CN106674390A - Method for preparing ultra-high molecular weight polystyrene under room temperature through emulsion polymerization - Google Patents
Method for preparing ultra-high molecular weight polystyrene under room temperature through emulsion polymerization Download PDFInfo
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- CN106674390A CN106674390A CN201611258871.9A CN201611258871A CN106674390A CN 106674390 A CN106674390 A CN 106674390A CN 201611258871 A CN201611258871 A CN 201611258871A CN 106674390 A CN106674390 A CN 106674390A
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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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- 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
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/30—Inorganic compounds
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Abstract
The invention discloses a method for preparing ultra-high molecular weight polystyrene under room temperature through emulsion polymerization and belongs to the field of polymer synthesis. The method comprises the following steps: by taking peroxysulphate as an initiator, water as a medium, an anionic surfactant as an emulsifying agent, sodium bicarbonate as a pH regulator and phenylethylene as a monomer, performing polymerization reaction for 1-6 hours under room temperature and normal pressure, thereby successfully acquiring the ultra-high molecular weight polystyrene with weight-average molecular weight above 250*10<4>g/mol, wherein the monomer conversion rate is 85% or above. According to the invention, the polymerization system is simple and stable; due to the use of the commoditized reaction materials, the polymerization cost is greatly lowered; the operation is easy, the condition is mild and the influence on the environment is less; temperature control and pressurizing are not required by the reaction; the energy consumption is low; the reaction time is short and the monomer conversion rate is high; the acquired ultra-high molecular weight polystyrene is high in molecular weight and narrow in molecular weight distribution; and the molecular weight can be regulated within a wider scope. The method disclosed by the invention has important significance in theoretical research and large-scale application of the ultra-high molecular weight polystyrene.
Description
Technical field
The invention belongs to field of functional polymer preparation in Polymer Synthesizing, and in particular to a kind of room temperature prepares supra polymer
The emulsion polymerization synthetic technology of amount polystyrene.
Background technology
Polystyrene is a kind of thermoplastic resin, but ordinary polystyrene has impact strength low, and thermostability is not high
Shortcoming, thus application be restricted.Improving its performance has various methods, wherein it is in recent years to prepare polystyrene with super-high molecular weight
One of research direction.Polystyrene with super-high molecular weight had both remained excellent optical property specific to general polystyrene, easily
Processing characteristics, and with higher mechanical strength and thermostability.Therefore, development and the synthesis of abundant polystyrene with super-high molecular weight
Method has important value.
Mainly adopt polysubstituted Bibenzyl compound (carbon-to-carbon of bonding compound) at present and cause styrene body for initiator
Polymerisation in solution；Rare earth catalyst, Calixarene and Mg (n-Bu)2, the ternary complex catalysts that constituted of HMPA Jing under high pressure
Coordination polymerization；Azo compound is initiator, and organic tellurium is chain-transferring agent, and Jing active free radical soap-free emulsion polymerizations cause
Styrene is prepared into polystyrene with super-high molecular weight.Initiator system is complicated, and efficiency of initiation is relatively low, and more impurity is introduced in product.
Coordination polymerization system is complicated, operating difficultiess, and condition is harsh.The reaction system of activity/controllable soap-free emulsion radical polymerization is complicated,
Severe reaction conditions, polyreaction are wayward.Above-mentioned polymerization during polystyrene with super-high molecular weight is prepared, also
Two common shortcomings, polymerization time needed for high monomer conversion ratio is longer, and carries out at a relatively high temperature in reaction, has
Reaction is even carried out under high pressure, and the molecular weight of gained polystyrene is still affected by various factors.These deficiencies are to a certain degree
On limit the development of polystyrene with super-high molecular weight scale application.And emulsion polymerization is with water as medium, Environmental Safety, polymerization
Speed is fast, and the response time is short, and free radical is isolated in emulsion, reduces the probability of radical termination, reduces to a certain extent
Chain termination speed, therefore resulting polymers molecular weight is high and molecular weight distribution is narrower.
The content of the invention
Object of the present invention is to provide a kind of method that emulsion polymerization room temperature prepares polystyrene with super-high molecular weight, should
Method reaction system is simple to operation, and rate of polymerization is fast, and monomer conversion is high, and gained polystyrene molecular weight is high and molecular weight divides
Cloth is narrow.It is characterized in that with potassium peroxydisulfate or Ammonium persulfate. as initiator, under Conditions of Emulsion Polymerization, room temperature causes styrene, directly
Deliver a child into polystyrene with super-high molecular weight, polymerization system is simple and stable, operate easy, the response time is short and monomer conversion
Height, the molecular weight height of gained polystyrene and narrow molecular weight distribution, and the molecule of polystyrene can be adjusted according to polymerizing condition
Amount.
A kind of method that emulsion polymerization room temperature prepares polystyrene with super-high molecular weight, including：Persulfate is adopted to cause
Agent, water is medium, and anionic surfactant is emulsifying agent, and sodium bicarbonate is pH adjusting agent, and styrene is polymerized monomer, is led to
Free-radical emulsion polymerization is crossed, reaction at room temperature obtains polystyrene with super-high molecular weight.
In preferred technical scheme, described initiator is potassium peroxydisulfate or Ammonium persulfate.；
In preferred technical scheme, described initiator:The molal weight ratio of polymerized monomer is 1~5:100；
In preferred technical scheme, described water:The mass ratio of polymerized monomer is 2~5:1；
In preferred technical scheme, polymeric reaction temperature：Room temperature；Polymerization reaction time is controlled to 1-6 hours；
In preferred technical scheme, described polymerization is emulsion polymerization, and mechanism of polymerization is radical polymerization；
In preferred technical scheme, described surfactant is dodecylbenzene sodium sulfonate or lauryl sulphate acid
Sodium；
In preferred technical scheme, described surfactant:The mass ratio of polymerized monomer is 4-6%；
In preferred technical scheme, the consumption of described pH adjusting agent sodium bicarbonate is 2~4wt% of polymerized monomer, is protected
Card polymerization system is stable and pH value is in alkalescence for 7~8.
In the present invention, with persulfate as initiator, under Conditions of Emulsion Polymerization, room temperature normal pressure causes styrene, generates
Polystyrene with super-high molecular weight.Wherein, emulsion polymerization is safe and reliable using water as reaction medium, has both saved cost, improves again
Impact to environment；Using suitable emulsion polymerization condition so that persulfate decomposes at room temperature, at a normal initiation benzene
Vinyl polymerization, polymerization speed is fast, and the response time is short and monomer conversion is high, and the molecular weight height of gained polystyrene and molecular weight divide
Cloth is narrow, and molecular weight and molecular weight distribution can be adjusted according to polymeric reaction condition.Whole system is simple and stable, mild condition,
Operation is easy, it is adaptable to carry out the popularization of scale application.
Compared with prior art, the present invention has following beneficial technique effect：
1st, the use of the initiator of commercialization greatly reduces polymerization cost in the inventive method；Whole reaction system is simple
And it is stable, reaction condition is gentle, does not need temperature control, and operation is simple, and the impact to environment is less, and energy consumption is low, is suitably applied
Industrialization large-scale production.
2nd, the response time is short and monomer conversion is high in the inventive method, and the molecular weight of gained polystyrene is high and molecular weight
Narrowly distributing, and its molecular weight and molecular weight distribution can be regulated and controled in relative broad range, be conducive to precise control superelevation point
Son amount polystyrene synthesis technique, so as to prepare the polystyrene with super-high molecular weight product that disclosure satisfy that in different demands.This is right
It is equally also significant in the theoretical research of polystyrene with super-high molecular weight synthesis technique.
Description of the drawings
Fig. 1 is the molecular weight differential distribution curve of the gained polystyrene with super-high molecular weight of embodiment 1.
Specific embodiment
Embodiment 1
Styrene (5.0002g, 0.0480mol) is added to dissolved with sodium lauryl sulphate (0.2500g, 5wt% benzene second
Alkene), sodium bicarbonate (0.1500g, 3wt% styrene), potassium peroxydisulfate (0.4321g, 0.0016mol) and water (20.0053g,
400wt% styrene) reaction bulb in, stir, after evacuation deoxygenation, at being placed in 35 DEG C react 4 hours, measure styrene
Conversion ratio is 90.27%.Ethanol breakdown of emulsion, tri- washing post-dryings of Jing, then tri- purification post-dryings of Jing are used, polymer is obtained.Adopt
Polymer is analyzed with three detection volume removing chromatogram instrument, it is as a result as follows：Light scattering weight average molecular weight Mw.MALLS=
2693000g/mol, molecular weight distribution PDI=3.60.Fig. 1 is micro- for the molecular weight of the gained polystyrene with super-high molecular weight of embodiment 1
Divide distribution curve.
Embodiment 2
Styrene (5.0002g, 0.0480mol) is added to dissolved with sodium lauryl sulphate (0.3003g, 6wt% benzene second
Alkene), sodium bicarbonate (0.2001g, 4wt% styrene), Ammonium persulfate. (0.5472g, 0.0024mol) and water (25.0005g,
500wt% styrene) reaction bulb in, stir, after evacuation deoxygenation, at being placed in 35 DEG C react 1 hour, measure styrene
Conversion ratio is 89.77%.Ethanol breakdown of emulsion, tri- washing post-dryings of Jing, then tri- purification post-dryings of Jing are used, polymer is obtained.Adopt
Polymer is analyzed with three detection volume removing chromatogram instrument, it is as a result as follows：Light scattering weight average molecular weight Mw.MALLS=
3730000g/mol, molecular weight distribution PDI=2.07.
Embodiment 3
Styrene (5.0002g, 0.0480mol) is added to dissolved with sodium lauryl sulphate (0.2003g, 4wt% benzene second
Alkene), sodium bicarbonate (0.1002g, 2wt% styrene), potassium peroxydisulfate (0.1309g, 0.0005mol) and water (10.0006g,
200wt% styrene) reaction bulb in, stir, after evacuation deoxygenation, at being placed in 35 DEG C react 6 hours, measure styrene
Conversion ratio is 88.65%.Ethanol breakdown of emulsion, tri- washing post-dryings of Jing, then tri- purification post-dryings of Jing are used, polymer is obtained.Adopt
Polymer is analyzed with three detection volume removing chromatogram instrument, it is as a result as follows：Light scattering weight average molecular weight Mw.MALLS=
5847000g/mol, molecular weight distribution PDI=2.06.
Embodiment 4
Styrene (5.0001g, 0.0480mol) is added to dissolved with sodium lauryl sulphate (0.2502g, 5wt% benzene second
Alkene), sodium bicarbonate (0.1500g, 3wt% styrene), potassium peroxydisulfate (0.4322g, 0.0016mol) and water (20.0007g,
400wt% styrene) reaction bulb in, stir, after evacuation deoxygenation, at being placed in 25 DEG C react 4 hours, measure styrene
Conversion ratio is 88.97%.Ethanol breakdown of emulsion, tri- washing post-dryings of Jing, then tri- purification post-dryings of Jing are used, polymer is obtained.Adopt
Polymer is analyzed with three detection volume removing chromatogram instrument, it is as a result as follows：Light scattering weight average molecular weight Mw.MALLS=
5502000g/mol, molecular weight distribution PDI=2.25.
Embodiment 5
Styrene (5.0001g, 0.0480mol) is added to dissolved with sodium lauryl sulphate (0.2500g, 5wt% benzene second
Alkene), sodium bicarbonate (0.1500g, 3wt% styrene), potassium peroxydisulfate (0.3242g, 0.0012mol) and water (20.0053g,
400wt% styrene) reaction bulb in, stir, after evacuation deoxygenation, at being placed in 35 DEG C react 6 hours, measure styrene
Conversion ratio is 92.74%.Ethanol breakdown of emulsion, tri- washing post-dryings of Jing, then tri- purification post-dryings of Jing are used, polymer is obtained.Adopt
Polymer is analyzed with three detection volume removing chromatogram instrument, it is as a result as follows：Light scattering weight average molecular weight Mw.MALLS=
3558000g/mol, molecular weight distribution PDI=4.20.
Embodiment 6
Styrene (5.0002g, 0.0480mol) is added to dissolved with dodecylbenzene sodium sulfonate (0.3000g, 6wt% benzene
Ethylene), sodium bicarbonate (0.1500g, 3wt% styrene), potassium peroxydisulfate (0.4321g, 0.0016mol) and water (20.0053g,
400wt% styrene) reaction bulb in, stir, after evacuation deoxygenation, at being placed in 25 DEG C react 4 hours, measure styrene
Conversion ratio is 91.54%.Ethanol breakdown of emulsion, tri- washing post-dryings of Jing, then tri- purification post-dryings of Jing are used, polymer is obtained.Adopt
Polymer is analyzed with three detection volume removing chromatogram instrument, it is as a result as follows：Light scattering weight average molecular weight Mw.MALLS=
4331000g/mol, molecular weight distribution PDI=2.40.
Claims (8)
1. the method that emulsion polymerization room temperature prepares polystyrene with super-high molecular weight, including：Persulfate is adopted for initiator, water is
Medium, anionic surfactant is emulsifying agent, and sodium bicarbonate is pH adjusting agent, and styrene is polymerized monomer, by freedom
Emulsion polymerization, at room temperature emulsion polymerization obtain polystyrene with super-high molecular weight, its weight average molecular weight more than 250 ×
104g/mol。
2. the method that emulsion polymerization room temperature according to claim 1 prepares polystyrene with super-high molecular weight, it is characterised in that
Described initiator is potassium peroxydisulfate or Ammonium persulfate..
3. the method that emulsion polymerization room temperature according to claim 1 prepares polystyrene with super-high molecular weight, it is characterised in that
Described initiator:The molal weight ratio of polymerized monomer is 1~5:100.
4. the method that emulsion polymerization room temperature according to claim 1 prepares polystyrene with super-high molecular weight, it is characterised in that
Described water:The mass ratio of polymerized monomer is 2~5:1.
5. the method that emulsion polymerization room temperature according to claim 1 prepares polystyrene with super-high molecular weight, it is characterised in that
Polymeric reaction temperature is room temperature, and polymerization reaction time is 1-6 hours.
6. the method that emulsion polymerization room temperature according to claim 1 prepares polystyrene with super-high molecular weight, it is characterised in that
Described surfactant is dodecylbenzene sodium sulfonate or sodium lauryl sulphate.
7. the method that emulsion polymerization room temperature according to claim 1 prepares polystyrene with super-high molecular weight, it is characterised in that
Described surfactant:The mass ratio of polymerized monomer is 4-6%.
8. the method that emulsion polymerization room temperature according to claim 1 prepares polystyrene with super-high molecular weight, it is characterised in that
The consumption of described pH adjusting agent sodium bicarbonate is 2~4wt% of polymerized monomer, it is ensured that polymerization system is stable and pH value is 7~8
In alkalescence.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611258871.9A CN106674390B (en) | 2016-12-30 | 2016-12-30 | The method that emulsion polymerization room temperature prepares polystyrene with super-high molecular weight |
| US15/742,407 US20180371143A1 (en) | 2016-12-30 | 2017-04-20 | A process for preparing an ultra-high molecular weight polymer via emulsion polymerization at room temperature |
| PCT/CN2017/081177 WO2018120526A1 (en) | 2016-12-30 | 2017-04-20 | Method for preparing ultra-high molecular weight polymer at room temperature through emulsion polymerization |
| US17/188,760 US11866539B2 (en) | 2016-12-30 | 2021-03-01 | Process for preparing an ultra-high molecular weight polymer via emulsion polymerization at room temperature |
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| CN201611258871.9A CN106674390B (en) | 2016-12-30 | 2016-12-30 | The method that emulsion polymerization room temperature prepares polystyrene with super-high molecular weight |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113683394A (en) * | 2021-09-11 | 2021-11-23 | 景德镇陶瓷大学 | High-performance self-cleaning sanitary ceramic and preparation method thereof |
| CN114014964A (en) * | 2021-11-24 | 2022-02-08 | 广东天银实业有限公司 | Polystyrene seed emulsion and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5284269A (en) * | 1976-01-01 | 1977-07-13 | Japan Synthetic Rubber Co Ltd | Preparation of super-high-molecular-weight polymers |
| CN1074223A (en) * | 1992-01-10 | 1993-07-14 | 兰州大学 | The synthetic method of polystyrene with super-high molecular weight |
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2016
- 2016-12-30 CN CN201611258871.9A patent/CN106674390B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5284269A (en) * | 1976-01-01 | 1977-07-13 | Japan Synthetic Rubber Co Ltd | Preparation of super-high-molecular-weight polymers |
| CN1074223A (en) * | 1992-01-10 | 1993-07-14 | 兰州大学 | The synthetic method of polystyrene with super-high molecular weight |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113683394A (en) * | 2021-09-11 | 2021-11-23 | 景德镇陶瓷大学 | High-performance self-cleaning sanitary ceramic and preparation method thereof |
| CN114014964A (en) * | 2021-11-24 | 2022-02-08 | 广东天银实业有限公司 | Polystyrene seed emulsion and preparation method thereof |
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