CN108794672A - A kind of monodisperse polystyrene microsphere and its preparation method and application - Google Patents
A kind of monodisperse polystyrene microsphere and its preparation method and application Download PDFInfo
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- CN108794672A CN108794672A CN201810548792.4A CN201810548792A CN108794672A CN 108794672 A CN108794672 A CN 108794672A CN 201810548792 A CN201810548792 A CN 201810548792A CN 108794672 A CN108794672 A CN 108794672A
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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
- C08F112/00—Homopolymers 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
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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Abstract
The invention discloses a kind of preparation methods of monodisperse polystyrene microsphere, and under ultrasound condition, small molecular alcohol, which is added, makes styrene be scattered in redistilled water, forms homogeneous and transparent mixed liquor；Initiator is added, target product can be obtained by stirring lower reaction.Product prepared by the present invention can be widely used for market for manufactured goods turned out by light industry, also can be used for powder class and type of latex type cosmetics.Compared with prior art, polystyrene microsphere monodispersity produced by the present invention is good, and size tunable is strong, and using one pot reaction, preparation method is simple, and product can be prepared in batches, and without using stabilizer in reaction process, synthesis process is environmental-friendly.
Description
Technical field
The invention belongs to Emulsifier-free Emulsion Polymerization Technology field, it is related to a kind of monodisperse polystyrene microsphere and its preparation side
Method and application.
Background technology
Emulsion polymerization is monomer by emulsifier and mechanical agitation, makes monomer be dispersed in water to form lotion, adds and draw
A kind of reaction that agent causes monomer polymerization is sent out, is an important preparation method for synthesizing high molecular material.It the advantage is that：(1)
Polymerization speed is fast, and molecular weight product is high；(2) make dispersant media with water, be conducive to the temperature control that conducts heat；(3) reaction reaches high conversion
Afterwards, the viscosity of newborn aggressiveness system is still very low, and dispersion is stablized, and is relatively easy to control and realizes continuous operation etc..But traditional lotion is poly-
In conjunction, after emulsion film forming, emulsifier can mutually move to surface and the enrichment of latex film by polymer body, be brought into final production
In product, the aftertreatment technologies such as washing also are difficult to it is completely cleared.The factors such as isolation, water suction, exudation in the presence of emulsifier drop
The low water resistance of polymeric articles, solvent resistance and mechanical property make its application be restricted, while emulsifier price is high
It is expensive, increase product cost.Matsumoto and Ochi (document) under conditions of being entirely free of emulsifier, is synthesized in nineteen sixty
Polystyrene, polymethyl methacrylate and polyvinyl acetate emulsion with granularity monodispersity emulsion particle, hereafter
Emulsifier-free emulsion polymerization prepares polymer microballoon and just develops rapidly.Emulsifier-free emulsion polymerization is not added with breast completely during the reaction
Micro emulsifier (its concentration is less than critical micelle concentration CMC), the grain of the more conventional emulsion polymerization of microspherulite diameter is only added in agent
Sub big, the single dispersion of latex particle size, clean surface need not remove emulsifier this post-processing.Product is widely used in facing
The fields such as bed medicine, cytology, material science, chromatographic isolation.
Monodisperse polymer microballoon is because having controllable form, adjustable molecular weight, being easy to introduce difference on surface in recent years
The characteristics such as functional group, receive significant attention.It is the widest with the preparation and application of polystyrene microsphere in polymer microballoon
It is general, provide template or construction unit for constructing for orderly low-dimensional nano structure.
Application No. is 200710098739.0 Chinese invention patents to disclose a kind of monodisperse polystyrene microsphere
The preparation method of size tunable, for this method using styrene as monomer, potassium peroxydisulfate is initiator, and water is reaction media, with poly- second
Alkene pyrrolidone is stabilizer, using the method for emulsifier-free emulsion polymerization, prepares polystyrene microsphere；Prepare the monodispersity of gained
The particle size range of polystyrene microsphere is 250-1400nm.Different from above-mentioned patented technology, the present invention is to make small molecule alcohol
For surfactant, it is introduced into the polymerization system of styrene, and the present invention is without using stabilizer.It is special compared to above-mentioned
Profit, technological merit of the invention are mainly reflected in the following aspects：1) without using stabilizer, product need not additionally be removed
In stabilizer；2) material toxicity is small, and preparation method is simple.
Invention content
To overcome defect of the existing technology, the present invention provides a kind of preparation sides of monodisperse polystyrene microsphere
Method, using redistilled water as solvent, is prepared using styrene as monomer by emulsifier-free emulsion polymerization reaction.When preparation, super
Under the conditions of sound, small molecular alcohol, which is added, makes styrene be scattered in redistilled water, forms homogeneous and transparent mixed liquor；It is added and causes
After agent, mixed liquor is placed in 70 DEG C of water-baths, according to the addition of styrene, stirs lower reaction, 5-48 hours through vapor
Distillation centrifuges (alcohol is washed, washed), can obtain target product.Gained target product of the invention is that a kind of monodispersity is good, stores
The good monodisperse polystyrene microsphere of excellent in stability, optical property.
The present invention provides a kind of preparation methods of monodisperse polystyrene microsphere；This method specifically includes following step
Suddenly：
Step (1)：Styrene is first washed with solution, is then cleaned with solvent, is obtained after purification by vacuum distillation
Styrene.
Step (2)：Identical solvent is added the styrene after purification that above-mentioned steps (1) are obtained with above-mentioned steps (1)
In container, small molecular alcohol, ultrasound to mixed liquor clear is then added dropwise.
Step (3)：Initiator is added into the mixed liquor of above-mentioned steps (2) clear.
Step (4)；Container is positioned in water-bath, reaction is stirred.
Step (5)：By step (4) product obtained by the reaction through centrifugation, washing, redisperse, circular treatment removes incomplete
The monodisperse polystyrene microsphere of uniform particle sizes is made in styrene and initiator of reaction etc..
In step (1), the solution is one kind in sodium hydroxide solution, alkali alumina etc.；Preferably, it is hydroxide
Sodium solution.
In step (1), a concentration of 5-10wt% of the solution；Preferably, it is 10wt%.
In step (1), the purpose that styrene is washed with solution is the polymerization inhibitor removed in styrene, and criterion is
The sodium hydroxide that liquid separation goes out is clear.
In step (1), the number of the solution washing is 1-3 times；Preferably, it is 3 times.
In step (1), the solvent is a kind or several in redistilled water, high purity water etc., to reduce exogenous impurity
It influences；Preferably, it is redistilled water.
In step (1), described with the purpose of solvent is cleaning styrene to neutrality.
In step (1), the number of the solvent washing is 2-4 times；Preferably, it is 4 times.
In step (1), the temperature of the vacuum distillation is 18-25 DEG C；Preferably, it is 25 DEG C.
In step (1), the time of the vacuum distillation is 20-50min；Preferably, it is 40min.
In step (1), in the vacuum distillation process, 20 DEG C or so evaporate takes the styrene of object as after purification.
In step (1), further comprise, styrene after purification is placed in drier household freezer and is preserved.
In step (2), the container can be three-neck flask or the flask of other specifications.
In step (2), the small molecular alcohol refers to the alcohol of C1-C8, includes commonly：Methanol, ethyl alcohol, normal propyl alcohol, isopropyl
One or more of alcohol, n-butanol, tert-butyl alcohol etc.；Preferably, it is methanol, ethyl alcohol, isopropanol, the tert-butyl alcohol.It is drop that it, which is acted on,
The surface tension of low distilled water, is scattered in convenient for styrene in distilled water.
In step (2), the temperature of the ultrasound is 20-25 DEG C；Preferably, it is 25 DEG C.
In step (2), the time of the ultrasound is 20-30min；Preferably, it is 30min.
In step (2), the operation of small molecular alcohol, which is added dropwise, to be carried out under ultrasound condition.
In step (2), the volume ratio of the solvent and styrene after purification is (100-110)：(4-5)；Preferably, it is
100：4.6.
Small molecular alcohol is selected to do surface reactive material in step (2), the organic matters such as more previous macromolecular do surface-active substance
For matter, toxicity is low and environmental pollution is small, and controllability is strong.
In step (3), the initiator is potassium peroxydisulfate (KPS), azodiisobutyronitrile (AIBN), dibenzoyl peroxide
One or more of (BPO) etc.；Preferably, it is potassium peroxydisulfate (KPS).
In step (3), the mass ratio of the initiator and styrene after purification is (1-1.5)：(40-42)；Preferably,
It is 1：40.
In step (4), according to the content of styrene, the time of the reaction is generally 5-48 hours.
In step (4), the temperature of the reaction is 60-75 DEG C；Preferably, it is 70 DEG C.
In step (4), the stirring operation, the magnetic agitation that additional agitating device or water-bath can be used to carry turns
Speed is suitable.
In step (5), the grain size of the polystyrene is 120-200nm；Preferably, it is 140nm.
The invention also provides the monodisperse polystyrene microspheres obtained by above-mentioned preparation method.
Wherein, the grain size of the polystyrene is 120-200nm；Preferably, it is 140nm.
The present invention also provides application of the polystyrene microsphere in market for manufactured goods turned out by light industry, powder class and type of latex type cosmetics.
The beneficial effects of the present invention are：The preparation method of monodisperse polystyrene microsphere provided by the invention and existing skill
Art is compared, and is had the following advantages：
(1) the polystyrene microsphere monodispersity being prepared is good, and size tunable is strong；
(2) the polystyrene microsphere emulsion being prepared, storage stability；
(3) use one pot reaction, preparation process simple；
(4) small molecular alcohol small toxicity, environmental pollution are small；
(5) without using stabilizer, the stabilizer in product need not additionally be removed；
(6) present invention selects small molecular alcohol to do surface reactive material, and the organic matters such as more previous macromolecular do surface-active substance
For matter, toxicity is low and environmental pollution is small, and controllability is strong；
(7) product can be prepared in batches.
Description of the drawings
Fig. 1 (a) is the monodisperse polystyrene microsphere electron microscope that embodiment 1 is prepared；
Fig. 1 (b) is the dynamic light scattering diagram for the monodisperse polystyrene that embodiment 1 is prepared；
Fig. 2 (a) is the monodisperse polystyrene microsphere electron microscope that embodiment 2 is prepared；
Fig. 2 (b) is the monodisperse polystyrene microsphere dynamic light scattering diagram that embodiment 2 is prepared；
Fig. 3 (a) is the monodisperse polystyrene microsphere electron microscope that embodiment 3 is prepared；
Fig. 3 (b) is the monodisperse polystyrene microsphere dynamic light scattering diagram that embodiment 3 is prepared；
Fig. 4 (a) is the monodisperse polystyrene microsphere electron microscope that embodiment 4 is prepared；
Fig. 4 (b) is the monodisperse polystyrene microsphere dynamic light scattering diagram that embodiment 4 is prepared.
Specific implementation mode
It elaborates in conjunction with the following drawings to the embodiment of the present invention.Specific embodiment is with technical scheme of the present invention
Premised on implemented, including detailed embodiment and specific operating process, but protection scope of the present invention is not limited to down
State embodiment.
Embodiment 1
The method that the present embodiment prepares monodisperse polystyrene microsphere includes the following steps：
It measures in the styrene monomer 4.6ml purified, redistilled water 100ml addition 250mL three-neck flasks, beaker is put
(ultrasonic power is set as 99%, and ultrasonic time is set as 30min) is placed in Ultrasound Instrument, and it is (selected that methanol is added in ultrasound
Methanol specification is to analyze pure, content >=99.7%) become uniform, clear to mixed liquor, record methanol is 175ml.It weighs
0.1013g potassium peroxydisulfate solid powders are added in beaker, beaker are positioned in water-bath, temperature is set as 70 DEG C and opens magnetic
Power stirs button (mixing speed is suitable ,~300rmp), and the reaction time controlled at 6-7 hours, and reaction terminates, steam distillation 1h.
Under stirring, lotion natural cooling washes-ultrasonic disperse/centrifugation-washing/ultrasonic dispersion cycle behaviour by centrifuging ethyl alcohol
Make, processing product 3 times (rotating speed 16000rmp, time 20min are chosen in centrifugation) can obtain target product.The present embodiment is prepared
Polystyrene microsphere (134nm or so) such as Fig. 1 (containing figure a, b) shown in.
Embodiment 2
The method that the present embodiment prepares monodisperse polystyrene microsphere includes the following steps：
It measures in the styrene monomer 4.6ml purified, redistilled water 100ml addition 250mL three-neck flasks, beaker is put
(ultrasonic power is set as 99%, and ultrasonic time is set as 30min) is placed in Ultrasound Instrument, and it is (selected that ethyl alcohol is added in ultrasound
Ethyl alcohol specification is to analyze pure, content >=99.5%) become uniform, clear to mixed liquor, record ethyl alcohol is 120ml.It weighs
Mixed liquor is added in 0.1124g potassium peroxydisulfate solid powders, beaker is positioned in water-bath, temperature is set as 70 DEG C and opens magnetic
Power stirs button (mixing speed is suitable ,~300rmp), and the reaction time controlled at 6-7 hours, and reaction terminates, steam distillation 1h.
Under stirring, lotion natural cooling washes-ultrasonic disperse/centrifugation-washing/ultrasonic dispersion cycle behaviour by centrifuging ethyl alcohol
Make, processing product 3 times (rotating speed 16000rmp, time 20min are chosen in centrifugation) can obtain target product.The present embodiment is prepared
Polystyrene microsphere (140nm or so) such as Fig. 2 (containing figure a, b) shown in.
Embodiment 3
The method that the present embodiment prepares monodisperse polystyrene microsphere includes the following steps：
It measures in the styrene monomer 4.6ml purified, redistilled water 100ml addition 250mL three-neck flasks, beaker is put
(ultrasonic power is set as 99%, and ultrasonic time is set as 30min) is placed in Ultrasound Instrument, and it is (selected that isopropanol is added in ultrasound
It is to analyze pure, content >=99.7% with isopropanol specification) become uniform, clear to mixed liquor, record isopropanol is 90ml.
It weighs 0.1052g potassium peroxydisulfate solid powders and mixed liquor is added, beaker is positioned in water-bath, temperature is set as 70 DEG C and opens
Magnetic agitation button (mixing speed is suitable ,~300rmp) is opened, the reaction time controlled at 6-7 hours, and reaction terminates, steam distillation
1h.Under stirring, lotion natural cooling washes-ultrasonic disperse/centrifugation-washing/ultrasonic dispersion cycle by centrifuging ethyl alcohol
Operation, processing product 3 times (rotating speed 16000rmp, time 20min are chosen in centrifugation), can obtain target product.The present embodiment is prepared into
Shown in the polystyrene microsphere (144nm or so) arrived such as Fig. 3 (a, b containing figure).
Embodiment 4
The method that the present embodiment prepares monodisperse polystyrene microsphere includes the following steps：
It measures in the styrene monomer 4.6ml purified, redistilled water 100ml addition 250mL three-neck flasks, beaker is put
(ultrasonic power is set as 99%, and ultrasonic time is set as 30min) is placed in Ultrasound Instrument, and it is (selected that the tert-butyl alcohol is added in ultrasound
With tert-butyl alcohol specification, chemical pure, content >=98.0%) to mixed liquor become uniform, clear, the record tert-butyl alcohol is 80ml.
It weighs 0.1025g potassium peroxydisulfate solid powders to be added in mixed liquor, beaker is positioned in water-bath, temperature is set as 70 DEG C simultaneously
Magnetic agitation button (mixing speed is suitable ,~300rmp) is opened, the reaction time controlled at 6-7 hours, and reaction terminates, and vapor steams
Evaporate 1h.Under stirring, lotion natural cooling, washed by centrifuging ethyl alcohol-ultrasonic disperse/centrifugation-washing/ultrasonic disperse follows
Ring operates, and processing product 3 times (rotating speed 16000rmp, time 20min are chosen in centrifugation) can obtain target product.It is prepared by the present embodiment
Shown in obtained polystyrene microsphere (146nm or so) such as Fig. 4 (a, b containing figure).
The protection content of the present invention is not limited to above example.Without departing from the spirit and scope of the invention, originally
Field technology personnel it is conceivable that variation and advantage be all included in the present invention, and with appended claims be protect
Protect range.
Claims (14)
1. a kind of preparation method of monodisperse polystyrene microsphere, which is characterized in that this approach includes the following steps：
(1) styrene is first washed with solution, is then cleaned with solvent, styrene after purification is obtained by vacuum distillation；
(2) identical solvent is added to the container the styrene after purification for obtaining step (1) with above-mentioned steps (1), is then dripped
Add small molecular alcohol, ultrasound to mixed liquor clear；
(3) initiator is added into the mixed liquor of above-mentioned steps (2) clear；
(4) container is positioned in water-bath, is stirred reaction；
(5) by step (4) product obtained by the reaction through centrifugation, washing, redisperse, circular treatment removes the benzene not reacted completely
The monodisperse polystyrene microsphere of uniform particle sizes is made in ethylene and initiator.
2. according to the method described in claim 1, it is characterized in that, in step (1), the solution is sodium hydroxide solution, alkali
One or both of property aluminium oxide；A concentration of 5-10wt% of the solution.
3. according to the method described in claim 1, it is characterized in that, in step (1), the solvent is redistilled water, high-purity
1 kind in water or 2 kinds, to reduce the influence of exogenous impurity.
4. according to the method described in claim 1, it is characterized in that, in step (1), the temperature of the vacuum distillation is 18-25
℃；The time of the vacuum distillation is 20-50min；In the vacuum distillation process, 20 DEG C evaporate takes the benzene of object as after purification
Ethylene.
5. according to the method described in claim 1, it is characterized in that, in step (2), the small molecular alcohol refers to the alcohol of C1-C8,
Including：One or more of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, tert-butyl alcohol.
6. according to the method described in claim 1, it is characterized in that, in step (2), the temperature of the ultrasound is 20-25 DEG C；
The time of the ultrasound is 20-30min.
7. according to the method described in claim 1, it is characterized in that, in step (2), the solvent and styrene after purification
Volume ratio is (100-110)：(4-5).
8. according to the method described in claim 1, it is characterized in that, in step (3), the initiator is potassium peroxydisulfate KPS, idol
One or more of nitrogen bis-isobutyronitrile AIBN, dibenzoyl peroxide BPO.
9. according to the method described in claim 1, it is characterized in that, in step (3), the initiator and styrene after purification
Mass ratio be (1-1.5)：(40-42).
10. according to the method described in claim 1, it is characterized in that, in step (4), the temperature of the reaction is 60-75 DEG C；
The time of the reaction is 5-48 hours.
11. according to the method described in claim 1, it is characterized in that, in step (5), the grain size of the polystyrene is 120-
200nm。
12. the monodisperse polystyrene microsphere that a kind of any one method such as claim 1-11 is prepared.
13. polystyrene microsphere as claimed in claim 12, which is characterized in that the grain size of the polystyrene is 120-
200nm。
14. application of the polystyrene microsphere as claimed in claim 12 in market for manufactured goods turned out by light industry, powder class and type of latex type cosmetics.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5714610A (en) * | 1980-06-30 | 1982-01-25 | Sekisui Chem Co Ltd | Production of latex for serodiagnotic reagent |
| CN103130935A (en) * | 2013-03-15 | 2013-06-05 | 湖南科技大学 | Simple method for preparing monodisperse anionic polystyrene microsphere |
| CN103159878A (en) * | 2013-04-03 | 2013-06-19 | 湖南科技大学 | Simple method for preparing monodisperse cationic polystyrene microspheres |
-
2018
- 2018-05-31 CN CN201810548792.4A patent/CN108794672B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5714610A (en) * | 1980-06-30 | 1982-01-25 | Sekisui Chem Co Ltd | Production of latex for serodiagnotic reagent |
| CN103130935A (en) * | 2013-03-15 | 2013-06-05 | 湖南科技大学 | Simple method for preparing monodisperse anionic polystyrene microsphere |
| CN103159878A (en) * | 2013-04-03 | 2013-06-19 | 湖南科技大学 | Simple method for preparing monodisperse cationic polystyrene microspheres |
Non-Patent Citations (1)
| Title |
|---|
| 朱雯: "无皂乳液聚合法制备单分散聚苯乙烯微球", 《功能材料》 * |
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Address after: 200241 No. 500, Dongchuan Road, Shanghai, Minhang District Patentee after: EAST CHINA NORMAL University Address before: 200062 No. 3663, Putuo District, Shanghai, Zhongshan North Road Patentee before: EAST CHINA NORMAL University |