CN101012297A - Method of preparing surface fluorine-containing monodisperse polymer microsphere - Google Patents
Method of preparing surface fluorine-containing monodisperse polymer microsphere Download PDFInfo
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- CN101012297A CN101012297A CN 200710051382 CN200710051382A CN101012297A CN 101012297 A CN101012297 A CN 101012297A CN 200710051382 CN200710051382 CN 200710051382 CN 200710051382 A CN200710051382 A CN 200710051382A CN 101012297 A CN101012297 A CN 101012297A
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Abstract
The invention discloses a making method of single-dispersing polymer microball with fluorine on the surface, which comprises the following steps: 1. adding 4-6g monomer A, 0.1-0.2g initiator and 100-120g deionized water in the container within one time; controlling stirring speed; heating to 85 deg.c; insulating to react 2h; 2. dipping 10-20g composite monomer at 1 drop/10s; setting the weight rate of fluorine monomer and monomer A at 0.5-2: 10-20; dripping 5-10ml initiator at 1drop/min with density at 0.05g/ml and 3-6ml pH value buffer solution with density at 0.1g/mL; 3. heating to 85 deg.c to react 2h; obtaining the product.
Description
Technical field
The present invention relates to the polymer microballoon field, particularly a kind of method for preparing surface fluorine-containing monodisperse polymer microsphere.
Background technology
The particle diameter monodisperse polymer micro-sphere is big because of its specific surface area, adsorptivity is strong and surface composition characteristic such as design, be with a wide range of applications in fields such as standard metering, biological chemistry, immune medical science and analytical chemistry.Vanderhoff (J.Polym.Sci., 1956,21:225) wait the people under below-G conditions, successfully to synthesize monodisperse polystyrene microsphere, but this kind preparation method need carry out under the zero gravity condition, severe reaction conditions, its development has been subjected to considerable restraint.In order to overcome the constraint of this reaction conditions, Vanderhoff (J.Colloid Interface Sci., 1968,28:336) wait the people to utilize the way of conventional emulsion polymerization to prepare monodisperse polystyrene microsphere again, because this kind method reaction conditions is easy to repetition, and the polyalcohol microspherulite diameter of preparation is single dispersion, makes to utilize the synthetic monodisperse polymer micro-sphere of this kind method to become the focus of Chinese scholars research.
Okubo (Colloid Polymer Sci., 1991,269:217) wait human seed dispersion copolymerization method to prepare the surface and have the monodisperse polymer micro-sphere of vinyl and the monodisperse polymer micro-sphere of chloromethyl.(Colloid Polymer Sci. such as Wang P.H, 2001,279:98) wait the people to utilize seed emulsion polymerization to prepare surperficial carboxylic polystyrene mono-dispersion microballoon, this microballoon has the potential using value in biological chemistry such as cellular segregation separate nucleic acid, immunodetection and targeted drug and biomedicine etc.Yet above-mentioned prepared polymer microballoon unstable chemcial property, thermostability is bad.
Fluorinated acrylate polymer has excellent physical and chemical performance, at first, in the side chain-CF
3End group guarantees that the fluorate acrylic acid ester polymer has than containing on the main chain-CF
2The fluoropolymer of the class tetrafluoroethylene of group has lower surface energy; Secondly, the acrylate copolymer main chain has makes the fluorate acrylic acid ester polymer have good adhesion property to multiple base material.At last, compare with other compound, organofluorine compound not only has high surface, thermotolerance and chemical stability, and all there is incomparable advantage aspects such as its hydrophobic and lyophobic property, washing fastness, rub resistance.By in acrylic acid esters co-polymer, introducing the structure that fluoro-containing group can change multipolymer, make the acrylic acid esters co-polymer after the modification not only keep the original characteristic of multipolymer, and improve the endurance quality and the chemical stability of polymkeric substance effectively, thereby further widen its application prospect.But fluoroacrylate monomer price is very high, and a large amount of uses will certainly increase substantially the cost of multipolymer, make it lose the market competitiveness.
Linemann R.F (Macromolecules, 1999,32:1715) wait the people to utilize the way of conventional emulsion polymerization to prepare fluorine-containing polymer microballoon, but the particle size dispersion of microballoon is not high, though added a large amount of fluorine monomers, but have only a little fluorine monomer to participate in reaction, and the stability of emulsion is not high.
Summary of the invention
The objective of the invention is at deficiencies such as the prepared surface-functionalized monodisperse polymer micro-sphere unstable chemcial property of prior art, poor heat stability, complex process, utilize the advantage of two stage emulsion polymerizations, and a kind of method for preparing surface fluorine-containing monodisperse polymer microsphere that provides.The characteristics of this method are: 1. Zhi Bei polymer microballoon fluorine-contained surface, and chemical property is stable, Heat stability is good; 2. Zhi Bei microspherulite diameter is single dispersion; 3. reaction conditions is less demanding, and method is simple, is easy to repetition.
The objective of the invention is to adopt following technological line to realize:
At first, the monomer A of disposable adding 4～6g, 0.1～0.2g initiator and 100～120g deionized water in the 250ml four-hole boiling flask, the control stirring velocity, be warmed up to 85 ℃, isothermal reaction 2h, then drip 10～20g mix monomer with 1/10 seconds speed, the mass ratio of fluorochemical monomer and monomer A is 0.5～2: 10～20 in the mix monomer, and is that 0.05g/mL initiator and 3～6mL concentration are the pH value buffer agent solution of 0.1g/mL with speed Dropwise 5～10mL concentration of 1 droplet/minute; 3. after monomer to be mixed, initiator and pH value buffer agent solution dropwise,, get surface fluorine-containing monodisperse polymer microsphere in 85 ℃ of continuation isothermal reaction 2h.
Monomer A described in the above preparation method is vinylbenzene (St) or methyl methacrylate (MMA); Fluorochemical monomer is vinylformic acid trifluoro ethyl ester, vinylformic acid hexafluoro isopropyl ester, vinylformic acid seven fluorine normal butane base esters, trifluoroethyl methacrylate or methacrylic acid hexafluoro isopropyl ester; Initiator is ammonium persulfate or Potassium Persulphate; PH value buffer agent solution is a sodium hydrogen carbonate solution.
The present invention has following advantage: the polymer microballoon fluorine-contained surface of (1) preparation, and chemical property is stable, Heat stability is good; (2) Zhi Bei microspherulite diameter is single dispersion; (3) reaction conditions is less demanding, and method is simple, is easy to repetition.
It is to put into clean cuvette after 0.1% the emulsion that the surface fluorine-containing monodisperse polymer microsphere emulsion concentration of preparation is diluted to volume fraction, in cuvette, insert the slide glass that cleaned simultaneously, put into the baking oven of 65 ℃ of temperature and humidity 70% then, monodisperse polymer micro-sphere moves to slide glass under the effect of capillary force, behind the 12h, monodisperse polymer micro-sphere forms one deck colloid crystal film in the slide surface self-assembly.Then under the condition of 25 ℃ and humidity 60%, adopt the JGW-360B contact angle instrument to measure the Static Water contact angle of colloid crystal film, the water contact angle of film is big more, shows that the content of fluorine is big more.After floride-free and fluorine-containing monodisperse polymer micro-sphere is self-assembled into colloid crystal film, carry out water contact angle test, its water contact angle data such as following table in order to last method.
Floride-free and fluorine-containing monodisperse polymer micro-sphere is self-assembled into the water contact angle data of colloid crystal film
| Sample type | Water contact angle |
| Floride-free mono-dispersion microballoon | 93° |
| Fluorine-containing mono-dispersion microballoon | 121° |
Embodiment
Embodiment 1
At first, disposable adding 5gSt in the 250ml four-hole boiling flask, 0.16g Potassium Persulphate and 110g deionized water, the control stirring velocity, be warmed up to 85 ℃, isothermal reaction 2h, then, drip the mix monomer of 0.5g vinylformic acid trifluoro ethyl ester and 15gSt with 1/10 seconds speed, and to drip 6mL concentration with 1 droplet/minute speed be that Potassium Persulphate and the 5mL concentration of 0.05g/mL is the sodium hydrogen carbonate solution of 0.1g/mL, monomer to be mixed, after initiator and sodium hydrogen carbonate solution dropwise, continue isothermal reaction 2h in 85 ℃, discharging promptly gets surface fluorine-containing monodisperse polymer microsphere.The colloid crystal film that is self-assembled into to microballoon carries out the water contact angle test, and the contact angle of film is 120 °, shows that fluorine-containing mono-dispersion microballoon colloid crystal film that self-assembly becomes has good hydrophobicity.
Embodiment 2
At first, disposable adding 4.5gSt in the 250ml four-hole boiling flask, 0.12g Potassium Persulphate and 110g deionized water, the control stirring velocity, be warmed up to 85 ℃, isothermal reaction 2h, then, drip the mix monomer of 0.5g methacrylic acid hexafluoro isopropyl ester and 15gSt with 1/10 seconds speed, and to drip 6mL concentration with 1 droplet/minute speed be that Potassium Persulphate and the 5.5mL concentration of 0.05g/mL is the sodium hydrogen carbonate solution of 0.1g/mL, monomer to be mixed, after initiator and sodium hydrogen carbonate solution dropwise, continue isothermal reaction 2h in 85 ℃, discharging promptly gets surface fluorine-containing monodisperse polymer microsphere.The colloid crystal film that is self-assembled into to microballoon carries out the water contact angle test, and the contact angle of film is 120 °, shows that fluorine-containing mono-dispersion microballoon colloid crystal film that self-assembly becomes has good hydrophobicity.
Embodiment 3
At first, disposable adding 4.8gSt in the 250ml four-hole boiling flask, 0.14g Potassium Persulphate and 110g deionized water, the control stirring velocity, be warmed up to 85 ℃, isothermal reaction 2h, then, drip the mix monomer of 0.6g vinylformic acid hexafluoro isopropyl ester and 14gSt with 1/10 seconds speed, and to drip 7mL concentration with 1 droplet/minute speed be that Potassium Persulphate and the 4mL concentration of 0.05g/mL is the sodium hydrogen carbonate solution of 0.1g/mL, monomer to be mixed, after initiator and sodium hydrogen carbonate solution dropwise, continue isothermal reaction 2h in 85 ℃, discharging promptly gets surface fluorine-containing monodisperse polymer microsphere.The colloid crystal film that is self-assembled into to microballoon carries out the water contact angle test, and the contact angle of film is 118 °, shows that fluorine-containing mono-dispersion microballoon colloid crystal film that self-assembly becomes has good hydrophobicity.
Embodiment 4
At first, disposable adding 5.6gSt in the 250ml four-hole boiling flask, 0.15g Potassium Persulphate and 120g deionized water, the control stirring velocity, be warmed up to 85 ℃, isothermal reaction 2h, then, drip the mix monomer of 0.6g vinylformic acid seven fluorine normal butane base esters and 16gSt with 1/10 seconds speed, and to drip 8mL concentration with 1 droplet/minute speed be that ammonium persulfate and the 5mL concentration of 0.05g/mL is the sodium hydrogen carbonate solution of 0.1g/mL, monomer to be mixed, after initiator and sodium hydrogen carbonate solution dropwise, continue isothermal reaction 2h in 85 ℃, discharging promptly gets surface fluorine-containing monodisperse polymer microsphere.The colloid crystal film that is self-assembled into to microballoon carries out the water contact angle test, and the contact angle of film is 119 °, shows that fluorine-containing mono-dispersion microballoon colloid crystal film that self-assembly becomes has good hydrophobicity.
Embodiment 5
At first, disposable adding 4.5gMMA in the 250ml four-hole boiling flask, 0.1g Potassium Persulphate and 110g deionized water, the control stirring velocity, be warmed up to 85 ℃, isothermal reaction 2h, then, drip the mix monomer of 0.45g trifluoroethyl methacrylate and 12gMMA with 1/10 seconds speed, and be that Potassium Persulphate and the 5mL concentration of 0.05g/mL is the sodium hydrogen carbonate solution of 0.1g/mL with 1 droplet/minute speed Dropwise 5 mL concentration, monomer to be mixed, after initiator and sodium hydrogen carbonate solution dropwise, continue isothermal reaction 2h in 85 ℃, discharging promptly gets surface fluorine-containing monodisperse polymer microsphere.The colloid crystal film that is self-assembled into to microballoon carries out the water contact angle test, and the contact angle of film is 120 °, shows that fluorine-containing mono-dispersion microballoon colloid crystal film that self-assembly becomes has good hydrophobicity.
Embodiment 6
At first, disposable adding 5.8gMMA in the 250ml four-hole boiling flask, 0.1g Potassium Persulphate and 110g deionized water, the control stirring velocity, be warmed up to 85 ℃, isothermal reaction 2h, then, drip the mix monomer of 1.2g vinylformic acid trifluoro ethyl ester and 14gSt with 1/10 seconds speed, and to drip 7mL concentration with 1 droplet/minute speed be that ammonium persulfate and the 4mL concentration of 0.05g/mL is the sodium hydrogen carbonate solution of 0.1g/mL, monomer to be mixed, after initiator and sodium hydrogen carbonate solution dropwise, continue isothermal reaction 2h in 85 ℃, discharging promptly gets surface fluorine-containing monodisperse polymer microsphere.The colloid crystal film that is self-assembled into to microballoon carries out the water contact angle test, and the contact angle of film is 115 °, shows that fluorine-containing mono-dispersion microballoon colloid crystal film that self-assembly becomes has good hydrophobicity.
Claims (5)
1, a kind of method for preparing surface fluorine-containing monodisperse polymer microsphere, it is characterized in that: carry out according to the following steps: the 1. monomer A of disposable adding 4～6g, 0.1～0.2g initiator and 100～120g deionized water in container, the control stirring velocity is warmed up to 85 ℃, isothermal reaction 2h; 2. drip 10～20g mix monomer with 1/10 seconds speed, the mass ratio of fluorochemical monomer and monomer A is 0.5～2: 10～20 in the mix monomer, and is that 0.05g/mL initiator and 3～6mL concentration are the pH value buffer agent solution of 0.1g/mL with speed Dropwise 5～10mL concentration of 1 droplet/minute; 3. after monomer to be mixed, initiator and pH value buffer agent solution dropwise,, get surface fluorine-containing monodisperse polymer microsphere in 85 ℃ of continuation isothermal reaction 2h.
2, the method for preparing surface fluorine-containing monodisperse polymer microsphere according to claim 1 is characterized in that: monomer A is vinylbenzene (St) or methyl methacrylate (MMA).
3, the method for preparing surface fluorine-containing monodisperse polymer microsphere according to claim 1 is characterized in that: fluorochemical monomer is vinylformic acid trifluoro ethyl ester, vinylformic acid hexafluoro isopropyl ester, vinylformic acid seven fluorine normal butane base esters, trifluoroethyl methacrylate or methacrylic acid hexafluoro isopropyl ester.
4, the method for preparing surface fluorine-containing monodisperse polymer microsphere according to claim 1 is characterized in that: initiator is ammonium persulfate or Potassium Persulphate.
5, the method for preparing surface fluorine-containing monodisperse polymer microsphere according to claim 1 is characterized in that: pH value buffer agent solution is a sodium hydrogen carbonate solution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883336A (en) * | 2016-12-13 | 2017-06-23 | 济南大学 | A kind of preparation method of the fluorine-containing porous polymer material of controllable hole structure |
| CN110898820A (en) * | 2019-12-10 | 2020-03-24 | 西南石油大学 | Fluorine-containing super-hydrophobic porous material for oil-water separation and preparation method thereof |
| CN114058222A (en) * | 2021-12-02 | 2022-02-18 | 新化县中润化学科技有限公司 | Dual self-repairing super-hydrophobic coating and preparation method thereof |
-
2007
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883336A (en) * | 2016-12-13 | 2017-06-23 | 济南大学 | A kind of preparation method of the fluorine-containing porous polymer material of controllable hole structure |
| CN110898820A (en) * | 2019-12-10 | 2020-03-24 | 西南石油大学 | Fluorine-containing super-hydrophobic porous material for oil-water separation and preparation method thereof |
| CN114058222A (en) * | 2021-12-02 | 2022-02-18 | 新化县中润化学科技有限公司 | Dual self-repairing super-hydrophobic coating and preparation method thereof |
| CN114058222B (en) * | 2021-12-02 | 2022-04-19 | 新化县中润化学科技有限公司 | Dual self-repairing super-hydrophobic coating and preparation method thereof |
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