CN100528905C - Fluorine-contained cation type emulsion and preparing method - Google Patents
Fluorine-contained cation type emulsion and preparing method Download PDFInfo
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- CN100528905C CN100528905C CNB2007100227250A CN200710022725A CN100528905C CN 100528905 C CN100528905 C CN 100528905C CN B2007100227250 A CNB2007100227250 A CN B2007100227250A CN 200710022725 A CN200710022725 A CN 200710022725A CN 100528905 C CN100528905 C CN 100528905C
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- fluorine
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- emulsifying agent
- emulsification
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Abstract
This invention relates to a fluorine cationoid latices and preparation method. The invention takes amphipathy fluorine block polymer as macromolecule emulsifying agent to apply to fine emulsion polymerization, obtain a kind of emulsion particle that has fluorine chain segment and protonated chain segment on surface, namely fluorine cationoid latices. This invention overcomes the traditional process shortcoming of high production cost, at the same time proceed functionalization to the emulsion particle.
Description
Technical field
The present invention relates to a kind of fluorine-containing cation type emulsion, be specifically related to utilize a kind of fluorine-containing amphipathic three block copolymer to be applied in the mini-emulsion polymerization, to obtain the functional latex particle of the positively charged and fluoro-containing group of particle surface as emulsifying agent.
Background technology
Fluorine-containing latex is an environmentally friendly machine, has excellent weather resisteant, high chemical stability, water and oil-resistant, is expected to obtain to use at many key areas.Because the C-F bond energy of fluoropolymer is big than the C-C bond energy,, thereby determined fluoropolymer emulsion to have good weathering resistance, thermotolerance, gloss retention, antiacid rain etc. again because of fluorine atom protects carbon skeleton after replacing hydrogen atom; Fluorine material is because of having extremely low surface energy, and filming of gained has good resistance to crocking.Thereby, exploitation fluoropolymer emulsion product innovation, and make great efforts its application of developing, have great importance.
At present institute's synthetic fluoropolymer emulsion mainly is that fluorochemical monomer and acrylic ester monomer or other vinyl monomer are made by emulsion copolymerization, and fluorochemical monomer commonly used is tetrafluoroethylene, trifluorochloroethylene etc.These fluorochemical monomers are gas often at normal temperatures and pressures, thus in polymerization process often by a series of measures make it to become liquid state could with the acrylic ester monomer copolymerization, this can cause the fluorine-containing latex preparation cost to increase.Along with progress of research, more fluorochemical monomer has been introduced in the fluorine-containing latex preparation, and many fluorochemical monomers are liquid state, and the problems referred to above have obtained solution.The modal method of preparation fluorine-containing latex is to implement by letex polymerization.Because fluorochemical monomer has the character of hydrophobic oleophobic, therefore, traditional emulsion polymerization process will run into such problem: promptly fluorochemical monomer is difficult for shifting in micella from the big drop of monomer, thereby has caused transformation efficiency very low, fluorochemical monomers a large amount of in the system are wasted [Linemann, R F.; Malner T E.; Brandsch R.; Bar G.; Ritter W.; Macromolecules, 1999,32,1715-1721.].Landfester etc. replace conventional emulsion polymerization preparation to have the fluorine-containing latex particle of nucleocapsid structure by mini-emulsion polymerization, have overcome the problem [LandfesterK. that transformation efficiency is low in the letex polymerization simultaneously; Rothe R.; Antonietti M..Macromolecules, 2002,35,1658-1662.].At present, the way for preparing fluorine-containing microballoon mainly is with various polymerization processs fluorochemical monomer and non-fluorochemical monomer to be carried out copolyreaction, the fluorine material of preparation hydridization, but the emulsifying agent that uses in these preparation process still is the emulsifying agent of small molecular weight, has emulsion instability, problem that the fluorochemical monomer consumption is big all the time.
Summary of the invention
The object of the invention provides a kind of fluorine-containing cation type emulsion and preparation method thereof, in the stability that improves emulsion, reduces the preparation cost of fluorine-containing latex.
For achieving the above object, the technical solution used in the present invention is: a kind of fluorine-containing cation type emulsion, and the oil phase of being made by reaction monomers joins the aqueous phase that contains macromole emulsifying agent, obtain through emulsification, polymerization, wherein, described macromole emulsifying agent is the polymkeric substance that following general formula is expressed
In the formula, x is 10～20, and y is 15～60, and z is 5～10,
R
1Be selected from
R
2Be selected from-CH
2CF
3,-CH
2CF
2CHFCF
3,-CH
2CF
2CF
2CF
2CHF
2,-CH
2CF
2CF
2CF
2CF
2CF
2CHF
2, or-CH
2CF
2CF
2CF
2CF
2CF
2CF
2CF
2CF
2CF
3
The preparation method of above-mentioned fluorine-containing cation type emulsion is, adopts the mini-emulsion polymerization method, comprise the following steps,
(1) preparation water: the described emulsifying agent of claim 1 is dissolved in the deionized water, fully stirs, emulsifying agent is fully dissolved, form uniform water;
(2) preparation oil phase: take by weighing reaction monomers according to the solid content ratio, initiator and assistant for emulsifying agent are dissolved in the reaction monomers, fully stir, form uniform oil phase, wherein, described reaction monomers is vinylbenzene or methyl acrylic ester monomer;
(3) pre-emulsification: oil phase is slowly splashed into the aqueous phase of high-speed stirring, stirred 20～30 minutes;
(4) thin emulsification: the emulsion after the pre-emulsification under the protection of outside ice-water bath, is carried out thin emulsification 5～10 minutes by ultrasonic wave to emulsion;
(5) mini-emulsion polymerization: the emulsion after the thin emulsification put into be equipped with in agitator, reflux condensing tube, thermometer and the nitrogen conduit, and feed nitrogen in advance, be warming up to polymeric reaction temperature and reacted 3～7 hours.
In the technique scheme, can require to regulate the pH value of water, in preparation water process, must guarantee that fluorine-containing emulsifier fully dissolves according to reaction.
Optimized technical scheme, in the described water preparation, the consumption of emulsifying agent is 0.11%～0.44% of deionized water in mass; In the described oil phase preparation, solid content is 10%～25%, and described solid content i.e. " oil phase quality/(oil phase quality+water quality) "; The consumption of initiator is 0.10%～1.0% of a monomer mass; The consumption of assistant for emulsifying agent is 1.0%～4.0% of a monomer mass.
In the technique scheme, described initiator is Diisopropyl azodicarboxylate (AIBN) or 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN); Used assistant for emulsifying agent is n-Hexadecane or hexadecanol.
In thin emulsification ultrasonic procedure, the emulsion after the pre-emulsification must be carried out under the protection of ice-water bath, and the ultrasonic wave parameter is: intensity 550W, and impulse ultrasound 50 times, each ultrasonic time is 2 seconds, be 1 second pitch time.
In the technique scheme, in the mini-emulsion polymerization process, before emulsion dropped into reaction system, whole reaction system need feed nitrogen protection in advance, and Fan Ying system is heated to polymeric reaction temperature in advance simultaneously, and described polymeric reaction temperature is 65 ℃～75 ℃.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. the present invention utilizes macromole emulsifying agent, when obtaining stable emulsion, obtained the functional latex particle of " hair " type of a kind of surface band fluorine-containing groups, this emulsion is when filming, and fluorine-containing groups is because its special nature is carried out auto arrangement in film process, be in the surface that film contacts with air, form the film of surface, carry out film performance with the emulsion of utilizing the non-fluorochemical monomer copolymerization of fluorochemical monomer and other to obtain and compare, have similar effects with fluorine-containing layer.
2. the present invention utilizes fluorine-containing emulsifier that the miniemulsion particle surface is modified, and replaces fluorochemical monomer directly to prepare fluorine-containing particle by mini-emulsion polymerization, thereby has reduced the cost for preparing fluorine-containing latex particle and fluorine-containing latex.
3. the emulsifying agent that uses among the present invention not only plays the effect of functionalization emulsion particle, can also stablize mini-emulsion polymerization simultaneously, obtains stable emulsion.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one: fluorine-containing cation type emulsion and preparation thereof
(1) preparation water: the emulsifying agent (PMMA that takes by weighing 0.1g
10-b-PDMAEMA
15-b-POFPMA
5) be dissolved in the 90.0g deionized water, fully stir, emulsifying agent is fully dissolved, form uniform water, regulate aqueous pH values to 3.0 then, standby to treat.
(2) preparation oil phase: according to the solid content ratio is 10%, take by weighing the 10.0g monomer styrene, take by weighing 0.10g initiator Diisopropyl azodicarboxylate (AIBN) (for monomeric 1.0%) then, assistant for emulsifying agent hexadecyl 0.40g (for monomeric 4.0%) is dissolved in the reaction monomers, fully stir, form uniform oil phase, standby to treat.
(3) pre-emulsification: oil phase is slowly splashed into the aqueous phase of high-speed stirring, stirred 20～30 minutes.
(4) thin emulsification: the emulsion after the pre-emulsification immediately under the protection of outside ice-water bath, is carried out thin emulsification 5～10 minutes by ultrasonic wave to emulsion.
(5) mini-emulsion polymerization: the emulsion after the thin emulsification is put in the four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed immediately, and whole reaction system feeds nitrogen in advance and is warming up to 65 ℃, and reaction 7h postcooling is to the room temperature discharging.
Embodiment two: fluorine-containing cation type emulsion and preparation thereof
(1) preparation water: the emulsifying agent (PMMA that takes by weighing 0.2g
10-b-PDMAEMA
15-b-POFPMA
5) be dissolved in the 90.0g deionized water, fully stir, emulsifying agent is fully dissolved, form uniform water, regulate aqueous pH values to 5.0 then, standby to treat.
(2) preparation oil phase: according to the solid content ratio is 10%, take by weighing the 10.0g monomer styrene, take by weighing 0.10g initiator Diisopropyl azodicarboxylate (AIBN) (for monomeric 1.0%) then, assistant for emulsifying agent hexadecyl 0.40g (for monomeric 4.0%) is dissolved in the reaction monomers, fully stir, form uniform oil phase, standby to treat.
(3) pre-emulsification: oil phase is slowly splashed into the aqueous phase of high-speed stirring, stirred 20～30 minutes.
(4) thin emulsification: the emulsion after the pre-emulsification immediately under the protection of outside ice-water bath, is carried out thin emulsification 5～10 minutes by ultrasonic wave to emulsion.
(5) mini-emulsion polymerization: the emulsion after the thin emulsification is put in the four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed immediately, and whole reaction system feeds nitrogen in advance and is warming up to 65 ℃, and reaction 6h postcooling is to the room temperature discharging.
Embodiment three: fluorine-containing cation type emulsion and preparation thereof
(1) preparation water: the emulsifying agent (PMMA that takes by weighing 0.3g
10-b-PDMAEMA
15-b-POFPMA
5) be dissolved in the 90.0g deionized water, fully stir, emulsifying agent is fully dissolved, form uniform water, regulate aqueous pH values to 7.0 then, standby to treat.
(2) preparation oil phase: according to the solid content ratio is 10%, take by weighing the 10.0g monomer styrene, take by weighing 0.10g initiator Diisopropyl azodicarboxylate (AIBN) (for monomeric 1.0%) then, assistant for emulsifying agent hexadecyl 0.40g (for monomeric 4.0%) is dissolved in the reaction monomers, fully stir, form uniform oil phase, standby to treat.
(3) pre-emulsification: oil phase is slowly splashed into the aqueous phase of high-speed stirring, stirred 20～30 minutes.
(4) thin emulsification: the emulsion after the pre-emulsification immediately under the protection of outside ice-water bath, is carried out thin emulsification 5～10 minutes by ultrasonic wave to emulsion.
(5) mini-emulsion polymerization: the emulsion after the thin emulsification is put in the four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed immediately, and whole reaction system feeds nitrogen in advance and is warming up to 65 ℃, and reaction 4h postcooling is to the room temperature discharging.
Embodiment four: fluorine-containing cation type emulsion and preparation thereof
(1) preparation water: the emulsifying agent (PMMA that takes by weighing 0.1g
10-b-PDEAEMA
30-b-PHFBMA
5) be dissolved in the 90.0g deionized water, fully stir, emulsifying agent is fully dissolved, form uniform water, regulate aqueous pH values to 3.0 then, standby to treat.
(2) preparation oil phase: according to the solid content ratio is 10%, take by weighing the 10.0g monomers methyl methacrylate, take by weighing 0.10g initiator Diisopropyl azodicarboxylate (AIBN) (for monomeric 1.0%) then, assistant for emulsifying agent hexadecyl 0.40g (for monomeric 4.0%) is dissolved in the reaction monomers, fully stir, form uniform oil phase, standby to treat.
(3) pre-emulsification: oil phase is slowly splashed into the aqueous phase of high-speed stirring, stirred 20～30 minutes.
(4) thin emulsification: the emulsion after the pre-emulsification immediately under the protection of outside ice-water bath, is carried out thin emulsification 5～10 minutes by ultrasonic wave to emulsion.
(5) mini-emulsion polymerization: the emulsion after the thin emulsification is put in the four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed immediately, and whole reaction system feeds nitrogen in advance and is warming up to 65 ℃, and reaction 4h postcooling is to the room temperature discharging.
Embodiment five: fluorine-containing cation type emulsion and preparation thereof
(1) preparation water: the emulsifying agent (PMMA that takes by weighing 0.2g
10-b-PDMAEMA
60-b-POFPMA
5) be dissolved in the 90.0g deionized water, fully stir, emulsifying agent is fully dissolved, form uniform water, regulate aqueous pH values to 5.0 then, standby to treat.
(2) preparation oil phase: according to the solid content ratio is 20%, take by weighing the 22.5g monomers methyl methacrylate, take by weighing 0.225g initiator Diisopropyl azodicarboxylate (AIBN) (for monomeric 1.0%) then, assistant for emulsifying agent hexadecyl 0.50g (for monomeric 2.0%) is dissolved in the reaction monomers, fully stir, form uniform oil phase, standby to treat.
(3) pre-emulsification: oil phase is slowly splashed into the aqueous phase of high-speed stirring, stirred 20～30 minutes.
(4) thin emulsification: the emulsion after the pre-emulsification immediately under the protection of outside ice-water bath, is carried out thin emulsification 5～10 minutes by ultrasonic wave to emulsion.
(5) mini-emulsion polymerization: the emulsion after the thin emulsification is put in the four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed immediately, and whole reaction system feeds nitrogen in advance and is warming up to 65 ℃, and reaction 4h postcooling is to the room temperature discharging.
Embodiment six: fluorine-containing cation type emulsion and preparation thereof
(1) preparation water: the emulsifying agent (PMMA that takes by weighing 0.3g
10-b-PDMAEMA
60-b-PHFBMA
5) be dissolved in the 90.0g deionized water, fully stir, emulsifying agent is fully dissolved, form uniform water, regulate aqueous pH values to 7.0 then, standby to treat.
(2) preparation oil phase: according to the solid content ratio is 20%, take by weighing the 22.5g monomers methyl methacrylate, take by weighing 0.225g initiator Diisopropyl azodicarboxylate (AIBN) (for monomeric 1.0%) then, assistant for emulsifying agent hexadecyl 0.50g (for monomeric 2.0%) is dissolved in the reaction monomers, fully stir, form uniform oil phase, standby to treat.
(3) pre-emulsification: oil phase is slowly splashed into the aqueous phase of high-speed stirring, stirred 20～30 minutes.
(4) thin emulsification: the emulsion after the pre-emulsification immediately under the protection of outside ice-water bath, is carried out thin emulsification 5～10 minutes by ultrasonic wave to emulsion.
(5) mini-emulsion polymerization: the emulsion after the thin emulsification is put in the four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed immediately, and whole reaction system feeds nitrogen in advance and is warming up to 65 ℃, and reaction 4h postcooling is to the room temperature discharging.
Claims (6)
1. fluorine-containing cation type emulsion, the oil phase of being made by reaction monomers joins the aqueous phase that contains macromole emulsifying agent, obtain through emulsification, polymerization, described reaction monomers is vinylbenzene or methyl acrylic ester monomer, it is characterized in that: described macromole emulsifying agent is the polymkeric substance that following general formula is expressed
In the formula, x is 10～20, and y is 15～60, and z is 5～10,
R
1Be selected from
R
2Be selected from-CH
2CF
3,-CH
2CF
2CHFCF
3,-CH
2CF
2CF
2CF
2CHF
2,-CH
2CF
2CF
2CF
2CF
2CF
2CHF
2, or-CH
2CF
2CF
2CF
2CF
2CF
2CF
2CF
2CF
2CF
3
2. the preparation method of the described fluorine-containing cation type emulsion of claim 1 is characterized in that: adopts the mini-emulsion polymerization method, comprises the following steps,
(1) preparation water: the described macromole emulsifying agent of claim 1 is dissolved in the deionized water, fully stirs, emulsifying agent is fully dissolved, form uniform water; The consumption of described emulsifying agent is 0.11%～0.44% of deionized water in mass;
(2) preparation oil phase: take by weighing reaction monomers according to the solid content ratio, initiator and assistant for emulsifying agent are dissolved in the reaction monomers, fully stir, form uniform oil phase, wherein, described reaction monomers is vinylbenzene or methyl acrylic ester monomer;
(3) pre-emulsification: oil phase is slowly splashed into the aqueous phase of high-speed stirring, stirred 20～30 minutes;
(4) thin emulsification: the emulsion after the pre-emulsification under the protection of outside ice-water bath, is carried out thin emulsification 5～10 minutes by ultrasonic wave to emulsion;
(5) mini-emulsion polymerization: the emulsion after the thin emulsification put into be equipped with in agitator, reflux condensing tube, thermometer and the nitrogen conduit, and feed nitrogen in advance, be warming up to polymeric reaction temperature, reacted 3～7 hours.
3. the preparation method of fluorine-containing cation type emulsion according to claim 2 is characterized in that: in the described oil phase preparation, solid content is 10%～25%, and described solid content i.e. " oil phase quality/(oil phase quality+water quality) "; The consumption of initiator is 0.10%～1.0% of a monomer mass; The consumption of assistant for emulsifying agent is 1.0%～4.0% of a monomer mass.
4. the preparation method of fluorine-containing cation type emulsion according to claim 2, it is characterized in that: described initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile); Used assistant for emulsifying agent is n-Hexadecane or hexadecanol.
5. the preparation method of fluorine-containing cation type emulsion according to claim 2; it is characterized in that: in thin emulsification ultrasonic procedure; emulsion after the pre-emulsification must be carried out under the protection of ice-water bath; the ultrasonic wave parameter is: intensity 550W; impulse ultrasound 50 times; each ultrasonic time is 2 seconds, and be 1 second pitch time.
6. the preparation method of fluorine-containing cation type emulsion according to claim 2; it is characterized in that: in mini-emulsion polymerization; the reaction flask domestic demand feeds nitrogen protection in advance, and Fan Ying system is heated to polymeric reaction temperature in advance simultaneously, and described polymeric reaction temperature is 65 ℃～75 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100227250A CN100528905C (en) | 2007-05-23 | 2007-05-23 | Fluorine-contained cation type emulsion and preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100227250A CN100528905C (en) | 2007-05-23 | 2007-05-23 | Fluorine-contained cation type emulsion and preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101070356A CN101070356A (en) | 2007-11-14 |
| CN100528905C true CN100528905C (en) | 2009-08-19 |
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|---|---|---|---|
| CNB2007100227250A Expired - Fee Related CN100528905C (en) | 2007-05-23 | 2007-05-23 | Fluorine-contained cation type emulsion and preparing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110872363A (en) * | 2018-08-31 | 2020-03-10 | 浙江大学 | Cross-linkable fluorine-containing macromolecular emulsifier, fluorine-containing emulsion containing emulsifier, and preparation and use methods thereof |
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2007
- 2007-05-23 CN CNB2007100227250A patent/CN100528905C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| Latex Blends of Fluorinated and Fluorine-FreeAcrylates: Emulsion POlymerization and Tapping ModeAtomatic Force Microscopy of Film Formation. Reinhard F.LInemann, Thomas E.Malner, Rainer Brandsch,Georg Bar, Wolfgang Ritter, Rolf Mulhaupt.Macromolecules,Vol.32 No.6. 1999 |
| Latex Blends of Fluorinated and Fluorine-FreeAcrylates: Emulsion POlymerization and Tapping ModeAtomatic Force Microscopy of Film Formation. Reinhard F.LInemann, Thomas E.Malner, Rainer Brandsch,Georg Bar, Wolfgang Ritter, Rolf Mulhaupt.Macromolecules,Vol.32 No.6. 1999 * |
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Address after: Suzhou City, Jiangsu province 215137 Xiangcheng District Ji Road No. 8 Patentee after: Soochow University Address before: 215123 Suzhou City, Suzhou Province Industrial Park, No. love road, No. 199 Patentee before: Soochow University |
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Granted publication date: 20090819 Termination date: 20170523 |