CN103554318B - Method and device for preparing fluorine-containing polymer under micro-emulsion form - Google Patents
Method and device for preparing fluorine-containing polymer under micro-emulsion form Download PDFInfo
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- CN103554318B CN103554318B CN201310495146.3A CN201310495146A CN103554318B CN 103554318 B CN103554318 B CN 103554318B CN 201310495146 A CN201310495146 A CN 201310495146A CN 103554318 B CN103554318 B CN 103554318B
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Abstract
The invention discloses a method for preparing a fluorine-containing polymer under a micro-emulsion form, comprises the following steps: A, sufficiently mixing purified water, a surfactant, a cosurfactant, a liquid state fluorine-containing monomer and a photo-initiator in a reactor to form an O/W micro-emulsion composed of a fluorine-containing monomer and water; B, placing the O/W micro-emulsion formed in the step A under an ultraviolet lamp to irradiate to trigger poly reaction, forming a fluorine-containing polymer in a micro-emulsion form, wherein the unpolymerized liquid state fluorine-containing monomer is transferred into a gaseous fluorine-containing monomer under the effect of reaction heat; C, separating the fluorine-containing polymer forming the micro-emulsion form from the gaseous fluorine-containing monomer in the step B, and recycling the gaseous fluorine-containing monomer. The invention further discloses a device for preparing the fluorine-containing polymer using the above method. The method and device have the beneficial effect that the polymerization speed is fast, the polymerization can be triggered at a low temperature, the poly reaction is high in security, the reaction device is simple, the investment is less, the production cost is low, and the product quality is excellent.
Description
Technical field
The present invention relates to chemical field, more particularly to prepares the method and apparatus of fluoropolymer under microemulsion form.
Background technology
If after two or more blended emulsifying of immiscible liquid, the diameter of dispersant liquid drop is in 5nm～100nm
Between, then the system is referred to as microemulsion.Microemulsion is transparent dispersion system, and its formation is relevant with the solubilization of micelle, also known as
For " by swelling micellar solution " or " micelle emulsion ".Generally by oil, water, surfactant, cosurfactant and electrolyte
Deng the transparent or semitransparent liquid stabilising system of composition.The particle of dispersion phase is less than 0.1 μm, or even little to tens of angstroms.It is special
Point is dispersion phase particle size between 0.01～0.1 μm, and particle is uniform in size, and microscope is invisible；Particle is in spherical；Microemulsion
It is translucent to transparent, Thermodynamically stable, if system is transparent, good fluidity, and with the centrifugal acceleration of centrifuge 100g
Separate five minutes and not stratified be regarded as microemulsion；It is miscible within the specific limits with oil, water.Dispersion phase is oil, dispersion is situated between
Matter is referred to as O/W type micro emulsions for the system of water, otherwise is then referred to as w/o type micro emulsion.O/W type micro-emulsion polymerizations are characterized in that
The place of polyreaction is not solubilization micelle, but emulsified monomer drop, the generation of seed nucleus and the growth of particle, in monomer
Occur in drop；The mean diameter of polymer particle is essentially identical with the diameter of initial monomer drop.From stoffer in 1980 etc.
Since reported first is with microemulsion as polymerisation medium, micro-emulsion polymerization has caused people as an important branch of emulsion polymerization
Great attention.It is micro-emulsion polymerization reacting balance, quick, course of reaction need not stirring, therefore equipment is simple, safe and reliable；
Polymerizate is the macromolecule microemulsion that particle diameter is minimum, monodispersity is preferable, stability is high, and relative point is obtained after treatment
Son amount is high, the polymer of narrowly distributing；For the properties for improving polymer have highly important realistic meaning；Micro-emulsion polymerization
Application prospect it is boundless.
Also there is micro-emulsion polymerization perfluoroethylene-propylene in prior art and by hexafluoropropene, tetrafluoroethene, trifluoro propene three
The method of unit's polymerization microemulsion, but, there is problems with：1st, gaseous monomer is passed directly in polymeric kettle, or gas phase
In the established microemulsion of material " being mixed into " after polymerization, or gaseous phase materials are dissolved in the polyreaction in microemulsion, but
It is not micro-emulsion polymerization truly；And, due to the aggregation of gaseous monomer in polymeric kettle, there is the danger of implode
Property；2nd, caused using radical initiator and be polymerized, its polymerization temperature is higher；3rd, need constantly to add list in polymerization process
Body and initiator.
The content of the invention
In order to solve the above problems, the present invention provides a kind of method that fluoropolymer is prepared under microemulsion form.This
The invention technical problem to be solved is：Prior art polymerization speed is slow, causes polymerization temperature high, and polyreaction is dangerous big, instead
Answer equipment complicated, investment is high, production cost is high.In order to realize above-mentioned technical purpose, the technical scheme is that：In microemulsion
The method that fluoropolymer is prepared under form, it is characterised in that：Comprise the following steps：
A. by pure water, surfactant, cosurfactant, liquid fluorinated monomer and light trigger in reaction vessel
It is sufficiently mixed, forms the o/w microemulsion of fluorochemical monomer and water composition；
B. the o/w microemulsion that step A is formed is placed under Burdick lamp and is irradiated, initiated polymerization generates microemulsion shape
The fluoropolymer of state, unpolymerized liquid fluorinated monomer is converted into gaseous fluorinated monomer in the presence of reaction heat；
C. fluoropolymer and gaseous fluorinated monomer that microemulsion form is generated in step B are separated, the gaseous state is contained
Fluorine monomer recycling use.
In such scheme, the fluorochemical monomer is tetrafluoroethene, hexafluoropropene, trifluoro propene, CTFE, inclined fluorine second
The mixture of one or more in alkene, fluorothene, hexafluoro-isobutene, perfluoroalkyl vinyl ether, or for ethylene or propylene and four
In fluorothene, hexafluoropropene, trifluoro propene, CTFE, vinylidene, fluorothene, hexafluoro-isobutene, perfluoroalkyl vinyl ether
At least one mixture.
In such scheme, the surfactant is nonionic surfactant；The cosurfactant is low-carbon (LC)
Chain alcohol；The light trigger is selected from methylol Benzoinum, Benzoin derivative, 4- benzoyl -1,3- dioxolane derivatives, connection
Benzoyl ketal, α, α-Dialkoxy acetophenones, alpha-aminoacetophenone, 2,4,6- trimethylbenzoyl diphenylphosphide hydroxides
Any one of thing.
In such scheme, polymerization temperature is 32 DEG C～23 DEG C in step B.
In such scheme, polymerization pressure is 3.92MPa～4.42MPa in step B.
In such scheme, polymerization time is 1～60 minute in step B.
In such scheme, the main crest of the Burdick lamp transmitting light is 480nm～300nm.
The invention also discloses the equipment that fluoropolymer is prepared under microemulsion form：Including microchannel reaction unit,
Burdick lamp, gas-liquid separation device and by the microchannel reaction unit and gas-liquid separation device couple together conveying reaction
The pipeline of material, is provided with reaction heat cooler in the microchannel reaction unit, the gas-liquid separation device is provided with microemulsion row
Outlet and monomer gas outlet, the Burdick lamp is arranged at microchannel reaction unit top.
In such scheme, the microchannel reaction unit is single micro passage reaction, or two or more microchannel plate
The micro passage reaction group for answering device to constitute by serial or parallel connection；The micro passage reaction includes mixing section and polymeric segment, institute
State the top that Burdick lamp is arranged at polymeric segment；The polymeric segment is glass or quartz material.
In such scheme, the depth and width of the micro passage reaction are 0.1 μm～100 μm.
The invention provides the method and apparatus that fluoropolymer is prepared under microemulsion form, advantages of the present invention and have
Beneficial effect is：Polymerization speed is fast, can low temperature cause polymerization, polyreaction is safe, and consersion unit is simple, small investment, raw
Low cost is produced, properties of product are superior.
Description of the drawings
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, without having to pay creative labor, may be used also
To obtain other accompanying drawings according to these accompanying drawings.
Fig. 1 is the structural representation of present device.
In figure：1st, the polymeric segment 2, gas of the mixing section 12, micro passage reaction of micro passage reaction 11, micro passage reaction
It is the monomer gas outlet 3 of the microemulsion outlet 22, gas-liquid separation device of liquid separating apparatus 21, gas-liquid separation device, ultraviolet
Line lamp
Specific embodiment
With reference to the accompanying drawings and examples, the specific embodiment of the present invention is further described.Following examples are only
For clearly illustrating technical scheme, and can not be limited the scope of the invention with this.
As shown in figure 1, the equipment of the present invention includes：Including micro passage reaction 1, Burdick lamp 3, gas-liquid separation device 2,
And the micro passage reaction 1 and gas-liquid separation device 2 are coupled together into the pipeline of conveying reaction mass；Micro passage reaction
1 includes mixing section 11 and polymeric segment 12, and Burdick lamp 2 is arranged at the top of micro passage reaction polymeric segment 12, and microchannel plate should
The discharging opening of the polymeric segment 12 of device 1 is connected by pipeline with the charging aperture of gas/liquid separator device 2, and gas-liquid separation device 2 sets
There are microemulsion outlet 21 and monomer gas outlet 22.Burdick lamp used in embodiment is capillary tube supertension hydrargyrum
Lamp, the main crest of its isolychn is 300nm～480nm.
Embodiment 1
The species of reactant, title and weight such as following table：
The micro passage reaction fully cleaned with nitrogen, by above-mentioned reactant the mixing section of micro passage reaction is input into, on
State after reactant is sufficiently mixed, spontaneously form microemulsion；Capillary tube extra-high-pressure mercury vapour lamp is opened, microemulsion should into microchannel plate
The polymeric segment of device, polymerization temperature is controlled at 25 DEG C～28 DEG C；Polymerization pressure is controlled in 3.95MPa～4.05MPa；Polymerization time is
25min；Then the reaction system in micro passage reaction polymeric segment is conveyed into into gas-liquid separation device, in gas-liquid separation device
In, the isolated politef microemulsion 5575g of reaction system, unpolymerized tetrafluoroethylene gas recycling.
Embodiment 2
The species of reactant, title and weight such as following table：
The micro passage reaction fully cleaned with nitrogen, by above-mentioned reactant the mixing section of micro passage reaction is input into, on
State after reactant is sufficiently mixed, spontaneously form microemulsion；Capillary tube extra-high-pressure mercury vapour lamp is opened, microemulsion should into microchannel plate
The polymeric segment of device, polymerization temperature is controlled at 27 DEG C～30 DEG C；Polymerization pressure is controlled in 3.95MPa～4.05MPa；Polymerization time is
35min；Then the reaction system in micro passage reaction polymeric segment is conveyed into into gas-liquid separation device, in gas-liquid separation device
In, the isolated politef microemulsion of reaction system；Politef microemulsion heating breakdown of emulsion is processed, is filtered and is cleaned
Material, 130 DEG C of drying, obtains fine polytetrafluoroethylpowder powder 465g；Reclaim tetrafluoroethene 33g.
Embodiment 3
The species of reactant, title and weight such as following table：
The micro passage reaction fully cleaned with nitrogen, by above-mentioned reactant the mixing section of micro passage reaction is input into, on
State after reactant is sufficiently mixed, spontaneously form microemulsion；Capillary tube extra-high-pressure mercury vapour lamp is opened, microemulsion is input into into microchannel plate
The polymeric segment of device, polymerization temperature is answered to control at 26 DEG C～28 DEG C；Polymerization pressure is controlled in 3.95MPa～4.05MPa；Polymerization time
For 40min；Then the reaction system in micro passage reaction polymeric segment is conveyed into into gas-liquid separation device, in gas-liquid separation device
In, the isolated perfluoroethylene-propylene microemulsion of reaction system；Perfluoroethylene-propylene microemulsion heating breakdown of emulsion is processed, is filtered simultaneously
Cleaning material, 130 DEG C of constant temperature are dried for 2 hours, then heat to 190 DEG C, and constant temperature 4 hours obtains the perfluoroethylene third without caking
Alkene fine powder 503g.
Embodiment 4
The species of reactant, title and weight such as following table：
The micro passage reaction fully cleaned with nitrogen, by above-mentioned reactant the mixing section of micro passage reaction is input into, on
State after reactant is sufficiently mixed, spontaneously form microemulsion；Capillary tube extra-high-pressure mercury vapour lamp is opened, microemulsion is input into into microchannel plate
The polymeric segment of device, polymerization temperature is answered to control at 30 DEG C～32 DEG C；Polymerization pressure is controlled in 3.95MPa～4.05MPa；Polymerization time
For 60min；Then the reaction system in micro passage reaction polymeric segment is conveyed into into gas-liquid separation device, in gas-liquid separation device
In, the isolated copolymer microemulsion 5576g of reaction system.
Embodiment 5
The species of reactant, title and weight such as following table：
The micro passage reaction fully cleaned with nitrogen, by above-mentioned reactant the mixing section of micro passage reaction is input into, on
State after reactant is sufficiently mixed, spontaneously form microemulsion；Capillary tube extra-high-pressure mercury vapour lamp is opened, microemulsion is input into into microchannel plate
The polymeric segment of device, polymerization temperature is answered to control at 29 DEG C～30 DEG C；Polymerization pressure is controlled in 3.92MPa～4.05MPa；Polymerization time
For 25min；Then the reaction system in micro passage reaction polymeric segment is conveyed into into gas-liquid separation device, in gas-liquid separation device
In, the isolated politef microemulsion of reaction system；Politef microemulsion heating breakdown of emulsion is processed, is filtered and is cleaned
Material, 130 DEG C of constant temperature dryings, obtains fine polytetrafluoroethylpowder powder 463g；Reclaim tetrafluoroethene 35g.
Embodiment 6
The species of reactant, title and weight such as following table：
The micro passage reaction fully cleaned with nitrogen, by above-mentioned reactant the mixing section of micro passage reaction is input into, on
State after reactant is sufficiently mixed, spontaneously form microemulsion；Capillary tube extra-high-pressure mercury vapour lamp is opened, microemulsion is input into into microchannel plate
The polymeric segment of device, polymerization temperature is answered to control at 27 DEG C～28 DEG C；Polymerization pressure is controlled in 3.95MPa～4.42MPa；Polymerization time
For 20min；Then the reaction system in micro passage reaction polymeric segment is conveyed into into gas-liquid separation device, in gas-liquid separation device
In, the isolated perfluoroethylene-propylene microemulsion of reaction system；Perfluoroethylene-propylene microemulsion heating breakdown of emulsion is processed, is filtered simultaneously
Cleaning material, 130 DEG C of constant temperature are dried for 2 hours, then heat to 190 DEG C, and constant temperature 3 hours obtains the perfluoroethylene third without caking
Alkene fine powder 501g.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Within god and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (5)
1. the method that fluoropolymer is prepared under microemulsion form, it is characterised in that：Comprise the following steps：
A. it is pure water, surfactant, cosurfactant, liquid fluorinated monomer and light trigger is abundant in reaction vessel
Mixing, forms the o/w microemulsion of fluorochemical monomer and water composition；The surfactant is nonionic surfactant；
B. the o/w microemulsion that step A is formed is placed under Burdick lamp and is irradiated, initiated polymerization generates microemulsion form
Fluoropolymer, unpolymerized liquid fluorinated monomer is converted into gaseous fluorinated monomer in the presence of reaction heat；Wherein be polymerized temperature
Spend for 32 DEG C～23 DEG C；
C. fluoropolymer and gaseous fluorinated monomer that microemulsion form is generated in step B are separated, by the fluorine-containing list of the gaseous state
Body recycling use；
The equipment for preparing above-mentioned fluoropolymer, including microchannel reaction unit, Burdick lamp, gas-liquid separation device and general
The microchannel reaction unit and gas-liquid separation device couple together the pipeline of conveying reaction mass, the microchannel reaction unit
Reaction heat cooler is inside provided with, the gas-liquid separation device is provided with microemulsion outlet and monomer gas outlet.
2. the method that fluoropolymer is prepared under microemulsion form according to claim 1, it is characterised in that described to contain
Fluorine monomer is tetrafluoroethene, hexafluoropropene, trifluoro propene, CTFE, vinylidene, fluorothene, hexafluoro-isobutene, perfluor
The mixture of one or more in vinyl ethers, or for ethylene or propylene and tetrafluoroethene, hexafluoropropene, trifluoro propene,
At least one mixture in CTFE, vinylidene, fluorothene, hexafluoro-isobutene, perfluoroalkyl vinyl ether.
3. the method that fluoropolymer is prepared under microemulsion form according to claim 1, it is characterised in that described to help
Surfactant is low carbon chain alcohol；The light trigger is selected from methylol Benzoinum, Benzoin derivative, 4- benzoyl -1,3-
Dioxolane derivatives, dibenzoyl ketal, α, α-Dialkoxy acetophenones, alpha-aminoacetophenone, 2,4,6- trimethylbenzene first
Any one of acyl diphenylphosphide hydroxide.
4. the method that fluoropolymer is prepared under microemulsion form according to claim 1, it is characterised in that the step
Polymerization pressure is 3.92MPa～4.42MPa in rapid B.
5., according to the arbitrary described method that fluoropolymer is prepared under microemulsion form of Claims 1 to 4, its feature exists
In the main crest of the Burdick lamp transmitting light is 480nm～300nm.
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| CN104098730B (en) * | 2014-07-10 | 2016-05-11 | 中昊晨光化工研究院有限公司 | The high fluorine content of low Mooney fluorubber and preparation method thereof |
| CN109651539B (en) * | 2018-11-23 | 2023-11-17 | 宜宾天原集团股份有限公司 | Micro-reaction system for producing polyvinyl chloride and polyvinyl chloride production method based on micro-reaction system |
| CN113880978A (en) * | 2021-08-31 | 2022-01-04 | 泰兴梅兰新材料有限公司 | Method and device for preparing microchannel of fluoropolyether carboxylic acid for fluorinated ethylene propylene |
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| CN101186669A (en) * | 2007-11-20 | 2008-05-28 | 山东东岳神舟新材料有限公司 | Method for preparing microemulsion of fluorinated ethylene propylene powder |
| CN101274969A (en) * | 2007-11-20 | 2008-10-01 | 山东东岳神舟新材料有限公司 | Microemulsion polymerization method for fluoropolymer |
| CN103333278A (en) * | 2013-01-30 | 2013-10-02 | 应悦 | A device and a preparation technology for preparing fluoropolymers and fluorocopolymers |
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2013
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| CN1173189A (en) * | 1995-01-18 | 1998-02-11 | W·L·戈尔及同仁股份有限公司 | Aqueous microemulsion polymerization of tetrafluoroethylene |
| CN101186669A (en) * | 2007-11-20 | 2008-05-28 | 山东东岳神舟新材料有限公司 | Method for preparing microemulsion of fluorinated ethylene propylene powder |
| CN101274969A (en) * | 2007-11-20 | 2008-10-01 | 山东东岳神舟新材料有限公司 | Microemulsion polymerization method for fluoropolymer |
| CN103333278A (en) * | 2013-01-30 | 2013-10-02 | 应悦 | A device and a preparation technology for preparing fluoropolymers and fluorocopolymers |
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| Controlled Synthesis of Nonspherical Microparticles Using Microfluidics;Dhananjay Dendukuri et al.;《Langmuir》;20050211;第21卷(第6期);2113-2116 * |
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