CN106674390B - The method that emulsion polymerization room temperature prepares polystyrene with super-high molecular weight - Google Patents
The method that emulsion polymerization room temperature prepares polystyrene with super-high molecular weight Download PDFInfo
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- CN106674390B CN106674390B CN201611258871.9A CN201611258871A CN106674390B CN 106674390 B CN106674390 B CN 106674390B CN 201611258871 A CN201611258871 A CN 201611258871A CN 106674390 B CN106674390 B CN 106674390B
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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
Abstract
The invention discloses the methods that emulsion polymerization room temperature prepares polystyrene with super-high molecular weight, belong to Macroscopic single crystal field.Using persulfate as initiator, water is medium, and anionic surfactant is emulsifier, sodium bicarbonate is pH adjusting agent, and styrene is monomer, polymerization reaction 1-6 hours at room temperature, at a normal, monomer conversion successfully obtains weight average molecular weight greater than 250 × 10 up to 85% or more4The polystyrene with super-high molecular weight of g/mol.Polymerization system of the present invention is simple and stablizes, the use of reaction raw materials is commercialized, polymerization cost is greatly reduced, easy, mild condition is operated, influence to environment is smaller, reaction does not need temperature control to pressurize, and low energy consumption, and the reaction time is short and monomer conversion is high, the molecular weight height and narrow molecular weight distribution of gained polystyrene with super-high molecular weight, and it is regulated and controled in a wider range.The invention has great importance to polystyrene with super-high molecular weight theoretical research and scale application.
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
Measure the emulsion polymerization synthetic technology of polystyrene.
Background technique
Polystyrene is a kind of thermoplastic resin, but ordinary polystyrene has impact strength low, and heat resistance is not high
Disadvantage, therefore application is restricted.Method there are many improving its performance, wherein preparing polystyrene with super-high molecular weight is in recent years
One of research direction.Polystyrene with super-high molecular weight had both remained excellent optical property specific to general polystyrene, easily
Processing performance, and mechanical strength with higher and heat resistance.Therefore, the synthesis of development and abundant polystyrene with super-high molecular weight
Method has important value.
Polysubstituted Bibenzyl compound (carbon-to-carbon bond type compound) is mainly used to cause styrene ontology for initiator at present
Polymerisation in solution；Rare earth catalyst, Calixarene and Mg (n-Bu)2, ternary complex catalyst composed by HMPA passes through under high pressure
Coordination polymerization；Azo compound is initiator, and organic tellurium is chain-transferring agent, through active free radical soap-free emulsion polymerization, is caused
Styrene is prepared into polystyrene with super-high molecular weight.Initiation system is complicated, and efficiency of initiation is lower, and more impurity is introduced in product.
Coordination polymerization system is complicated, operating difficulties, and condition is harsh.Activity/controllable soap-free emulsion free radical polymerization reaction system is complicated,
Severe reaction conditions, polymerization reaction are not easy to control.Above-mentioned polymerization is during preparing polystyrene with super-high molecular weight, also
Two common disadvantages, polymerization time needed for high monomer conversion ratio is longer, and carries out at a relatively high temperature in reaction, has
Reaction even carries out under high pressure, and the molecular weight of gained polystyrene is still affected by various factors.These are insufficient to a certain degree
On limit the development of polystyrene with super-high molecular weight scale application.And emulsion polymerization is using water as medium, Environmental Safety, polymerization
Speed is fast, and the reaction time is short, and free radical is isolated in lotion, reduces the probability of radical termination, reduces to a certain extent
Chain termination rate, therefore resulting polymers molecular weight is high and molecular weight distribution is relatively narrow.
Summary of the invention
The object of the present invention is to provide a kind of methods 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 under Conditions of Emulsion Polymerization, room temperature causes styrene, directly using potassium peroxydisulfate or ammonium persulfate as initiator
Deliver a child into polystyrene with super-high molecular weight, polymerization system is simple and stablizes, and operates easy, and the reaction time is short and monomer conversion
Height, the molecular weight height and narrow molecular weight distribution of gained polystyrene, 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, comprising: use persulfate to cause
Agent, water are medium, and anionic surfactant is emulsifier, and sodium bicarbonate is pH adjusting agent, and styrene is polymerized monomer, are led to
Free-radical emulsion polymerization is crossed, reaction obtains polystyrene with super-high molecular weight at room temperature.
In preferred technical solution, the initiator is potassium peroxydisulfate or ammonium persulfate；
In preferred technical solution, the initiator: the molal weight ratio of polymerized monomer is 1~5:100；
In preferred technical solution, the water: the mass ratio of polymerized monomer is 2~5:1；
In preferred technical solution, polymeric reaction temperature: room temperature；Polymerization reaction time control is 1-6 hours；
In preferred technical solution, the polymerization is emulsion polymerization, and mechanism of polymerization is free radical polymerization；
In preferred technical solution, the surfactant is neopelex or dodecyl sulphate
Sodium；
In preferred technical solution, the surfactant: the mass ratio of polymerized monomer is 4-6%；
In preferred technical solution, the dosage of the pH adjusting agent sodium bicarbonate is 2~4wt% of polymerized monomer, is protected
It demonstrate,proves polymerization system stabilization and pH value is 7~8 in alkalescent.
In the present invention, using 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 using water as reaction medium, securely and reliably, not only saves cost, but also improve
Influence to environment；Using suitable emulsion polymerization condition, so that persulfate decomposes at room temperature, at a normal causes benzene
Vinyl polymerization, polymerization speed is fast, and the reaction time is short and monomer conversion is high, and the molecular weight of gained polystyrene is high and molecular weight divides
Cloth is narrow, and molecular weight and molecular weight distribution can be adjusted according to polymeric reaction condition.Whole system is simple and stablizes, mild condition,
Operate it is easy, suitable for carrying out the popularization of scale application.
Compared with prior art, the invention has the following beneficial technical effects:
1, the use for the initiator being commercialized in the method for the present invention greatly reduces polymerization cost；Entire reaction system is simple
And stablize, reaction condition is mild, does not need temperature control, and operation is simple, and the influence to environment is smaller, and low energy consumption, is suitably applied
Industrialization large-scale production.
2, the reaction time is short in the method for the present invention and monomer conversion is high, the molecular weight height and molecular weight of gained polystyrene
Narrowly distributing, and its molecular weight and molecular weight distribution can be regulated and controled in a wider range, be conducive to accurately control superelevation point
Son amount polystyrene synthesis technology, so that preparation can satisfy the polystyrene with super-high molecular weight product in different demands.This is right
It is equally also of great significance in the theoretical research of polystyrene with super-high molecular weight synthesis technology.
Detailed description of the invention
Fig. 1 is the molecular weight differential distribution curve of 1 gained polystyrene with super-high molecular weight of embodiment.
Specific embodiment
Embodiment 1
Styrene (5.0002g, 0.0480mol) is added to dissolved with lauryl sodium sulfate (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 flask in, stir evenly, after vacuumizing deoxygenation, be placed at 35 DEG C and react 4 hours, measure styrene
Conversion ratio is 90.27%.It is demulsified with ethyl alcohol, is dried after washing three times, then dried after purifying three times, obtain polymer.It adopts
Polymer is analyzed with three detection volume removing chromatogram instrument, as a result as follows: light scatters weight average molecular weight Mw.MALLS=
2693000g/mol, molecular weight distribution PDI=3.60.Fig. 1 is that the molecular weight of 1 gained polystyrene with super-high molecular weight of embodiment is micro-
Divide distribution curve.
Embodiment 2
Styrene (5.0002g, 0.0480mol) is added to dissolved with lauryl sodium sulfate (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 flask in, stir evenly, after vacuumizing deoxygenation, be placed at 35 DEG C and react 1 hour, measure styrene
Conversion ratio is 89.77%.It is demulsified with ethyl alcohol, is dried after washing three times, then dried after purifying three times, obtain polymer.It adopts
Polymer is analyzed with three detection volume removing chromatogram instrument, as a result as follows: light scatters 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 lauryl sodium sulfate (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 flask in, stir evenly, after vacuumizing deoxygenation, be placed at 35 DEG C and react 6 hours, measure styrene
Conversion ratio is 88.65%.It is demulsified with ethyl alcohol, is dried after washing three times, then dried after purifying three times, obtain polymer.It adopts
Polymer is analyzed with three detection volume removing chromatogram instrument, as a result as follows: light scatters 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 lauryl sodium sulfate (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 flask in, stir evenly, after vacuumizing deoxygenation, be placed at 25 DEG C and react 4 hours, measure styrene
Conversion ratio is 88.97%.It is demulsified with ethyl alcohol, is dried after washing three times, then dried after purifying three times, obtain polymer.It adopts
Polymer is analyzed with three detection volume removing chromatogram instrument, as a result as follows: light scatters 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 lauryl sodium sulfate (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 flask in, stir evenly, after vacuumizing deoxygenation, be placed at 35 DEG C and react 6 hours, measure styrene
Conversion ratio is 92.74%.It is demulsified with ethyl alcohol, is dried after washing three times, then dried after purifying three times, obtain polymer.It adopts
Polymer is analyzed with three detection volume removing chromatogram instrument, as a result as follows: light scatters 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 neopelex (0.3000g, 6wt% benzene
Ethylene), sodium bicarbonate (0.1500g, 3wt% styrene), potassium peroxydisulfate (0.4321g, 0.0016mol) and water (20.0053g,
400wt% styrene) reaction flask in, stir evenly, after vacuumizing deoxygenation, be placed at 25 DEG C and react 4 hours, measure styrene
Conversion ratio is 91.54%.It is demulsified with ethyl alcohol, is dried after washing three times, then dried after purifying three times, obtain polymer.It adopts
Polymer is analyzed with three detection volume removing chromatogram instrument, as a result as follows: light scatters weight average molecular weight Mw.MALLS=
4331000g/mol, molecular weight distribution PDI=2.40.
Claims (2)
1. the method that emulsion polymerization room temperature prepares polystyrene with super-high molecular weight, comprising: use persulfate for initiator, water is
Medium, anionic surfactant are emulsifier, and sodium bicarbonate is pH adjusting agent, and styrene is polymerized monomer, pass through freedom
Emulsion polymerization, emulsion polymerization obtains polystyrene with super-high molecular weight at room temperature, and weight average molecular weight is greater than 250 ×
104g/mol；The initiator is potassium peroxydisulfate or ammonium persulfate, and the mass ratio of the material of initiator and polymerized monomer is 1
~5:100；The anionic surfactant is neopelex or lauryl sodium sulfate, surface-active
The mass ratio of agent and polymerized monomer is 4-6%；The water: the mass ratio of polymerized monomer is 2~5:1；The pH adjusting agent
The dosage of sodium bicarbonate is 2~4wt% of polymerized monomer, guarantees that polymerization system is stable and pH value is 7~8 in alkalescent.
2. 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.
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| 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 |
| 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 |
| 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 |
| 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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| 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 |
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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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| 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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