CN1696161A - Method for preparing nucleus/shell type microemulsion fluid of copolymer in high inherent content - Google Patents
Method for preparing nucleus/shell type microemulsion fluid of copolymer in high inherent content Download PDFInfo
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- CN1696161A CN1696161A CNA2005100432970A CN200510043297A CN1696161A CN 1696161 A CN1696161 A CN 1696161A CN A2005100432970 A CNA2005100432970 A CN A2005100432970A CN 200510043297 A CN200510043297 A CN 200510043297A CN 1696161 A CN1696161 A CN 1696161A
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Abstract
A process for preparing the microemulsion of core-shell copolymer with high content of solid by ultrasonic emulsifying method features that the raw materials are sequentially added, that is, adding the monomer with low polymerizing competition power, vapor pressure and water solubility, adding trigger to polymerize core, and adding the second monomer to polymerize shell.
Description
Technical field:
The invention belongs to the Polymer Synthesizing field, at length say it is to adopt radical polymerization mechanism, replace traditional mechanical stirring with ultrasonic emulsification, control its reinforced order according to the physicochemical property of comonomer and promptly add reactivity ratio, vapour pressure and water-soluble all relatively little comonomer earlier, at the same time disposable whole adding polymerization-filling for some time of initiator are formed nuclear, and then add second comonomer and carry out two sections polymerizations and form shells, to produce the preparation method of nucleus/shell type microemulsion fluid of copolymer in high inherent content.
Background technology:
Over nearly twenties years, because the molecule designability of core/shell structure and core/shell structure and micro-emulsion polymerization excellent specific property separately more and more cause scientific effort personnel's concern.Seed emulsion polymerization is adopted in the preparation of traditional core/shell structure product more, and the adding mode of its comonomer can be divided into interrupter method, semi-continuous process and balance swelling method.These feed way were adding for the quantitative second monomeric while, also need add initiator and other various additives, polymerization is many based on grafting, the emulsion grain of gained is through bigger, as: Bai Ruke (Bai Ru-ke), Wang Mingzhe (Wang Ming-Zhe), He Weidong (He Wei-Dong) etc., " functional polymer journal " (Journal of Functional Polymers), 1995,8:128～134.And the content of emulsifying agent is more than 10% in the general micro-emulsion polymerization, and monomer mass concentration generally is lower than 10%; And carry out micro-emulsion polymerization, even the monomer of the micro-emulsion polymerization that carries out under ultrasonic emulsification all is a vapour pressure less (less than 1 normal atmosphere) or the water-soluble monomer of big (quality solubleness is greater than 1%), generally only limit to the emulsion homopolymerization or the copolymerization of the same vinyl cyanide of vinylbenzene, vinylformic acid, methacrylic acid and ester thereof, as UltrasonSonochem, 2002,9 (3): the ultrasound wave irradiation of different monomers such as 151～158 methyl methacrylates, butyl acrylate under different condition causes letex polymerization; J Polym Chem Ed, 1984,22:2197Core-shellemulsion copolymerization of styrene and acrylonitrile on polystyreneseed particles (the seed emulsion copolymerization of styrene-acrylonitrile); J Polym Sci Polym ChenEd, 1989,27 (2): 671～710, Microemulsion Polymerization of Styrene (cinnamic micro-emulsion polymerization).More than the characteristics of these reports all be the core/shell type letex polymerization, the report of micro-emulsion polymerization or ultrasonic emulsification (little) letex polymerization, and do not seen the copolymerization of the core/shell type microemulsion under the ultrasonic emulsification condition.
Summary of the invention:
The objective of the invention is to be to overcome the deficiency of prior art, proposed new technical scheme, the objective of the invention is to realize by following technical measures:
A kind of preparation method of nucleus/shell type microemulsion fluid of copolymer in high inherent content, it is to adopt radical polymerization mechanism, replace traditional mechanical stirring with ultrasonic emulsification, control its reinforced order according to the physicochemical property of copolymerization monomer, its characteristic is at first to add reactivity ratio, vapour pressure and water-soluble all relatively little first comonomer, at the same time with the disposable whole adding polymerization systems of initiator, form nuclear after polymerization for some time, and then add second polymerization single polymerization monomer and carry out two sections polymerizations and form shells, thereby successfully made high solids content, the polymer micro-emulsion of massfraction about 20%-25%, its particle diameter and is evenly distributed below 100nm.Two stage micro emulsion polymerization processs used in the present invention, macromolecular chain number in made each latex particle of core/shell type microemulsion seldom, even has only 2-3 bar macromolecular chain, every chain molecular formula majority is following structure (A) m-(B) n, wherein A, B represent interpolymer, and m, n represent comonomer A, B structural unit number separately.
The first comonomer of above-mentioned nucleation has vinylbenzene, vinyltoluene, dimethylbenzene ethene etc., becomes second comonomer of shell 1,3-butadiene, chloroprene to be arranged, pentadiene, isoprene etc.; Initiator belongs to oxidation-reducting system initiator, and its oxygenant adopts organo-peroxide, and reductive agent adopts ferrous salt; Nucleation, become comonomer water-soluble of shell all less than 1% (quality); Hyperacoustic duration of oscillation depends on the physicochemical property of ultrasonic frequency and comonomer.What the present invention adopted is common emulsifying agent, and its consumption is the consumption of general letex polymerization, and promptly its mass concentration in system is about 2%.
The preparation method of nucleus/shell type microemulsion fluid of copolymer in high inherent content of the present invention compares with the preparation method of prior art, has the following advantages:
1. it is 8-12 hour that traditional letex polymerization transformation efficiency reached for 60% required time, and the present invention replaces mechanical stirring to carry out emulsification with ultrasonic wave, and transformation efficiency just reaches 65% in 3-4 hour;
2. traditional letex polymerization latex particle size is more than 100nm, and latex particle size of the present invention is evenly distributed and has nucleocapsid structure below 100nm;
3. traditional micro-emulsion polymerization emulsifying agent consumption is more than 10%, monomer concentration is below 10%, what the present invention adopted is common emulsifying agent, and its consumption is a conventional emulsion polymeric consumption, be its mass concentration in system about 2%, and obtained emulsion solid content is between 20%-25%;
4. the relevant nuclear/shell polymerization single polymerization monomer of documents and materials reports, it all is the monomer of vapour pressure little (less than 1 normal atmosphere) or water-soluble big (quality solubleness is greater than 1%), the monomer of the core/shell type high solids content micro-emulsion polymerization that the present invention carries out is the big and water-soluble little monomer of vapour pressure, as divinyl.
Embodiment:
At first introduce the present invention and get each raw material relevant technologies requirement: emulsifying agent is made up of primary emulsion, assistant for emulsifying agent, electrolyte buffer agent and PH regulator solution (KOH solution), primary emulsion classification in the prescription mainly is a RA rosin acid, fatty acid soaps etc., the assistant for emulsifying agent classification is diffusant Tarnol-N, the effect of emulsifying agent is to reduce oil surface tension in water in the letex polymerization, makes oil be homodisperse in water; Activator is by ferrous salt, helps reductive agent, iron ion complexing agent, and oxygen scavenger (V-Brite B) is formed; The effect of activator is to produce free radical trigger monomer polymerization reaction take place with the effect of organic peroxy thing; For preventing the macromolecular branching of multipolymer and crosslinked, when conversion of monomer arrives to a certain degree, in polymerization system, add terminator and stop polyreaction, make the free radical of growth become stable polymer.Terminator is that Sodium dimethyldithiocarbamate 40min, nitrite and water is formulated by formula ratio; Dodecyl Mercaptan is a conditioning agent, the molecular weight distribution and the degree of branching of control and telomerized polymer in polymerization process; It is that the free radical that produces when making polymerization is not destroyed by oxygen and loses activity that deoxygenation is handled, the present invention is to prepare 10% NaOH solution earlier to cinnamic processing, and washing is removed stopper more than three times, and add the siccative drying, fill the nitrogen deoxygenation and protect nitrogen at last to put into refrigerator stand-by; The deoxidation of distilled water is handled, and is distilled water is added in 2 liters the single port flask, is heated to 100 ℃ of boilings 10 minutes, fills nitrogen and is cooled to that to protect nitrogen after the room temperature stand-by; The preparation of emulsifier solution: take by weighing disproportionated rosin acid soap, diffusant Tarnol-N solution, electrolyte buffer solution, complexing agent, V-Brite B and an amount of KOH regulator solution according to amount in the prescription, and put into the emulsifying agent bottle successively, seal then and vacuumize, the displacement ammonia some all over after, add the formula ratio oxygen-free water and be placed on 0-5 ℃ of water-bath to be cooled to constant temperature stand-by; The preparation of activator solution: with ferrous salt, help reductive agent and iron ion complexing agent to take by weighing to add in the activator bottle by the peace formula ratio, seal then and vacuumize, behind some times of the displacement ammonia, add the formula ratio oxygen-free water and be placed on 0-5 ℃ of water-bath to be cooled to constant temperature stand-by, activator solution needs matching while using system.
The present invention is described in detail in detail below for two example two.
Embodiment 1:
Basic recipe: (mass parts)
| Raw material | Quality (g) | Raw material | Quality (g) |
| Divinyl emulsifying agent reductive agent complexing agent distilled water terminator | ??71 ??4.8 ??0.04 ??0.07 ??200 ??0.1～0.15 | The vinylbenzene organo-peroxide helps reductive agent oxygen scavenger Dodecyl Mercaptan | ??29 ??0.15 ??0.1 ??0.025 ??0.18 |
Annotate: all reaction raw materials all need to carry out strict deoxygenation when obtain solution handles.Operating process is as follows:
1. preparation emulsifier solution, activator solution places 0～5 ℃ of water-bath to be cooled to constant temperature with the vinylbenzene of removing stopper then;
2. get the withstand voltage test tube of 30ml, vacuumize;
According to the oxygenants order of emulsifying agent → activator → vinylbenzene → all with medicine injecting tube successively;
4. test tube was placed the interior sonic oscillation of ultrasonic oscillator water-bath (0～5 ℃) 7.5 minutes, then 0～5 ℃ of water-bath internal reaction 40 minutes;
5. add an amount of divinyl that is dissolved with positive Dodecyl Mercaptan more in vitro, place the interior sonic oscillation of ultrasonic oscillator water-bath (0～5 ℃) after 7.5 minutes again, again 0～5 ℃ of water-bath internal reaction 150 minutes;
6. add terminator and stop polyreaction.Gained emulsion transformation efficiency reaches 67% in polymerization after 190 minutes, and emulsion solid content reaches 22.1%, and latex particle size is evenly distributed below 100nm, and has core/shell structure.
Embodiment 2:
Basic recipe: (mass parts)
| Raw material | Quality (g) | Raw material | Quality (g) |
| Isoprene emulsifying agent reductive agent complexing agent distilled water terminator | ??70 ??4.6 ??0.03 ??0.06 ??200 ??0.1～0.15 | The vinylbenzene organo-peroxide helps reductive agent oxygen scavenger Dodecyl Mercaptan | ??30 ??0.12 ??0.09 ??0.025 ??0.17 |
Annotate: all reaction raw materials all need to carry out strict deoxygenation when obtain solution handles.
Operating process is as follows:
1. preparation emulsifier solution, activator solution places 0～5 ℃ of water-bath to be cooled to constant temperature with the vinyltoluene of removing stopper then;
2. get the withstand voltage test tube of 30ml, vacuumize;
According to the oxygenants order of emulsifying agent → activator → vinylbenzene → all with medicine injecting tube successively;
4. test tube was placed the interior sonic oscillation of ultrasonic oscillator water-bath (0～5 ℃) 7.5 minutes, then 0～5 ℃ of water-bath internal reaction 80 minutes;
5. inject an amount of isoprene that is dissolved with positive Dodecyl Mercaptan in vitro again, place the interior sonic oscillation of ultrasonic oscillator water-bath (0～5 ℃) after 7.5 minutes again, again 0～5 ℃ of water-bath internal reaction 150 minutes;
6. add terminator and stop polyreaction.Gained emulsion transformation efficiency reaches 71% in polymerization after 230 minutes, and emulsion solid content 23.2%, latex particle size are evenly distributed below 100nm, and has core/shell structure.
Claims (6)
1. the preparation method of a nucleus/shell type microemulsion fluid of copolymer in high inherent content, it is to adopt radical polymerization mechanism, replace traditional mechanical stirring with ultrasonic emulsification, control its reinforced order according to the physicochemical property of comonomer, it is characterized in that at first adding reactivity ratio, vapour pressure and water-soluble all relatively little first comonomer, at the same time with the disposable whole adding polymerization systems of initiator, polymerization for some time forms nuclear, and then adds two sections polymerizations formation shells that second comonomer carries out.
2. in accordance with the method for claim 1, it is characterized in that the first comonomer of nucleation has vinylbenzene, vinyltoluene, dimethylbenzene ethene, become second comonomer of shell that 1,3-butadiene, chloroprene, pentadiene, isoprene are arranged.
3. in accordance with the method for claim 1, it is characterized in that initiator is the initiator that belongs to the oxidation-reduction system, its oxygenant adopts organo-peroxide, and reductive agent adopts ferrous salt.
4. in accordance with the method for claim 1, it is characterized in that forming comonomer water-soluble of nuclear or shell all less than 1% (quality).
5. according to the described method of claim 1～4, the time that it is characterized in that ultra-sonic oscillation is depended on the physicochemical property of ultrasonic frequency and comonomer.
6. according to the described method of claim 1～5, what it is characterized in that adopting is common emulsifying agent, and its consumption is conventional emulsion polymeric consumption, and promptly its mass concentration in system is about 2%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864040A (en) * | 2010-05-28 | 2010-10-20 | 青岛科技大学 | Preparation method of butyl acrylate-styrene-acrylonitrile graft copolymer |
| CN112375179A (en) * | 2020-11-10 | 2021-02-19 | 珠海冠宇动力电池有限公司 | Bimolecular-weight-distribution binder for negative electrode and preparation method and application thereof |
| CN112552459A (en) * | 2020-12-04 | 2021-03-26 | 山纳合成橡胶有限责任公司 | Chloroprene rubber latex with core-shell structure colloidal particles and preparation method thereof |
-
2005
- 2005-04-29 CN CNA2005100432970A patent/CN1696161A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864040A (en) * | 2010-05-28 | 2010-10-20 | 青岛科技大学 | Preparation method of butyl acrylate-styrene-acrylonitrile graft copolymer |
| CN112375179A (en) * | 2020-11-10 | 2021-02-19 | 珠海冠宇动力电池有限公司 | Bimolecular-weight-distribution binder for negative electrode and preparation method and application thereof |
| CN112375179B (en) * | 2020-11-10 | 2023-03-24 | 珠海冠宇动力电池有限公司 | Bimolecular-weight-distribution binder for negative electrode and preparation method and application thereof |
| CN112552459A (en) * | 2020-12-04 | 2021-03-26 | 山纳合成橡胶有限责任公司 | Chloroprene rubber latex with core-shell structure colloidal particles and preparation method thereof |
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