages that and beneficial effect：
(1) sulfonic group introducing Surfaces of Polystyrene Microparticles is prepared micron order sulfonated polystyrene microballoon, microballoon by the present invention
Not only uniform particle diameter, reach 1.8 μm, and sulfonation degree is high, has fabulous hydrophily；
(2) the micron order sulfonated polystyrene microballoon for preparing of the present invention, specific surface area is big, have quick adsorption lead, arsenic,
The effect of the cationic functionals such as calcium, magnesium, have the characteristics that capacity is big, processing speed is fast, can be in 5 minutes, a quick adsorption huge sum of money
Category, has good advantage in the emergency processing material of the heavy metal pollution of drinking water and industrial wastewater.
Brief description of the drawings
Fig. 1 is the sem test result figure of the gained micron order sulfonated polystyrene microballoon of the embodiment of the present invention 1；
Fig. 2 is present invention gained micron order sulfonated polystyrene microballoon to Pb2+The adsorption effect figure.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) 2g PVP-30 are taken to be added in the three-necked flask containing 200mL absolute ethyl alcohols, ultrasonic disperse, stirring, and fill
Nitrogen is protected, and is warming up to 75 DEG C, adds 50mL styrene, 0.4g azodiisobutyronitriles, and 24h, gained polymerization are reacted under stirring condition
Thing microballoon is washed more than three times with absolute ethyl alcohol, and 24h is dried in vacuo at 60 DEG C, obtains PS microballoons.
(2) it is 1 according to PS microballoons and concentrated sulfuric acid ratio:PS is added in the concentrated sulfuric acid by 40g/mL, in 40 DEG C, mechanical agitation
Lower reaction 24h, through water, absolute ethyl alcohol, alternately washing for several times, is dried in vacuo 12h at 60 DEG C, obtains powdered breast reaction product
White micron order sulfonated polystyrene microballoon.
Gained micron order sulfonated polystyrene microballoon is scanned Electronic Speculum test, as a result as shown in Figure 1.Can by Fig. 1 results
To find out, present invention gained polystyrene microsphere uniform particle diameter, reach 1.8 micron orders.
Embodiment 2
(1) 0.8g PVP-30 are taken to be added in the three-necked flask containing 200mL absolute ethyl alcohols, ultrasonic disperse, stirring, and
Nitrogen filled protection, 70 DEG C are warming up to, add 50mL styrene, 0.5g azodiisobutyronitriles, react 20h under stirring condition, gained gathers
Compound microballoon is washed more than three times with absolute ethyl alcohol, and 24h is dried in vacuo at 50 DEG C, obtains PS microballoons.
(2) it is 1 according to PS microballoons and concentrated sulfuric acid ratio:PS is added in the concentrated sulfuric acid by 30g/mL, in 60 DEG C, mechanical agitation
Lower reaction 20h, through water, absolute ethyl alcohol, alternately washing for several times, is dried in vacuo 12h at 60 DEG C, obtains powdered breast reaction product
White micron order sulfonated polystyrene microballoon.
Embodiment 3
(1) 1.5g PVP-30 are taken to be added in the three-necked flask containing 200mL absolute ethyl alcohols, ultrasonic disperse, stirring, and
Nitrogen filled protection, 68 DEG C are warming up to, add 50mL styrene, 0.2g azodiisobutyronitriles, react 20h under stirring condition, gained gathers
Compound microballoon is washed more than three times with absolute ethyl alcohol, and 24h is dried in vacuo at 50 DEG C, obtains PS microballoons.
(2) it is 1 according to PS microballoons and concentrated sulfuric acid ratio:PS is added in the concentrated sulfuric acid by 30g/mL, in 60 DEG C, mechanical agitation
Lower reaction 12h, through water, absolute ethyl alcohol, alternately washing for several times, is dried in vacuo 12h at 60 DEG C, obtains powdered breast reaction product
White micron order sulfonated polystyrene microballoon.
Embodiment 4
(1) 0.8g PVP-30 are taken to be added in the three-necked flask containing 200mL absolute ethyl alcohols, ultrasonic disperse, stirring
30min, and nitrogen filled protection, 72 DEG C are warming up to, add 50mL styrene, 0.4g azodiisobutyronitriles, reacted under stirring condition
20h, resulting polymers microballoon are washed more than three times with absolute ethyl alcohol, and 24h is dried in vacuo at 50 DEG C, obtain PS microballoons.
(2) it is 1 according to PS microballoons and concentrated sulfuric acid ratio:PS is added in the concentrated sulfuric acid by 30g/mL, in 60 DEG C, mechanical agitation
Lower reaction 10h, through water, absolute ethyl alcohol, alternately washing for several times, is dried in vacuo 12h at 60 DEG C, obtains powdered breast reaction product
White micron order sulfonated polystyrene microballoon.
Embodiment 5
(1) take 3g PVP-30 to be added in the three-necked flask containing 200mL absolute ethyl alcohols, ultrasonic disperse, stir 30min,
And nitrogen filled protection, 68 DEG C are warming up to, 50mL styrene, 0.5g azodiisobutyronitriles is added, reacts 20h, gained under stirring condition
Polymer microballoon is washed more than three times with absolute ethyl alcohol, and 24h is dried in vacuo at 50 DEG C, obtains PS microballoons.
(2) it is 1 according to PS microballoons and concentrated sulfuric acid ratio:PS is added in the concentrated sulfuric acid by 30g/mL, in 60 DEG C, mechanical agitation
Lower reaction 20h, through water, absolute ethyl alcohol, alternately washing for several times, is dried in vacuo 12h at 60 DEG C, obtains powdered breast reaction product
White micron order sulfonated polystyrene microballoon.
Gained micron order sulfonated polystyrene microballoon of the invention is tested the absorption property of heavy metal ion in water：
(1) 0.05g micron order sulfonated polystyrene microballoons are taken to be put into containing 100mL about 9mg/L Pb2+Solution, 28~40
Concussion absorption 5min, centrifugation, supernatant Pb at a temperature of DEG C2+Concentration is less than 0.5mg/L, reaches domestic water standard.Micron order sulphur
Change polystyrene microsphere to Pb2+Adsorption effect see Fig. 2.
(2) 0.05g micron order sulfonated polystyrene microballoons are taken to be put into containing 100mL about 10mg/L Zn2+Solution, 28~
Concussion absorption 5min, centrifugation, supernatant Zn at a temperature of 40 DEG C2+Concentration is less than 1.0mg/L, reaches domestic water standard.
(3) 0.05g micron order sulfonated polystyrene microballoons are taken to be put into containing 100mL about 10mg/L Cu2+Solution, 28~
Concussion absorption 5min, centrifugation, supernatant C u at a temperature of 40 DEG C2+Concentration is less than 1.0mg/L, reaches domestic water standard.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of micron order sulfonated polystyrene microballoon, it is characterised in that including following preparation process：
(1) styrene monomer, dispersant and initiator are added in absolute ethyl alcohol, are warming up to 65~78 DEG C of 10~24h of reaction,
Solid product is scrubbed, dries, and obtains polystyrene microsphere；
(2) polystyrene microsphere obtained by step (1) is added in the concentrated sulfuric acid, 30~80 DEG C of 8~24h of sulfonating reaction, reaction production
Thing is scrubbed, dries, and obtains micron order sulfonated polystyrene microballoon.
A kind of 2. preparation method of micron order sulfonated polystyrene microballoon according to claim 1, it is characterised in that：Step
(1) dispersant described in is polyvinylpyrrolidone, and the addition of dispersant is the 1.0~6.0% of styrene monomer quality.
A kind of 3. preparation method of micron order sulfonated polystyrene microballoon according to claim 1, it is characterised in that：It is described
Initiator is azodiisobutyronitrile, and the addition of initiator is the 0.3~1.0% of styrene monomer quality.
A kind of 4. preparation method of micron order sulfonated polystyrene microballoon according to claim 1, it is characterised in that：Step
(1) washing described in refers to wash using absolute ethyl alcohol；Described drying refers to be dried in vacuo 24h at 50~60 DEG C.
A kind of 5. preparation method of micron order sulfonated polystyrene microballoon according to claim 1, it is characterised in that：Step
(2) ratio that polystyrene microsphere described in and the concentrated sulfuric acid add is 1:(10~40) g/mL.
A kind of 6. preparation method of micron order sulfonated polystyrene microballoon according to claim 1, it is characterised in that：Step
(2) washing described in refers to alternately wash using water and absolute ethyl alcohol；Described drying refers to be dried in vacuo at 60 DEG C
12h。
A kind of 7. preparation method of micron order sulfonated polystyrene microballoon according to claim 1, it is characterised in that：Step
(2) temperature of sulfonating reaction described in is 30~60 DEG C, and the time is 10~24h.
A kind of 8. micron order sulfonated polystyrene microballoon, it is characterised in that：Pass through the method described in any one of claim 1~7
It is prepared.
9. application of the micron order sulfonated polystyrene microballoon described in claim 8 in water in heavy metal pollution processing.
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Cited By (3)
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| CN110124637A (en) * | 2019-05-30 | 2019-08-16 | 湖南省环境保护科学研究院 | A kind of waste water containing thallium adsorbent material and preparation method thereof |
| CN113845610A (en) * | 2021-09-22 | 2021-12-28 | 西安纳瑞工控科技有限公司 | Sodium polystyrene sulfonate and preparation method thereof |
| CN114395082A (en) * | 2022-02-21 | 2022-04-26 | 武汉纺织大学 | Preparation method of sulfonated polystyrene nano-microspheres |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110124637A (en) * | 2019-05-30 | 2019-08-16 | 湖南省环境保护科学研究院 | A kind of waste water containing thallium adsorbent material and preparation method thereof |
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| CN113845610B (en) * | 2021-09-22 | 2023-09-01 | 西安纳瑞工控科技有限公司 | Sodium polystyrene sulfonate and preparation method thereof |
| CN114395082A (en) * | 2022-02-21 | 2022-04-26 | 武汉纺织大学 | Preparation method of sulfonated polystyrene nano-microspheres |
| CN114395082B (en) * | 2022-02-21 | 2024-02-06 | 武汉纺织大学 | Preparation method of sulfonated polystyrene nano-microsphere |
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Effective date of registration: 20180613 Address after: 510640 No. five, 381 mountain road, Guangzhou, Guangdong, Tianhe District Applicant after: Xiao Kaijun Applicant after: Guangzhou South China University of Technology science and Technology Park Co., Ltd. Address before: 510640 No. five, 381 mountain road, Guangzhou, Guangdong, Tianhe District Applicant before: South China University of Technology Applicant before: Guangzhou Environmental Protection Technology Co., Ltd. |
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Effective date of registration: 20190325 Address after: 528313 Shunlian Machinery City, 18 Xingye Road, Guanglong Industrial Park, Chencun Town, Shunde District, Foshan City, Guangdong Province, 22 415 and 416 Applicant after: Guangdong Huakaimingxin Technology Co., Ltd. Address before: 510640 No. five, 381 mountain road, Guangzhou, Guangdong, Tianhe District Applicant before: Xiao Kaijun Applicant before: Guangzhou South China University of Technology science and Technology Park Co., Ltd. |
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Application publication date: 20180109 |