CN114133591A - Preparation method of double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion - Google Patents

Preparation method of double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion Download PDF

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CN114133591A
CN114133591A CN202111344236.3A CN202111344236A CN114133591A CN 114133591 A CN114133591 A CN 114133591A CN 202111344236 A CN202111344236 A CN 202111344236A CN 114133591 A CN114133591 A CN 114133591A
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fluorine
acrylate
repairing
preparation
cellulose nanocrystal
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周建华
李燕
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/02—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to polysaccharides

Abstract

The invention discloses a preparation method of a double self-repairing type cellulose nanocrystalline/fluorine-containing polyacrylate composite emulsion, which comprises the steps of firstly adding amphiphilic block copolymer modified nanocellulose @ polydopamine powder and alkali into water, and then mixing with an acrylate mixed monomer to form a mixture; putting the formed mixture into ultrasound for mixing and emulsification to obtain Pickering emulsion; heating the Pickering emulsion, adding an initiator aqueous solution under the conditions of stirring and protective gas, cooling reactants after the reaction is finished, and finally obtaining the double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion. The introduction of the nano-cellulose makes up the defects of the fluorine-containing polyacrylate emulsion to a certain extent, and avoids the adverse effects of the surfactant on the performance of the latex film and the environment; the introduction of the long-chain acrylic ester monomer and the fluorine-containing acrylic ester monomer enables the emulsion to contain a large amount of hydrophobic long-chain alkyl and fluorine-containing groups, so that the emulsion has good hydrophobicity and the application field is expanded.

Description

Preparation method of double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion
Technical Field
The invention belongs to the technical field of composite emulsion preparation methods, and particularly relates to a preparation method of a double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion.
Background
Leather is a material frequently used in daily life, and is formed by tightly weaving natural collagen fibers in a three-dimensional space, and collagen contains a large number of amino groups, hydroxyl groups and other groups, so that the leather has strong affinity to water, and the use performance of the leather is seriously influenced, therefore, how to obtain a leather product with excellent hydrophobicity becomes a great concern in the leather making process. The fluorine-containing polyacrylate has excellent film forming property and bonding property of acrylic resin, and also has heat resistance, chemical stability, low surface energy, water and oil repellency of fluorine-containing polymer, and is widely applied to the fields of textile, leather, papermaking, coating, building and the like.
In the using process of leather, various damages on the surface, such as collision damage or abrasion, seriously affect the beauty and quality of leather products. It is easy for the damaged leather products to be left unused or discarded, resulting in resource waste and environmental pollution or other problems. In order to solve the problem, the self-repairing material can provide a good idea. Among the stimuli responsive self-healing materials, the photoresponsive self-healing material has unique advantages because light is a clean energy source, and has the advantages of cleanness, simplicity, adjustability and the like. The reversible or irreversible photoresponse behavior can be realized by introducing special photoresponse groups into molecular design. In the research of photo-reversible behavior, coumarin, azobenzene, anthryl derivatives and the like are the most representative photosensitive groups, which can realize reversible conversion of structures under different wavelengths of illumination, and the characteristics are often used in drug controlled release systems, shape memory materials and the like.
Pickering emulsion polymerization uses solid particles to replace a traditional small molecular surfactant as a stabilizer for polymerization reaction, has the advantages of low toxicity or no toxicity, low cost, no pollution and the like compared with the traditional emulsion polymerization, and is widely used for preparing composite materials with special structures and functions. Most of the solid particles used as the Pickering emulsion stabilizer at present are inorganic nanoparticles, and the use of the solid particles not only causes serious problems of accumulation and difficult degradation, but also has great influence on human bodies and environment. Therefore, natural organic particles with rich yield, which are based on the advantages of degradability, biocompatibility, low toxicity and the like, replace inorganic nanoparticles to serve as the Pickering stabilizer, and are more and more concerned by the majority of researchers.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a double self-repairing type cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion, wherein nano cellulose @ polydopamine modified by an amphiphilic block copolymer is used as a Pickering emulsifier, a fluorine-containing monomer and an acrylate monomer are added for Pickering emulsion polymerization, the modified nano cellulose @ polydopamine makes up the defects of the fluorine-containing polyacrylate emulsion, and the adverse effects of a surfactant on the performance of a latex film and the environment are avoided.
In order to achieve the above purpose, the technical scheme adopted by the invention comprises the following steps:
step 1, mixing the following components in percentage by mass (1-5): (3-7): (600-1500): (80-200) mixing and emulsifying the amphiphilic block copolymer modified nano-cellulose @ polydopamine powder, alkali, water and an acrylate mixed monomer to obtain a Pickering emulsion;
and 2, heating the Pickering emulsion obtained in the step 1 at 60-90 ℃, stirring under the condition of protective gas, adding an initiator aqueous solution, and cooling after the reaction is finished to obtain the double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion.
Preferably, the acrylate mixed monomer comprises the following components in percentage by mass (45-81): (30-65): (3-40): (1-14) acrylate soft monomers, acrylate hard monomers, fluorine-containing acrylate monomers and long-chain acrylate monomers.
Preferably, the acrylate soft monomer comprises butyl methacrylate or butyl acrylate; the acrylic hard monomer comprises methyl acrylate or methyl methacrylate; the fluorine-containing acrylate monomer comprises hexafluorobutyl methacrylate, hexafluorobutyl acrylate or dodecafluoroheptyl acrylate; the long-chain acrylic ester monomer comprises octadecyl acrylate or octadecyl methacrylate.
Preferably, the base comprises sodium hydroxide or potassium hydroxide.
Preferably, the emulsification in the step 1 adopts ultrasonic emulsification, and the ultrasonic emulsification time is 4min to 30 min.
Preferably, the aqueous initiator solution comprises ammonium persulfate, potassium persulfate, or sodium persulfate.
Preferably, the concentration of the initiator aqueous solution is 0.4-3 wt%, and the mass of the initiator is 0.5-2.0% of the mass of the acrylate mixed monomer.
Preferably, the stirring speed in the step 2 is 150 r/min-300 r/min, and argon is introduced for 20-40 min.
Preferably, the Pickering emulsion in the step 2 is heated at 60-90 ℃ for reaction for 90-150 min, and the initiator aqueous solution is added within 60-100 min.
Preferably, the Pickering emulsion in the step 2 is placed in a reactor provided with a stirrer, a condenser pipe, a gas-guide pipe and a constant-pressure funnel, and is placed in a water bath for heating, and the initiator aqueous solution is dropwise added or added at one time by a peristaltic pump.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the preparation method of the double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion, the modified cellulose nanocrystal is used as a stabilizer, the cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion is prepared by Pickering emulsion polymerization, and the obtained emulsion has the fluorine characteristic on the basis of keeping the excellent performance of the acrylate emulsion. The introduction of the nano-cellulose makes up the deficiency of the fluorine-containing polyacrylate emulsion to a certain extent, avoids the adverse effects of the surfactant on the performance of the latex film and the environment, and also widens the application field of the cellulose nanocrystal.
(2) In the preparation method of the double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion, the introduction of the long-chain acrylate monomer enables the emulsion to contain a large amount of hydrophobic long-chain alkyl, and the emulsion film prepared from the composite emulsion has good hydrophobicity, thereby expanding the application field of the polyacrylate emulsion film.
(3) The preparation method of the double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate can solve the problem of surface damage of a coating and has the characteristics of environmental protection; and the prepared double self-repairing type cellulose nanocrystalline/fluorine-containing polyacrylate has excellent self-repairing property, hydrophobic and oleophobic property and high film forming stability.
Drawings
FIG. 1 is a FT-IR spectrum of the emulsion film of the double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion prepared by the invention;
FIG. 2 is a drawing test chart of the double self-repairing type cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion prepared by the invention after the latex film is repaired.
Detailed Description
The present invention will be further explained with reference to the drawings and specific examples in the specification, and it should be understood that the examples described are only a part of the examples of the present application, and not all examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The invention provides a preparation method of a double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion, which specifically comprises the following steps:
step 1:
the preparation method comprises the following steps of (1-5) modifying nano cellulose @ polydopamine powder by an amphiphilic block copolymer, alkali, water and an acrylate mixed monomer according to the mass ratio: (3-7): (600-1500): (80-200) adding the mixture into a beaker, and mixing to form a mixture; emulsifying the formed mixture in ultrasound to obtain Pickering emulsion;
wherein the alkali is sodium hydroxide or potassium hydroxide; the ultrasonic emulsification time is 4min to 30 min;
the acrylate mixed monomer is respectively an acrylate soft monomer, an acrylate hard monomer, a fluorine-containing acrylate monomer and a long-chain acrylate monomer, and the mass ratio of the acrylate soft monomer to the acrylate hard monomer is (45-81): (30-65): (3-40): (1-14); the acrylic ester soft monomer comprises butyl methacrylate or butyl acrylate; the acrylic hard monomer comprises methyl acrylate or methyl methacrylate; the fluorine-containing acrylate monomer comprises hexafluorobutyl methacrylate, hexafluorobutyl acrylate or dodecafluoroheptyl acrylate; the long-chain acrylic ester monomer is octadecyl acrylate or octadecyl methacrylate.
Step 2:
step 2.1, adding the Pickering emulsion into a three-neck flask provided with a mechanical stirrer, a condenser pipe, an air duct and a constant-pressure funnel, placing the three-neck flask into a water bath kettle, and introducing argon into the three-neck flask for 20-40 min under the condition that the mechanical stirring speed is 150-300 r/min;
and 2.2, turning on a power supply, after the temperature is raised to 60-90 ℃, dropwise adding an initiator aqueous solution within 60-100 min, then preserving the temperature for 90-150 min, cooling reactants after the reaction in the three-neck flask is finished, and finally obtaining the double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion.
Wherein the initiator aqueous solution comprises ammonium persulfate, potassium persulfate or sodium persulfate; the concentration of the initiator is 0.4-3 wt%, and the mass of the initiator is 0.5-2.0% of that of the acrylate mixed monomer; the dropping mode of the initiator aqueous solution is dropping by a peristaltic pump or adding at one time.
The double self-repairing type cellulose nanocrystalline/fluorine-containing polyacrylate composite emulsion obtained by the preparation method is prepared into an emulsion film, and FT-IR analysis is carried out on the emulsion film, and the result is shown in figure 1, wherein the result is 2953cm-1Is represented by-CH3and-CH2Absorption peak of stretching vibration of 1729cm-1The peak appeared at (1) was an expansion and contraction vibration absorption peak of C ═ O, 1453cm-1The peak at (A) is the stretching vibration absorption peak of C ═ C in the benzene ring, 1350cm-1A stretching vibration absorption peak of 960cm at C-O-C-1，841cm-1The peak is the bending vibration absorption peak of C-H in the benzene ring, 1190cm-1And 700cm-1Two peaks at are-CF2-and-CF3Characteristic of C-F in the radicalAnd (4) peak collection, which indicates that the double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion is prepared.
The latex film was cut in half, the overlapped surfaces were pressed together, and after heating at 70 ℃ for 12 hours, the latex film was subjected to a tensile test, see fig. 2. As can be seen from the figure, the welded latex film can be stretched to more than three times the original length, and there is no fracture at the weld, indicating that the film exhibits excellent weldability.
The present invention will be described in detail with reference to specific examples.
Example 1
Step 1: amphiphilic block copolymer modified nano-cellulose @ polydopamine powder, sodium hydroxide, water and acrylate mixed monomer are mixed according to the mass ratio of 2: 3: 810: 92 into a beaker and mixing to form a mixture; emulsifying the formed mixture in ultrasound for 8min to obtain Pickering emulsion; wherein the acrylate mixed monomer is respectively butyl acrylate, methyl methacrylate, hexafluorobutyl acrylate and octadecyl acrylate, and the mass ratio of the acrylate mixed monomer to the octadecyl acrylate is 48: 30: 11: 3.
step 2: and (3) adding the Pickering emulsion obtained in the step (1) into a three-neck flask provided with a mechanical stirrer, a condenser pipe, an air duct and a constant-pressure funnel, placing the three-neck flask into a water bath kettle, and introducing argon into the three-neck flask for 25min under the condition that the mechanical stirring speed is 220 r/min. And (3) switching on a power supply, after the temperature is raised to 70 ℃, dropwise adding an initiator aqueous solution within 80min, then preserving the temperature for 100min, cooling reactants after the reaction in the three-neck flask is finished, and finally obtaining the double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion.
Example 2
Step 1: amphiphilic block copolymer modified nano-cellulose @ polydopamine powder, sodium hydroxide, water and acrylate mixed monomer are mixed according to the mass ratio of 3: 5: 1050: 127 adding into a beaker, and mixing to form a mixture; emulsifying the formed mixture in ultrasound for 13min to obtain Pickering emulsion; wherein the acrylate mixed monomer is respectively butyl acrylate, methyl methacrylate, hexafluorobutyl acrylate and octadecyl acrylate, and the mass ratio of the acrylate mixed monomer to the octadecyl acrylate is 58: 43: 20: 6.
step 2: and (3) adding the Pickering emulsion obtained in the step (1) into a three-neck flask provided with a mechanical stirrer, a condenser pipe, an air duct and a constant-pressure funnel, placing the three-neck flask into a water bath kettle, and introducing argon into the three-neck flask for 30min under the condition that the mechanical stirring speed is 260 r/min. And (3) switching on a power supply, after the temperature is raised to 80 ℃, dropwise adding an initiator aqueous solution within 90min, then preserving the temperature for 120min, cooling reactants after the reaction in the three-neck flask is finished, and finally obtaining the double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion.
Example 3
Step 1: amphiphilic block copolymer modified nano-cellulose @ polydopamine powder, sodium hydroxide, water and acrylate mixed monomer are mixed according to the mass ratio of 4: 7: 1470: 183 adding into a beaker and mixing to form a mixture; emulsifying the formed mixture in ultrasound for 16min to obtain Pickering emulsion; wherein the acrylate mixed monomer is butyl acrylate, methyl methacrylate, hexafluorobutyl acrylate and octadecyl acrylate respectively, and the mass ratio of the acrylate mixed monomer to the octadecyl acrylate is 76: 59: 37: 11.
step 2: and (3) adding the Pickering emulsion obtained in the step (1) into a three-neck flask provided with a mechanical stirrer, a condenser pipe, a gas guide pipe and a constant pressure funnel, placing the three-neck flask into a water bath kettle, and introducing argon into the three-neck flask for 35min under the condition that the mechanical stirring speed is 280 r/min. And (3) switching on a power supply, after the temperature is raised to 90 ℃, dropwise adding an initiator aqueous solution within 100min, then preserving the heat for 140min, cooling reactants after the reaction in the three-neck flask is finished, and finally obtaining the double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion.
Example 4
Step 1: amphiphilic block copolymer modified nano-cellulose @ polydopamine powder, sodium hydroxide, water and acrylate mixed monomer are mixed according to the mass ratio of 1: 3: 600: 80 adding into a beaker, and mixing to form a mixture; emulsifying the formed mixture in ultrasound for 4min to obtain Pickering emulsion; wherein the acrylate mixed monomer is butyl acrylate, methyl methacrylate, dodecafluoroheptyl acrylate and octadecyl methacrylate respectively, and the mass ratio of the acrylate mixed monomer to the octadecyl methacrylate is 45: 30: 3: 1.
step 2: adding the Pickering emulsion into a three-neck flask provided with a mechanical stirrer, a condenser pipe, an air guide pipe and a constant pressure funnel, placing the three-neck flask into a water bath, and introducing argon into the three-neck flask for 20min under the condition that the mechanical stirring speed is 150 r/min; and (3) switching on a power supply, after the temperature is raised to 60 ℃, dropwise adding 0.4 wt% ammonium persulfate initiator aqueous solution by using a peristaltic pump within 60min, wherein the mass of the ammonium persulfate is 0.5% of that of the acrylate mixed monomer, then preserving the heat for 90min, cooling the reactant after the reaction in the three-neck flask is finished, and finally obtaining the double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion.
Example 5
Step 1: amphiphilic block copolymer modified nano-cellulose @ polydopamine powder, potassium hydroxide, water and acrylate mixed monomer are mixed according to the mass ratio of 5: 7: 1500: 200 into a beaker to form a mixture; emulsifying the formed mixture in ultrasound for 30min to obtain Pickering emulsion; wherein the acrylate mixed monomer is butyl methacrylate, methyl acrylate, hexafluorobutyl acrylate and octadecyl acrylate respectively, and the mass ratio of the acrylate mixed monomer is 81: 65: 40: 14;
step 2: adding the Pickering emulsion into a three-neck flask provided with a mechanical stirrer, a condenser pipe, an air guide pipe and a constant pressure funnel, placing the three-neck flask into a water bath, and introducing argon into the three-neck flask for 40min under the condition that the mechanical stirring speed is 300 r/min; and (2) switching on a power supply, adding the potassium persulfate initiator aqueous solution once within 100min after the temperature rises to 90 ℃, keeping the concentration of the potassium persulfate aqueous solution at 3 wt% and the mass of potassium persulfate at 2.0% of the mass of the acrylate mixed monomer, then keeping the temperature for 150min, cooling the reactant after the reaction in the three-neck flask is finished, and finally obtaining the double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion.
Example 6
Step 1: amphiphilic block copolymer modified nano-cellulose @ polydopamine powder, sodium hydroxide, water and acrylate mixed monomer are mixed according to the mass ratio of 3: 5: 1050: 140 into a beaker and mixed to form a mixture; emulsifying the formed mixture in ultrasound for 17min to obtain Pickering emulsion; the acrylate mixed monomer is butyl methacrylate, methyl methacrylate, dodecafluoroheptyl acrylate and octadecyl methacrylate respectively, and the mass ratio of the acrylate mixed monomer to the octadecyl methacrylate is 63: 47: 20: 8;
step 2: adding the Pickering emulsion into a three-neck flask provided with a mechanical stirrer, a condenser pipe, an air guide pipe and a constant pressure funnel, placing the three-neck flask into a water bath, and introducing argon into the three-neck flask for 30min under the condition that the mechanical stirring speed is 225 r/min; and (3) switching on a power supply, after the temperature rises to 75 ℃, dropwise adding a sodium persulfate aqueous solution by a peristaltic pump within 80min, wherein the concentration of the sodium persulfate aqueous solution is 1.7 wt%, the mass of the sodium persulfate is 1.25% of the mass of the acrylate mixed monomer, then preserving heat for 120min, cooling the reactant after the reaction in the three-neck flask is finished, and finally obtaining the double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. The preparation method of the double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion is characterized by comprising the following steps of:
step 1, mixing the following components in percentage by mass (1-5): (3-7): (600-1500): (80-200) mixing and emulsifying the amphiphilic block copolymer modified nano-cellulose @ polydopamine powder, alkali, water and an acrylate mixed monomer to obtain a Pickering emulsion;
and 2, heating the Pickering emulsion obtained in the step 1 at 60-90 ℃, stirring under the condition of protective gas, adding an initiator aqueous solution, and cooling after the reaction is finished to obtain the double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion.
2. The preparation method of the double self-repairing type cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion according to claim 1, wherein the acrylate mixed monomer comprises the following components in a mass ratio of (45-81): (30-65): (3-40): (1-14) acrylate soft monomers, acrylate hard monomers, fluorine-containing acrylate monomers and long-chain acrylate monomers.
3. The preparation method of the double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion according to claim 2, wherein the acrylate soft monomer comprises butyl methacrylate or butyl acrylate; the acrylic hard monomer comprises methyl acrylate or methyl methacrylate; the fluorine-containing acrylate monomer comprises hexafluorobutyl methacrylate, hexafluorobutyl acrylate or dodecafluoroheptyl acrylate; the long-chain acrylic ester monomer comprises octadecyl acrylate or octadecyl methacrylate.
4. The preparation method of the double self-repairing cellulose nanocrystal/fluoroacrylate composite emulsion as claimed in claim 1, wherein the base comprises sodium hydroxide or potassium hydroxide.
5. The preparation method of the double self-repairing type cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion according to claim 1, wherein the emulsification in the step 1 is ultrasonic emulsification, and the ultrasonic emulsification time is 4-30 min.
6. The preparation method of the double self-repairing cellulose nanocrystal/fluoroacrylate composite emulsion as claimed in claim 1, wherein the aqueous initiator solution comprises ammonium persulfate, potassium persulfate, or sodium persulfate.
7. The preparation method of the double self-repairing type cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion according to claim 6, wherein the concentration of the initiator aqueous solution is 0.4-3 wt%, and the mass of the initiator is 0.5-2.0% of the mass of the acrylate mixed monomer.
8. The preparation method of the double self-repairing type cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion according to claim 1, wherein the stirring speed in the step 2 is 150r/min to 300r/min, and argon is introduced for 20 to 40 min.
9. The preparation method of the dual self-repairing type cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion according to claim 1, wherein the Pickering emulsion in the step 2 is heated at 60-90 ℃ for reaction for 90-150 min, and the initiator aqueous solution is added within 60-100 min.
10. The preparation method of the dual self-repairing type cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion according to claim 1, wherein the Pickering emulsion in the step 2 is placed in a reactor provided with a stirrer, a condenser tube, a gas guide tube and a constant pressure funnel, and is placed in a water bath for heating, and the initiator aqueous solution is added dropwise or at one time by using a peristaltic pump.
CN202111344236.3A 2021-11-15 2021-11-15 Preparation method of double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion Pending CN114133591A (en)

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