CN113105588A - Method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose - Google Patents
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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Abstract
The invention discloses a method for preparing fluorine-containing polyacrylate emulsion by utilizing light-responsive nano-cellulose. The invention discloses a method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose, which solves the problems that the performance of a product is reduced and the environment is polluted by a surfactant in the prior art.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose.
Background
The fluorine-containing polyacrylate not only has excellent film forming property, caking property and flexibility of polyacrylate, but also has excellent hydrophobicity and good chemical, thermal and photochemical stability of the fluorine-containing polymer. In recent years, fluorine-containing polyacrylate polymers have been widely used for biomaterials, microelectronics, and surface coatings for textiles, paper and leather, etc. due to their unique properties.
The emulsion polymerization technology is a main method for preparing the fluorine-containing polyacrylate due to the characteristics of mild conditions, simple and easily obtained raw materials, water as a reaction medium, environmental protection, safety and the like. However, the small molecule emulsifiers used in conventional emulsion polymerization easily migrate to the interface, negatively affecting the performance and environment of the material.
Pickering emulsion polymerization is the preparation of an emulsion using solid particles instead of traditional emulsifiers. Compared with the emulsion stabilized by the surfactant, the emulsion prepared by Pickering emulsion polymerization is thermodynamically more stable, is not easy to agglomerate and is easier to process. Accordingly, Pickering emulsion polymerization has attracted considerable attention in recent years. However, the Pickering stabilizers most used in Pickering emulsion polymerization are inorganic nanoparticles. With the concern of people on natural, green, rich and sustainable systems, the biodegradable Pickering stabilizer developed and obtained from renewable resources attracts the favor of the majority of researchers.
Nanocellulose (CNC) is an abundant natural nanomaterial with characteristics of low density, aspect ratio, hydrophilicity, high mechanical properties, environmental sustainability, and low cost, and is widely recognized as an ideal biomaterial. At present, many researches on CNC-stabilized Pickering emulsion polymerization are reported, however, there is no research on preparation of a fluorine-containing polyacrylate emulsion by Pickering emulsion polymerization with photoresponsive CNC as Pickering stabilizer.
Disclosure of Invention
The invention aims to provide a method for preparing fluorine-containing polyacrylate emulsion by utilizing light-responsive nano-cellulose, which solves the problems that the performance of a product is reduced and the environment is polluted by a surfactant in the prior art.
The technical scheme adopted by the invention is a method for preparing fluorine-containing polyacrylate emulsion by utilizing light-responsive nano-cellulose, which is implemented according to the following steps:
step 1, preparing photoresponsive nanocellulose aqueous dispersion
Weighing a proper amount of anionic photoresponsive nanocellulose powder and an alkaline aqueous solution, mixing, and forming a dispersion under the action of an ultrasonic cell crusher;
step 2, preparing mixed monomer and initiator aqueous solution
Weighing a proper amount of acrylate first monomer, acrylate second monomer and fluorine-containing acrylate monomer, and mixing by a high-shear emulsifying machine to obtain a mixed monomer; uniformly mixing a proper amount of initiator and deionized water to obtain an initiator aqueous solution for later use;
step 3, preparing Pickering emulsion
Adding the mixed monomer into the dispersion, and mixing and emulsifying in an ultrasonic cell crusher to obtain Pickering emulsion for later use;
and 4, adding the Pickering emulsion into the reactor, adding an initiator aqueous solution into the reactor under the conditions of mechanical stirring and argon protection, and discharging cold water after the reaction is finished to obtain the fluorine-containing polyacrylate emulsion.
The invention is also characterized in that:
in the step 1, the mass ratio of the anionic photoresponsive nano cellulose powder to the alkaline aqueous solution is 3-18: 3250-3900; the alkaline aqueous solution is sodium hydroxide solution or potassium hydroxide solution.
In the step 1, the power of the ultrasonic cell crusher is 5-50%, and the dispersion time is 5-20 min.
In the step 2, the mass ratio of the acrylate first monomer to the acrylate second monomer to the fluorine-containing acrylate monomer is 3-63: 27-81: 1-18;
the acrylate first monomer is methyl acrylate or methyl methacrylate; the acrylate second monomer is butyl methacrylate or butyl acrylate; the fluorine-containing acrylate monomer is hexafluorobutyl methacrylate, hexafluorobutyl acrylate, 2,2, 2-trifluoroethyl methacrylate, dodecafluoroheptyl methacrylate or dodecafluoroheptyl acrylate.
In the step 2, the concentration of the initiator is 0.5-4 wt%, and the mass of the initiator is 0.6-2.0% of that of the mixed monomer;
the initiator is ammonium persulfate, potassium persulfate or sodium persulfate.
In the step 2, the rotating speed of the high-shear emulsifying machine is 500-1000 r/min.
In the step 3, the power of the ultrasonic cell crusher is 20-35%, and the emulsifying time is 5-20 min.
The step 4 specifically comprises the following steps:
step 4.1, adding the Pickering emulsion into a reactor at room temperature, placing the reactor in a water bath, and introducing argon into the reactor for 20-30 min;
and 4.2, turning on a power supply, dripping an initiator aqueous solution within 30-90 min under the condition that the mechanical stirring speed is 100-250 r/min after the temperature of the water bath is raised to 70-85 ℃, keeping the temperature and stirring for 90-120 min at 80-90 ℃, and finally discharging cold water to obtain the fluorine-containing polyacrylate emulsion.
The dropping mode of the initiator aqueous solution is dropping by a peristaltic pump or adding at one time.
The invention has the beneficial effects that:
(1) the invention relates to a method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose, which is characterized in that nanocellulose grafted by an epoxy active group-containing anionic photoresponsive amphiphilic block copolymer prepared by a reversible addition-fragmentation chain transfer polymerization (RAFT) technology is used as a Pickering emulsifier, and the fluorine-containing polyacrylate emulsion is prepared by a Pickering emulsion polymerization method, is negatively charged and has an obvious core-shell structure, wherein CNC is a shell of a latex particle, a fluorine-containing polyacrylate polymer is a core, the emulsion stability is good, and the particle size distribution of the latex particle is small;
(2) the method for preparing the fluorine-containing polyacrylate emulsion by utilizing the photo-responsive nano-cellulose has the advantages of safety and environmental protection, the nano-cellulose modified by the anionic photo-responsive amphiphilic block copolymer is used as a Pickering emulsifier to replace a micromolecule emulsifier in the preparation process, the influence of the traditional surfactant on the product performance is eliminated, the excellent performances of the functionalized nano-cellulose and the fluorine-containing polyacrylate polymer are combined together, and the performance of the polymer is favorably improved;
(3) the method for preparing the fluorine-containing polyacrylate emulsion by utilizing the light-responsive nano-cellulose adopts the light-responsive nano-cellulose as a stabilizer, introduces the light-responsive nano-cellulose into the fluorine-containing polyacrylate polymer through Pickering emulsion polymerization, realizes good dispersion of the nano-cellulose in the fluorine-containing polyacrylate emulsion, widens the application field of the nano-cellulose, and provides a new idea for intelligent application of the fluorine-containing polyacrylate emulsion.
Drawings
FIG. 1 is a transmission electron microscope photograph of fluorine-containing polyacrylate latex particles prepared by the present invention;
FIG. 2 is a graph showing the DLS test results of the fluorine-containing polyacrylate emulsion prepared according to the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose, which is implemented according to the following steps:
step 1, preparing photoresponsive nanocellulose aqueous dispersion
Weighing a proper amount of anionic photoresponsive nanocellulose powder and an alkaline aqueous solution, mixing, and forming a dispersion under the action of an ultrasonic cell crusher;
the mass ratio of the anionic photoresponsive nano-cellulose powder to the alkaline aqueous solution is 3-18: 3250-3900; the alkaline aqueous solution is sodium hydroxide solution or potassium hydroxide solution; the power of the ultrasonic cell crusher is 5-50%, and the dispersion time is 5-20 min.
Step 2, preparing mixed monomer and initiator aqueous solution
Weighing a proper amount of acrylate first monomer, acrylate second monomer and fluorine-containing acrylate monomer, and mixing by a high-shear emulsifying machine to obtain a mixed monomer; uniformly mixing a proper amount of initiator and deionized water to obtain an initiator aqueous solution for later use;
the mass ratio of the acrylate first monomer to the acrylate second monomer to the fluorine-containing acrylate monomer is 3-63: 27-81: 1-18;
the acrylate first monomer is methyl acrylate or methyl methacrylate; the acrylate second monomer is butyl methacrylate or butyl acrylate; the fluorine-containing acrylate monomer is hexafluorobutyl methacrylate, hexafluorobutyl acrylate, 2,2, 2-trifluoroethyl methacrylate, dodecafluoroheptyl methacrylate or dodecafluoroheptyl acrylate;
the concentration of the initiator is 0.5-4 wt%, and the mass of the initiator is 0.6-2.0% of that of the mixed monomer; the initiator is ammonium persulfate, potassium persulfate or sodium persulfate; the dropping mode of the initiator aqueous solution is dropping by a peristaltic pump or adding at one time;
the rotating speed of the high-shear emulsifying machine is 500-1000 r/min;
step 3, preparing Pickering emulsion
Adding the mixed monomer into the dispersion, and mixing and emulsifying in an ultrasonic cell crusher to obtain Pickering emulsion for later use;
wherein the power of the ultrasonic cell crusher is 20-35%, and the emulsifying time is 5-20 min;
step 4, adding Pickering emulsion into a reactor, adding an initiator aqueous solution into the reactor under the conditions of mechanical stirring and argon protection, and discharging cold water after the reaction is finished to obtain the fluorine-containing polyacrylate emulsion; the method specifically comprises the following steps:
step 4.1, adding the Pickering emulsion into a reactor at room temperature, placing the reactor in a water bath, and introducing argon into the reactor for 20-30 min;
and 4.2, turning on a power supply, dripping an initiator aqueous solution within 30-90 min under the condition that the mechanical stirring speed is 100-250 r/min after the temperature of the water bath is raised to 70-85 ℃, keeping the temperature and stirring for 90-120 min at 80-90 ℃, and finally discharging cold water to obtain the fluorine-containing polyacrylate emulsion.
The invention takes nano-cellulose grafted by an anionic ultraviolet-responsive amphiphilic block copolymer containing thiocarbonate end groups and epoxy active groups as a Pickering emulsifier, takes a mixture containing an acrylate first monomer, an acrylate second monomer and a fluorine-containing acrylate monomer as an oil phase to prepare a Pickering emulsion, and prepares the fluorine-containing polyacrylate emulsion by a Pickering emulsion polymerization method.
The light-responsive nano-cellulose is obtained by grafting an anionic ultraviolet light-responsive block copolymer which is prepared by a reversible addition-fragmentation chain transfer polymerization technology and contains a thiocarbonate end group and an epoxy active group, and the block copolymer has an amphipathic property.
The preparation method of the anionic photoresponsive nano cellulose powder comprises the following steps:
step a, preparing a diblock copolymer containing carboxyl and epoxy units
According to the mass ratio of 1: 45: 25: 713, respectively weighing 4,4' -azobis (4-cyanovaleric acid), a carboxyl-containing hydrophilic macromolecule RAFT reagent, glycidyl methacrylate and 1, 4-dioxane, placing into a three-neck flask with magnetons, and stirring and dissolving to form a mixed solution;
introducing argon into a three-neck flask for 30min at room temperature, then heating the three-neck flask to 60 ℃ to enable 4,4' -azobis (4-cyanovaleric acid), a carboxyl-containing hydrophilic macromolecule RAFT reagent and glycidyl methacrylate to react for 6h under the protection of argon to obtain a product;
precipitating and purifying the product in normal hexane, and drying in a vacuum oven to obtain a diblock copolymer containing carboxyl and epoxy units;
step b: preparation of anionic UV-responsive Block copolymer
According to the mass ratio of 1: 50: 67: 20: 1450, respectively weighing 4,4' -azobis (4-cyanovaleric acid), a diblock copolymer containing carboxyl and epoxy units, hexafluorobutyl methacrylate, 7- (2-acryloyloxy) -4-methylcoumarin and 1, 4-dioxane, fully stirring the materials in a three-neck flask with magnetons until the materials are dissolved;
introducing argon into a three-neck flask for 30min at room temperature, heating to 80 ℃, and reacting 4,4' -azobis (4-cyanovaleric acid), a diblock copolymer containing carboxyl and epoxy units, hexafluorobutyl methacrylate and 7- (2-acryloyloxy) -4-methylcoumarin for 8h under the protection of argon to obtain a product;
precipitating and purifying the product in normal hexane, and drying in a vacuum oven to obtain an anionic ultraviolet light response block copolymer;
step c: preparation of anionic ultraviolet light response block copolymer grafted nano-cellulose
According to the mass ratio of 5: 15: 20: 165 respectively weighing nano cellulose (CNC), an anionic ultraviolet response block copolymer, dimethylaminopyridine and N' N dimethylformamide into a flask; putting the flask in an oil bath, heating to 50 ℃, and fully reacting reactants in the flask for 24 hours to obtain a product;
and (3) centrifuging the obtained product by using a centrifuge, washing the product for 3-4 times by using tetrahydrofuran, and drying the product in a vacuum oven to obtain the anionic photoresponse amphiphilic nano cellulose powder.
Example 1
The invention discloses a method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose, which comprises the following steps:
(1) preparation of photo-responsive aqueous nanocellulose dispersion
According to the mass ratio of 3: 3900 weighing anionic photoresponsive nanocellulose powder and sodium hydroxide solution, mixing, and dispersing for 20min under the action of an ultrasonic cell crusher with power of 15% to form dispersion liquid;
(2) preparation of mixed monomer and initiator aqueous solution
According to the mass ratio of 14: 69: 1, respectively weighing methyl methacrylate, butyl acrylate and hexafluorobutyl acrylate, and mixing in a high-shear emulsifying machine with the rotating speed of 600r/min to obtain a mixed monomer; uniformly mixing potassium persulfate with the concentration of 0.5 wt% with deionized water to obtain an initiator aqueous solution, wherein the mass of the potassium persulfate is 0.6% of that of the mixed monomer;
(3) preparation of Pickering emulsion
Adding the mixed monomer into the dispersion, and mixing and emulsifying for 10min in an ultrasonic cell crusher with the power of 20% to obtain Pickering emulsion;
(4) preparation of fluorine-containing polyacrylate emulsion
Adding the Pickering emulsion into a three-neck flask provided with a stirrer, a condenser, a dropping funnel and an argon connecting pipe at room temperature, placing the three-neck flask into a water bath kettle, and introducing argon into the three-neck flask for 20 min;
and (3) switching on a power supply, dripping an initiator aqueous solution by using a peristaltic pump within 30min under the condition that the mechanical stirring speed is 250r/min after the temperature of the water bath kettle rises to 80 ℃, keeping the temperature and stirring at 85 ℃ for 100min, and finally discharging cold water to obtain the fluorine-containing polyacrylate emulsion.
Example 2
The invention discloses a method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose, which comprises the following steps:
(1) preparation of photo-responsive aqueous nanocellulose dispersion
According to the mass ratio of 18: 3250 mixing anionic photoresponsive nanocellulose powder and sodium hydroxide solution, and dispersing for 15min under the action of an ultrasonic cell crusher with power of 5% to form dispersion;
(2) preparation of mixed monomer and initiator aqueous solution
According to the mass ratio of 10: 74: 18 respectively weighing methyl acrylate, butyl methacrylate and hexafluorobutyl methacrylate, and mixing in a high-shear emulsifying machine with the rotating speed of 800r/min to obtain a mixed monomer; uniformly mixing 4 wt% of ammonium persulfate with deionized water to obtain an initiator aqueous solution, wherein the mass of the ammonium persulfate is 2% of that of the mixed monomer;
(3) preparation of Pickering emulsion
Adding the mixed monomer into the dispersion, and mixing and emulsifying in an ultrasonic cell crusher with the power of 25% for 15min to obtain Pickering emulsion;
(4) preparation of fluorine-containing polyacrylate emulsion
Adding the Pickering emulsion into a three-neck flask provided with a stirrer, a condenser, a dropping funnel and an argon connecting pipe at room temperature, placing the three-neck flask into a water bath kettle, and introducing argon into the three-neck flask for 30 min;
and (3) switching on a power supply, dripping an initiator aqueous solution by using a peristaltic pump within 60min under the condition that the mechanical stirring speed is 100r/min after the temperature of the water bath kettle rises to 85 ℃, keeping the temperature and stirring for 90min at 85 ℃, and finally discharging cold water to obtain the fluorine-containing polyacrylate emulsion.
Example 3
The invention discloses a method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose, which comprises the following steps:
(1) preparation of photo-responsive aqueous nanocellulose dispersion
According to the mass ratio of 10: 3400 weighing anionic photoresponsive nanocellulose powder and sodium hydroxide solution, mixing, and dispersing for 5min under the action of an ultrasonic cell crusher with power of 50% to form dispersion liquid;
(2) preparation of mixed monomer and initiator aqueous solution
According to the mass ratio of 36: 54: 10 respectively weighing methyl methacrylate, butyl acrylate and hexafluorobutyl acrylate, and mixing in a high-shear emulsifying machine with the rotating speed of 1000r/min to obtain a mixed monomer; uniformly mixing 1.6 wt% of potassium persulfate with deionized water to obtain an initiator aqueous solution, wherein the mass of the potassium persulfate is 1% of that of the mixed monomer;
(3) preparation of Pickering emulsion
Adding the mixed monomer into the dispersion, and mixing and emulsifying for 10min in an ultrasonic cell crusher with power of 35% to obtain Pickering emulsion;
(4) preparation of fluorine-containing polyacrylate emulsion
Adding the Pickering emulsion into a three-neck flask provided with a stirrer, a condenser, a dropping funnel and an argon connecting pipe at room temperature, placing the three-neck flask into a water bath kettle, and introducing argon into the three-neck flask for 30 min;
and (3) switching on a power supply, dripping an initiator aqueous solution by using a peristaltic pump within 90min under the condition that the mechanical stirring speed is 100r/min after the temperature of the water bath kettle rises to 80 ℃, keeping the temperature and stirring for 120min at 90 ℃, and finally discharging cold water to obtain the fluorine-containing polyacrylate emulsion.
FIG. 1 is a transmission electron microscope photograph of fluorine-containing polyacrylate latex particles prepared by the present invention; as can be seen from FIG. 1, the particle size of the fluorine-containing polyacrylate latex particle is about 200nm, the photo-responsive nano-cellulose is located on the surface of the fluorine-containing polyacrylate latex particle, and the fluorine-containing polyacrylate polymer is wrapped in the inner layer by the photo-responsive nano-cellulose; the surface of the photoresponse nano-cellulose prepared by the method contains a reactive thiocarbonate end group, and the reactive group can continuously participate in the reaction in Pickering emulsion polymerization, so that the nano-particles are connected with the fluorine-containing polyacrylate polymer through covalent bonds.
FIG. 2 is a graph showing the DLS test results of the fluorine-containing polyacrylate emulsion prepared according to the present invention. As can be seen from fig. 2, the measured results are: 280.1nm (PDI 0.178), the diameter of the micelles measured by TEM is smaller than that measured by DLS, since the TEM samples need to be dried, during which the micelles shrink to have a size smaller than that in solution. The invention can effectively solve the problem that the nano particles and the polymer are easy to fall off due to physical adsorption combination, and can introduce the coumarin-containing anionic photoresponse nano-cellulose into the fluorine-containing polyacrylic acid polymer, thereby providing a new idea for intellectualization of the fluorine-containing polyacrylate emulsion.
Claims (9)
1. The method for preparing the fluorine-containing polyacrylate emulsion by utilizing the photoresponsive nanocellulose is characterized by comprising the following steps of:
step 1, preparing photoresponsive nanocellulose aqueous dispersion
Weighing a proper amount of anionic photoresponsive nanocellulose powder and an alkaline aqueous solution, mixing, and forming a dispersion under the action of an ultrasonic cell crusher;
step 2, preparing mixed monomer and initiator aqueous solution
Weighing a proper amount of acrylate first monomer, acrylate second monomer and fluorine-containing acrylate monomer, and mixing by a high-shear emulsifying machine to obtain a mixed monomer; uniformly mixing a proper amount of initiator and deionized water to obtain an initiator aqueous solution for later use;
step 3, preparing Pickering emulsion
Adding the mixed monomer into the dispersion, and mixing and emulsifying in an ultrasonic cell crusher to obtain Pickering emulsion for later use;
and 4, adding the Pickering emulsion into a reactor, adding the initiator aqueous solution into the reactor under the conditions of mechanical stirring and argon protection, and discharging cold water after the reaction is finished to obtain the fluorine-containing polyacrylate emulsion.
2. The method for preparing the fluorine-containing polyacrylate emulsion by using the photo-responsive nanocellulose according to claim 1, wherein in the step 1, the mass ratio of the anionic photo-responsive nanocellulose powder to the alkaline aqueous solution is 3 to 18: 3250-3900; the alkaline aqueous solution is sodium hydroxide solution or potassium hydroxide solution.
3. The method for preparing the fluorine-containing polyacrylate emulsion using photo-responsive nanocellulose according to claim 1, wherein in step 1, the power of the ultrasonic cell crusher is 5% to 50%, and the dispersion time is 5min to 20 min.
4. The method for preparing the fluorine-containing polyacrylate emulsion by using the photo-responsive nanocellulose as claimed in claim 1, wherein in step 2, the mass ratio of the acrylate first monomer, the acrylate second monomer and the fluorine-containing acrylate monomer is 3-63: 27-81: 1-18;
the acrylate first monomer is methyl acrylate or methyl methacrylate; the acrylate second monomer is butyl methacrylate or butyl acrylate; the fluorine-containing acrylate monomer is hexafluorobutyl methacrylate, hexafluorobutyl acrylate, 2,2, 2-trifluoroethyl methacrylate, dodecafluoroheptyl methacrylate or dodecafluoroheptyl acrylate.
5. The method for preparing fluorine-containing polyacrylate emulsion using photo-responsive nano-cellulose according to claim 4, wherein in step 2, the concentration of the initiator is 0.5-4 wt%, and the mass of the initiator is 0.6-2.0% of the mass of the mixed monomer;
the initiator is ammonium persulfate, potassium persulfate or sodium persulfate.
6. The method for preparing the fluorine-containing polyacrylate emulsion using the photo-responsive nano cellulose according to claim 1, wherein the rotation speed of the high shear emulsifying machine in the step 2 is 500 to 1000 r/min.
7. The method for preparing the fluorine-containing polyacrylate emulsion using photo-responsive nanocellulose according to claim 1, wherein in step 3, the power of the ultrasonic cell crusher is 20% to 35%, and the emulsification time is 5min to 20 min.
8. The method for preparing fluorine-containing polyacrylate emulsion using photo-responsive nanocellulose according to claim 1, wherein step 4 specifically comprises:
step 4.1, adding the Pickering emulsion into a reactor at room temperature, placing the reactor in a water bath, and introducing argon into the reactor for 20-30 min;
and 4.2, turning on a power supply, dripping an initiator aqueous solution within 30-90 min under the condition that the mechanical stirring speed is 100-250 r/min after the temperature of the water bath is raised to 70-85 ℃, keeping the temperature and stirring for 90-120 min at 80-90 ℃, and finally discharging cold water to obtain the fluorine-containing polyacrylate emulsion.
9. The method for preparing fluorine-containing polyacrylate emulsion using photo-responsive nanocellulose according to claim 1, wherein the aqueous initiator solution is added dropwise by using a peristaltic pump or added at one time.
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