CN115028781B - Liquid-like polymer nano emulsion and preparation method thereof - Google Patents
Liquid-like polymer nano emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses liquid-like polymer nanoemulsion and a preparation method thereof, and belongs to the technical field of fine chemical engineering. The preparation method of the liquid-like polymer nano emulsion comprises the steps of uniformly mixing a soft monomer, a hard monomer, an amphiphilic water-soluble monomer, a divinyl end-capped lubricating functional monomer, a fluorine-containing compatibilizer and an initiator, pouring the mixture into water, magnetically stirring, performing ultrasonic grinding in a cell grinder, and performing polymerization reaction under the ultrasonic vibration of an ultrasonic generator to obtain the liquid-like polymer nano emulsion. The method forms the liquid-like polymer nano emulsion with uniform dispersion and good stability without adding an emulsifier and an auxiliary emulsifier, and the whole process is carried out in a system which is full water and has no surfactant, thereby being environment-friendly and simple in process; the prepared liquid-like polymer nano emulsion has low surface energy and ultra-smooth lyophobic performance, and has wide application value in the preparation fields of anti-fouling self-cleaning, anti-fog and anti-icing, anti-biofouling, anti-corrosion and other coatings.
Description
Technical Field
The invention relates to liquid-like polymer nanoemulsion and a preparation method thereof, belonging to the technical field of fine chemical engineering.
Background
In recent years, low-surface-energy self-cleaning coatings have shown wide application prospects in the fields of daily life, industry, agriculture, military and the like due to excellent properties of stain resistance, fog resistance, ice resistance, corrosion resistance, adhesion resistance, drag resistance and the like. At present, two methods for cleaning surfaces are developed, one is prepared by a rough micro-nano composite structure assisted by low surface energy surface chemical modification. Although the surface has excellent self-cleaning performance, the surface has extremely strict requirements on the shape of the micro-nano composite structure, the preparation cost is high, and the process is complex. Another method is to prepare a smooth super-slip coating with a self-cleaning layer of lubricating fluid. In order to prepare the high-durability ultra-smooth self-cleaning coating, polydimethylsiloxane, perfluoroalkyl or perfluoropolyether is grafted into a polymer cross-linked network by utilizing polyurethane and other reactions, and the ultra-smooth self-cleaning coating is prepared by utilizing liquid-like polymers. However, current forms of such polymers are relatively single and, due to the incompatibility between the low surface energy lubricating fluid and the substrate, the polymer has a relatively low level of brush-like content, resulting in a coating with relatively poor ultra-slip properties.
The polyacrylate polymer has excellent film forming property and mechanical property and is widely applied to practical production and life. In order to improve the lyophobic and antifouling properties of polyacrylate polymers and expand the application range of the polyacrylate polymers, researchers develop a series of modification methods for the polyacrylate. The modifier added for realizing lyophobic and antifouling performance generally has high hydrophobicity and oleophobicity, and has extremely large difference with the acrylic ester monomer in surface energy and polarity, and the two monomers have poor compatibility and are difficult to generate polymerization reaction. In addition, the preparation of aqueous low surface energy acrylic polymers is difficult to achieve by conventional emulsion polymerization methods due to the extremely poor solubility of low surface energy materials in aqueous solutions.
The miniemulsion polymerization is to convert the water solvent and the reaction monomer into submicron monomer droplets as polymerization sites through ultrasonic emulsification under the combined action of an emulsifier and a coemulsifier. During the polymerization process, the emulsifier adsorbed on the surface of the droplets may provide electrostatic or steric stabilization to the monomer droplets, thereby preventing the small droplets from aggregating into large droplets to ensure the kinetic stability of the miniemulsion.
Therefore, the miniemulsion polymerization can effectively realize the copolymerization of the low-surface energy monomer and other vinyl monomers, and has higher system stability, smaller particle size of the product emulsion, easy control and moderate polymerization rate. However, the use of large amounts of emulsifiers and co-emulsifiers in conventional miniemulsion polymerizations generally reduces the purity properties of the product, and many products require removal of the emulsifiers before use. In addition, emulsifiers are generally expensive, increase product costs, and cause environmental pollution.
Although researchers at home and abroad modify the miniemulsion polymerization mode by various modes to prepare low surface energy liquid-like polymers, the polymer emulsion developed at present has a plurality of problems such as low reaction polymerization degree and monomer conversion rate, uneven particle size distribution, poor liquid repellency and the like.
Disclosure of Invention
In order to solve the problems, the invention discloses a preparation method for synchronously preparing liquid-like polymer nanoemulsion based on an ultrasonic auxiliary/compatibilizer method, which realizes the grafting type molecular structural design of a liquid-like lubrication liquid brush by selecting proper soft monomers, hard monomers, amphiphilic water-soluble monomers, fluorine-containing compatibilizer monomers and a lubrication functional monomer blocked by divinyl groups; the two hydrophilic soluble monomers are introduced to take part in the reaction and play a role in stabilizing the emulsion to prepare the self-emulsifying miniemulsion, and the stability of the emulsion is improved by an ultrasonic vibration assisted polymerization method, so that the use of an emulsifying agent and an auxiliary emulsifying agent is avoided, and the post-treatment of the polymer emulsion is eliminated; the fluorine-containing compatibilizer is introduced, the compatibility of the low-surface-energy lubricating functional monomer and other monomers is improved through the structural matching degree and the surface energy similarity, and the monomer conversion rate is improved; the particle size distribution and the dispersion uniformity of the polymer nano emulsion are regulated and controlled by regulating the polymerization process so as to meet the use requirements of the polymer nano emulsion in different application scenes. The liquid-like polymer nano emulsion prepared by the invention has high dispersibility, high monomer conversion rate and stable lyophobic lubricating liquid brush, can meet the requirements of common base material coating, and has the advantages of environment-friendly preparation process and simple and convenient application method.
It is an object of the present invention to provide a method for preparing a liquid-like polymer nanoemulsion, the method comprising the steps of:
uniformly mixing a soft monomer, a hard monomer, an amphiphilic water-soluble monomer, a divinyl end-capped lubricating functional monomer, a fluorine-containing compatibilizer and an initiator, and then pouring the mixture into water to obtain a reaction system, so as to prepare a pre-emulsion; and then crushing the pre-emulsion by ultrasonic, and then carrying out polymerization reaction to obtain the liquid-like polymer nano emulsion.
In one embodiment of the invention, the hard monomer comprises one or more of methyl acrylate, vinyl acetate, styrene, acrylonitrile, methyl methacrylate, glycidyl methacrylate.
In one embodiment of the invention, the soft monomer comprises one or more of ethyl acrylate, butyl acrylate, isooctyl acrylate, and lauryl acrylate.
In one embodiment of the present invention, the amphiphilic water-soluble monomer includes one or more of acrylic acid, itaconic acid, maleic acid, and acrylamide.
In one embodiment of the present invention, the fluorine-containing compatibilizer comprises one or more of hexafluorobutyl acrylate, hexafluorobutyl methacrylate, trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate.
In one embodiment of the present invention, the divinyl-terminated lubricating functional monomer comprises one or more of a divinyl-terminated polydimethylsiloxane, a divinyl-terminated perfluoropolyether.
In one embodiment of the invention, the initiator comprises one or more of azobisisobutyronitrile, dibenzoyl peroxide, cumene hydroperoxide.
In one embodiment of the present invention, the soft monomer is 2 to 7% by mass relative to the reaction system, the hard monomer is 0.5 to 5% by mass relative to the reaction system, the fluorine-containing monomer is1 to 10% by mass relative to the reaction system, the amphiphilic water-soluble monomer is 2 to 5% by mass relative to the reaction system, the vinyl-terminated lubricating fluid is 5 to 30% by mass relative to the reaction system, and the initiator is 0.1 to 0.5% by mass relative to the reaction system.
In one embodiment of the invention, the comminuting is carried out using a cell pulverizer; the working power of the cell grinder is 200-800W, the work is carried out for 2s, the pause is carried out for 2s, and the total working time is 5-20min.
In one embodiment of the invention, the polymerization reaction is carried out in an ultrasonic generator; the ultrasonic vibration conditions of the ultrasonic generator are as follows: the frequency is 30-50kHz, the time is 5-10s, the frequency is 70-90kHz, the time is 5-10s, the frequency is 100-120kHz, the time is 10-20s is a cycle period, and the reaction is carried out for 2-8h at the temperature of 60-100 ℃.
In one embodiment of the present invention, the ultrasonic vibration of the ultrasonic generator is performed under the protection of nitrogen.
The second object of the present invention is to provide a liquid-like polymer nanoemulsion prepared by the above-mentioned preparation method of a liquid-like polymer nanoemulsion.
In one embodiment of the present invention, the liquid-like polymer nanoemulsion has a particle size of from 50 to 800nm.
The third object of the invention is to provide an application of the liquid-like polymer nano emulsion in an anti-graffiti, anti-corrosion, anti-fouling self-cleaning, anti-fog and anti-icing functional coating.
The invention has the beneficial effects that:
(1) The invention solves the problem that the high surface tension monomer (> 40 dyne/cm) and the low surface energy monomer (< 20 dyne/cm) are difficult to polymerize by the way of the compatibilizer for the first time, and effectively improves the polymerization degree and the monomer conversion rate of the reaction.
(2) The invention utilizes the amphiphilic water-soluble monomer to play the role of the emulsifier to stabilize emulsion particles while participating in emulsion polymerization reaction, combines the stable dispersion effect of ultrasonic vibration on the emulsion, successfully prepares the high-dispersion nano emulsion in the water solvent under the condition of not using the emulsifier and the auxiliary emulsifier, improves the dispersibility of the emulsion, does not need to carry out purification post-treatment on the emulsion, and avoids the adverse effect of the emulsifier and the auxiliary emulsifier on the performance of the emulsion.
(3) The high-dispersibility polymer nano emulsion prepared by the invention has a liquid-like lubricating liquid brush grafted into a molecular chain, and is beneficial to the construction of a stable super-smooth lyophobic coating.
Drawings
FIG. 1 is a graph of particle size distribution (a) and transmission electron microscopy (b) of the liquid-like polymer nanoemulsion of example 1;
FIG. 2 shows the surface tension (a), centrifugal stability (b) and sliding process (c) of oil droplets on a super-slippery surface constructed with the liquid-like polymer of the liquid-like polymer nanoemulsion of example 1;
FIG. 3 shows the particle size (a) and the monomer conversion (b) of the nanoemulsion in comparative example 1.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for better illustration of the invention, and should not be construed as limiting the invention.
The testing method comprises the following steps:
particle size and Polydispersity (PDI): the particle size and PDI of the nanoemulsion were tested using a nanoparticle sizer. The test sample is prepared by diluting the emulsion to a suitable concentration. The test parameters were set as follows: the temperature was 25℃and the solvent was water. Each sample was tested 5 times to obtain the particle size, distribution, and average value of the sample.
Morphology: the morphology of the samples was tested using a transmission electron microscope (JEM-2100).
Chemical components: the chemical composition of the samples was characterized using a fourier transform infrared spectrometer (Nicoletis 10).
Emulsion centrifugal stability: the sample was placed in a centrifuge and tested for particle size after spinning at 6000rpm-14000rpm for 5 min.
Surface tension: the surface tension was measured by BP100 dynamic surface tensiometer.
Monomer conversion: accurately weighing 2-3 g of polymer emulsion, putting into a polytetrafluoroethylene mould, then putting into a blast oven with constant temperature of 120 ℃ for drying to constant weight, and calculating the solid content (omega) of the emulsion according to the following formula:
ω＝m 0 /m 1 ×100％
wherein omega-solid content,%; m is m 0 -the mass of the emulsion, g; m is m 1 -quality of the film after curing.
The monomer conversion (ψ) is calculated using the following formula:
ψ＝(w 1 ×ω-w 2 )/w 3 ×100％
wherein, psi-conversion rate,%; omega-solids,%; w (w) 1 -total dose, g; w (w) 2 -mass of non-volatile components, g; w (w) 3 Total monomer mass, g.
Example 1
2.5g of butyl acrylate, 1g of hydroxyethyl methacrylate, 2g of acrylamide, 2.5g of hexafluorobutyl methacrylate, 0.1g of azobisisobutyronitrile, 9g of a divinyl-terminated polydimethylsiloxane were taken in a 50mL beaker; after uniformly mixing the monomers, adding 40mL of deionized water, and stirring in an ice-water bath at a rotating speed of 200r/min for 20min to pre-emulsify; after the pre-emulsification is completed, the power of a cell grinder is regulated to 600W, and the cell grinder is ground for 10min in an ice water bath, so that the monomer is dispersed into tiny liquid drops with the particle size of about 100 nm; and then putting the dispersed emulsion into a 100mL three-neck flask, putting the flask into an ultrasonic generator, and continuously reacting for 4 hours at 70 ℃ under the protection of nitrogen to obtain the liquid-like polymer nano emulsion.
And performing performance test on the obtained liquid-like polymer nano emulsion, wherein the particle size and morphology, monomer conversion rate and chemical composition, stability and surface energy test results are shown in figures 1, 2 and 3.
As can be seen from fig. 1: the particle size of the nano emulsion is 109+/-3.8 nm, and the nano emulsion is kept at a nano scale, so that the subsequent assembly on base materials with different morphologies is facilitated. The PDI is only 0.075, which indicates that the nanoemulsion obtained by ultrasonic-assisted polymerization has excellent uniformity and dispersion stability.
As can be seen from fig. 2: under the action of the fluorine-containing compatibilizer, the vinyl blocked polydimethylsiloxane is successfully grafted into the polymer chain segment, and the liquid-like brush endows the emulsion with excellent lyophobic performance, and the surface tension of the emulsion is as low as 25mN/m. The low surface tension liquid-like polymer brush endows the coating with excellent super-slip performance, and oil drops with the surface tension of 28.4mN/m can slip on the surface of the liquid-like polymer coating with a very small dip angle.
As can be seen from FIG. 2b, the particle size of the aqueous polymer nanoemulsion prepared in this example is not changed at all at different rotational speeds of 3000-15000 r/min, and especially at rotational speeds up to 15000r/min, the particle size is still 109.7nm, and there is little difference compared with the particle size (109.6) of the aqueous nanoemulsion not subjected to rotational speed treatment; the nano emulsion prepared by the invention has excellent stability.
Example 2
The amount of acrylamide used in example 1 was adjusted as shown in table 2, and other parameters remained the same, resulting in different nanoemulsions.
The polymer nanoemulsion of example 2 was subjected to performance testing with the following table 1:
table 1 test results of example 3
As can be seen from Table 1, as the amount of acrylamide increases, the particle size of the emulsion obtained by polymerization tends to decrease first and then increase, and the monomer conversion increases first and then decreases. The hydrophilic monomer is used in an increased amount, so that the surface hydrophilicity of the monomer liquid drops can be increased, the surface hydrophilicity of the monomer liquid drops can interact with an aqueous phase interface, and the emulsion stability is improved. However, when the amount of acrylamide is too large, the reaction collision is severe due to the high reactivity, resulting in an increase in the emulsion particle size and a decrease in the monomer conversion.
Example 3
The amounts of vinyl polydimethylsiloxane used in example 1 were adjusted as shown in Table 2, and other parameters were kept consistent to obtain different nanoemulsions.
The performance of the nano-polymer emulsion of example 3 was tested and the test results are shown in table 2 below:
table 2 test results of example 3
As can be seen from table 2: when the coating does not contain the divinyl-terminated polydimethylsiloxane, the nano emulsion has smaller particle size, better dispersibility, low PDI, more complete polymerization reaction and higher monomer conversion rate. However, since there is no lyophobic lubricant brush, the surface tension is high, and the function of liquid repellency cannot be achieved. Along with the improvement of the mass fraction of the divinyl-terminated polydimethylsiloxane from 5% to 15%, the particle size of the nanoemulsion is kept at about 100nm, the PDI is kept at about 0.1, the monomer conversion rate is also kept at more than 90%, the surface tension is obviously reduced, and the subsequent lyophobic paint application is facilitated. And when the mass fraction of the polydimethylsiloxane is 20%, it is difficult for the nanoemulsion to maintain a stable state and the monomer conversion is significantly reduced. It was demonstrated that samples with 20% of the amount of divinyl-terminated polydimethylsiloxane provided good liquid repellency and stability simultaneously.
Example 4
The amount of hexafluorobutyl methacrylate in example 1 was adjusted as shown in table 3, and other parameters were kept consistent to obtain a liquid-like polymer nanoemulsion.
The glass of example 4 with an ultra-smooth, anti-fouling surface was subjected to performance testing, the results of which are given in table 3 below:
table 3 test results of example 4
As can be seen from table 4: increasing the amount of hexafluorobutyl methacrylate compatibilizer can reduce particle size and PDI by increasing the compatibility between the reacting monomers, improving dispersion stability and monomer conversion, but when the hexafluorobutyl methacrylate content is too high, the stability of the emulsion is affected due to its lower surface tension. In addition, the addition of the compatibilizer can effectively reduce the surface tension of the whole emulsion.
Comparative example 1
Referring to the method of example 1, the ultrasonic-assisted self-emulsifying miniemulsion polymerization is replaced by emulsifier-assisted miniemulsion polymerization, and the specific steps are as follows:
2.5g of butyl acrylate, 1g of hydroxyethyl methacrylate, 2g of acrylamide, 2.5g of hexafluorobutyl methacrylate, 0.1g of azobisisobutyronitrile, 9g of a divinyl-terminated polydimethylsiloxane were taken in a 50mL beaker. After the monomers were uniformly mixed, the mixture was poured into 40mL of deionized water containing 0.15g of sodium dodecyl sulfate and 0.1g of hexadecane, and stirred in an ice-water bath at a speed of 200r/min for 20min for pre-emulsification. After the completion of the pre-emulsification, the power of the cell pulverizer was adjusted to 600W, and the mixture was pulverized in an ice water bath for 10 minutes to disperse the monomers into fine droplets having a particle size of about 100 nm. The dispersed emulsion was placed in a 100mL three-necked flask, and the reaction was continued for 4 hours at 70℃under nitrogen protection. And (3) repeatedly carrying out high-speed centrifugal separation and cleaning on the mixture obtained by the reaction for three times to obtain the liquid-like polymer nano emulsion.
The polymer nanoemulsions were tested for infrared and particle size and the results are shown in fig. 3.
The result shows that the particle size of the nano emulsion prepared by adopting the traditional surfactant-assisted emulsion polymerization method is about 105nm, which is similar to the self-emulsifying nano emulsion prepared by the ultrasonic-assisted method, but the PDI is higher than that of the nano emulsion prepared by the ultrasonic-assisted method. The monomer conversion of the reaction was about 83%, indicating that the reaction was not complete.
The obtained nano emulsion is superior to the nano emulsion prepared by the traditional surfactant auxiliary method in dispersion stability and purity.
Comparative example 2
Referring to the method of example 1, the compatibilizer hexafluorobutyl methacrylate is replaced by perfluorooctyl ethyl methacrylate, and the specific steps are as follows:
2.5g of butyl acrylate, 1g of hydroxyethyl methacrylate, 2g of acrylamide, 2.5g of perfluorooctyl ethyl methacrylate, 0.1g of azobisisobutyronitrile, 9g of bisvinyl terminated polydimethylsiloxane were taken in a 50mL beaker. After the monomers were mixed uniformly, the mixture was added dropwise to 40mL of deionized water and stirred in an ice-water bath at a speed of 200r/min for 20min for pre-emulsification. After the completion of the pre-emulsification, the power of the cell pulverizer was adjusted to 600W, and the mixture was pulverized in an ice water bath for 10 minutes to disperse the monomers into fine droplets having a particle size of about 100 nm. And (3) putting the dispersed emulsion into a 100mL three-neck flask, putting the flask into an ultrasonic generator, and continuously reacting for 4 hours at 70 ℃ under the protection of nitrogen to obtain the liquid-like polymer nano emulsion.
Then accurately weighing 2-3 g of polymer emulsion, putting the polymer emulsion into a polytetrafluoroethylene mould, and then putting the polytetrafluoroethylene mould into a blast oven with constant temperature of 120 ℃ for drying to constant weight, wherein the polymer is observed to be still in a liquid state and can not form a solid coating. It is shown that both the molecular structure and the surface energy of the compatibilizer can severely affect the extent of the polymerization reaction.
While the invention has been described with reference to the preferred embodiments, it is not limited thereto, and various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. A method for preparing a liquid-like polymer nanoemulsion, the method comprising the steps of:
uniformly mixing a soft monomer, a hard monomer, an amphiphilic water-soluble monomer, a divinyl end-capped lubricating functional monomer, a fluorine-containing compatibilizer and an initiator, and then pouring the mixture into water to obtain a reaction system, so as to prepare a pre-emulsion; then crushing the pre-emulsion by ultrasonic, and then carrying out polymerization reaction to obtain liquid-like polymer nano emulsion; the hard monomer comprises one or more of methyl acrylate, vinyl acetate, styrene, acrylonitrile, methyl methacrylate and glycidyl methacrylate; the soft monomer comprises one or more of ethyl acrylate, butyl acrylate, isooctyl acrylate and lauryl acrylate; the amphiphilic water-soluble monomer comprises one or more of acrylic acid, itaconic acid, maleic acid and acrylamide; the fluorine-containing compatibilizer comprises one or more of hexafluorobutyl acrylate, hexafluorobutyl methacrylate, trifluoroethyl methacrylate and hexafluoroisopropyl methacrylate; the mass concentration of the soft monomer relative to the reaction system is 2-7%, the mass concentration of the hard monomer relative to the reaction system is 0.5-5%, the mass concentration of the fluorine-containing monomer relative to the reaction system is 1-10%, the mass concentration of the amphiphilic water-soluble monomer relative to the reaction system is 2-5%, the mass concentration of the vinyl-terminated lubricating fluid relative to the reaction system is 5-30%, and the mass concentration of the initiator relative to the reaction system is 0.1-0.5%.
2. The method of claim 1, wherein the comminuting is performed using a cell pulverizer; the working power of the cell grinder is 200-800W, the work is carried out for 2s, the pause is carried out for 2s, and the total working time is 5-20min.
3. The method of claim 1, wherein the polymerization reaction is ultrasonic in an ultrasonic generator; the ultrasonic vibration conditions are as follows: the frequency is 30-50kHz, the time is 5-10s, the frequency is 70-90kHz, the time is 5-10s, the frequency is 100-120kHz, the time is 10-20s is a cycle period, and the reaction is carried out for 2-8h at the temperature of 60-100 ℃.
4. The method of claim 1, wherein the divinyl-terminated lubricating functional monomer comprises one or more of a divinyl-terminated polydimethylsiloxane, a divinyl-terminated perfluoropolyether.
5. The method of claim 1, wherein the initiator comprises one or more of azobisisobutyronitrile, dibenzoyl peroxide, cumene hydroperoxide.
6. A liquid-like polymer nanoemulsion prepared by the method of any one of claims 1-5.
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