CN110606921B - Cationic fluorine-containing soap-free emulsion, and preparation method and application thereof - Google Patents

Cationic fluorine-containing soap-free emulsion, and preparation method and application thereof Download PDF

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CN110606921B
CN110606921B CN201810619227.2A CN201810619227A CN110606921B CN 110606921 B CN110606921 B CN 110606921B CN 201810619227 A CN201810619227 A CN 201810619227A CN 110606921 B CN110606921 B CN 110606921B
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emulsion
vinyl ether
structural formula
polymerization
emulsifier
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CN110606921A (en
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孙斌
陈科
张万里
高自宏
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Zhejiang Chemical Industry Research Institute Co Ltd
Sinochem Lantian Co Ltd
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Sinochem Lantian Co Ltd
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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints

Abstract

The invention discloses a cationic fluorine-containing soap-free emulsion, wherein polymerization monomers of the emulsion comprise chlorotrifluoroethylene, a water-soluble polymerizable macromonomer A, a polymerizable quaternary ammonium salt type emulsifier B and alkyl vinyl ether, and the emulsion is obtained by an emulsion polymerization method in the presence of the polymerizable quaternary ammonium salt type emulsifier shown in a structural formula (B). The cation type fluorine-containing soap-free emulsion provided by the invention has good stability, and the emulsion film prepared from the cation type fluorine-containing soap-free emulsion has low water absorption and excellent water resistance.

Description

Cationic fluorine-containing soap-free emulsion, and preparation method and application thereof
Technical Field
The invention belongs to the field of fluorine-containing high polymer materials, relates to a fluorine-containing emulsion, and particularly relates to a cationic fluorine-containing soap-free emulsion and a preparation method thereof.
Background
The fluorine-containing polymer emulsion has excellent water and oil resistance, stain resistance and solvent resistance, and is widely applied to the fields of textile water and oil resistance finishing, chemical anticorrosion and the like. The fluorine-containing polymer emulsion can be divided into anion and cation types, and the cation type fluorine-containing polymer emulsion can neutralize negative charges of materials such as fabrics due to positive charges on the surface, so that the fluorine-containing polymer emulsion can be applied to the fields of fabric finishing and antistatic materials.
For the preparation of cationic fluoropolymer emulsions, it is generally carried out by adding an emulsifier during the polymerization. Due to the addition of the emulsifier, the emulsifier remains in the finally prepared cationic fluoropolymer emulsion, so that the migration of the emulsifier occurs during the use of the emulsion, and the water resistance and the surface performance of the product are affected. Chinese patent CN104672369B discloses a method for preparing a cationic aqueous fluoropolymer emulsion, which takes chlorotrifluoroethylene, alkyl acid vinyl ester monomer, acrylic ester and/or methacrylic ester as comonomer, and takes quaternary ammonium salt polymerizable emulsifier and nonionic emulsifier as emulsifier to prepare the cationic fluoropolymer emulsion. The cationic aqueous fluoropolymer emulsion prepared by the method has good stability and high solid content, but a nonionic emulsifier is introduced for ensuring the stability of the emulsion under high solid content, so that the migration phenomenon of the emulsifier exists in the use process of the emulsion, and the water resistance and the surface performance of a final product are influenced.
To avoid the influence of emulsifier residues on the use properties of emulsions, the prior art has developed methods for preparing cationic fluorine-containing soap-free emulsions by soap-free emulsion polymerization. Although the method can overcome the influence of the residual emulsifier on the service performance of the emulsion, the prepared cationic fluorine-containing soap-free emulsion has low solid content and poor stability in the polymerization and storage processes, and the application field of the emulsion is limited. For example, chinese patent CN104031204B discloses a method for preparing a cationic fluorine-containing polyacrylate soap-free emulsion, which uses butyl acrylate, styrene, hexafluorobutyl methacrylate and (meth) acryloyloxyethyl trimethyl ammonium chloride as comonomers, uses poly (N, N-dimethylaminoethyl methacrylate-b-hexafluorobutyl acrylate) as an emulsifier, and prepares a fluorine-containing soap-free emulsion through seed emulsion polymerization in the presence of acid and deionized water. The method introduces polymethyl N, N-dimethylaminoethyl-b-poly (hexafluorobutyl acrylate) containing a hydrophilic chain segment and a hydrophobic chain segment in the polymerization process, the hydrophilic chain segment ensures the stability of the emulsion particles, the hydrophobic chain segment has good compatibility with the fluorine-containing monomer and is beneficial to the stability in the emulsion polymerization process, and the emulsifier contains a thiocarbonate active group and can be combined with the emulsion particles through a covalent bond, so that the migration of the emulsifier is avoided, the stability, water and oil repellency and the tightness of electrostatic combination with fabrics of the cationic fluorine-containing polyacrylate soap-free emulsion are improved, but the solid content of the emulsion is lower, and the application range is limited.
Therefore, there is a need for further technical improvements to cationic fluorine-containing emulsions.
Disclosure of Invention
The invention provides a cationic fluorine-containing soap-free emulsion, wherein polymerization monomers of the emulsion comprise chlorotrifluoroethylene, a water-soluble polymerizable macromonomer A, a polymerizable quaternary ammonium salt type emulsifier B and alkyl vinyl ether;
the water-soluble polymerizable macromonomer A is selected from a monomer represented by the following structural formula (A1) and/or a monomer represented by the structural formula (A2):
Figure BDA0001697646130000021
wherein: r1And R2Independently selected from hydrogen, C1-C6 alkyl, m and n are independently selected from integers of 6-20;
the polymerizable quaternary ammonium salt type emulsifier B is selected from monomers shown in the following structural formula (B):
Figure BDA0001697646130000022
wherein: r is selected from C1-C8 alkyl;
the emulsion is obtained by an emulsion polymerization method in the presence of a polymerizable quaternary ammonium salt emulsifier represented by a structural formula (B).
The cationic fluorine-containing soap-free emulsion provided by the invention uses the polymerization monomer comprising the water-soluble polymerizable macromonomer A, wherein the water-soluble polymerizable macromonomer A can be selected from a monomer shown in a structural formula (A1) and/or a monomer shown in a structural formula (A2). In the monomer represented by the formula (A1) and the monomer represented by the formula (A2), R1And R2Independently selected from hydrogen, C1-C6 alkyl.
Preferably, R is1And R2Independently selected from hydrogen, methyl, ethyl, n-propyl, n-butyl, isoamyl, cyclohexyl.
Further preferably, R1And R2Independently selected from hydrogen, ethyl.
In the monomer shown in the structural formula (A1) and the monomer shown in the structural formula (A2), m and n are independently selected from integers of 6-20.
Preferably, m and n are independently selected from integers of 8 to 16.
Further preferably, m and n are independently selected from integers of 10 to 12.
The cationic fluorine-containing soap-free emulsion provided by the invention uses a polymerization monomer comprising a polymerizable quaternary ammonium salt emulsifier B, wherein in the polymerizable quaternary ammonium salt emulsifier shown in the structural formula (B), a substituent R is selected from C1-C8 alkyl.
Preferably, the substituent R is selected from methyl, ethyl, tert-butyl, n-octyl.
Further preferably, the substituent R is selected from methyl and n-octyl.
The invention provides a cationic fluorine-containing soap-free emulsion, wherein the used polymerization monomers also comprise alkyl vinyl ether. The alkyl vinyl ether is preferably at least one selected from the group consisting of ethyl vinyl ether, n-hexyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, and isobutyl vinyl ether.
It is further preferred that the alkyl vinyl ether is selected from at least one of cyclohexyl vinyl ether and isobutyl vinyl ether.
The invention provides a cationic fluorine-containing soap-free emulsion, wherein the used polymerization monomers comprise chlorotrifluoroethylene, a water-soluble polymerizable macromonomer A, a polymerizable quaternary ammonium salt type emulsifier B and alkyl vinyl ether. The ratio of the four polymerization monomers is satisfied to ensure that the reaction is smoothly carried out, and the needed cationic fluorine-containing soap-free emulsion is prepared.
Preferably, the mass ratio of the chlorotrifluoroethylene, the water-soluble polymerizable macromonomer A, the polymerizable quaternary ammonium salt type emulsifier B and the alkyl vinyl ether is 1: 0.01-0.05: 0.8-1.2.
Further preferably, the mass ratio of the chlorotrifluoroethylene to the water-soluble polymerizable macromonomer A to the polymerizable quaternary ammonium salt emulsifier B to the alkyl vinyl ether is 1: 0.01-0.02: 0.02-0.03: 0.9-1.0.
When the water-soluble polymerizable macromonomer A includes both the monomer represented by the structural formula (A1) and the monomer represented by the structural formula (A2), the monomer represented by the structural formula (A1) and the monomer represented by the structural formula (A2) may be present in any ratio.
The invention also provides a preparation method of the cationic fluorine-containing soap-free emulsion, which comprises the following steps:
(1) preparing an emulsion: emulsifying a polymerizable quaternary ammonium salt emulsifier represented by a structural formula (B), alkyl vinyl ether, a water-soluble polymerizable macromonomer A and deionized water which account for 70-80% of the total weight of the emulsifier in a high-speed shearing emulsifying machine to prepare an emulsion;
(2) preparing an emulsion:
a) adding the emulsion accounting for 80-90% of the total weight of the emulsion into a polymerization kettle, and reducing the temperature in the polymerization kettle to be below 5 ℃;
b) adding chlorotrifluoroethylene gas into a polymerization kettle, heating to raise the temperature in the polymerization kettle to 55-65 ℃, adding an initiator accounting for 50-60% of the total weight of the initiator, and starting a polymerization reaction;
c) and B) after polymerizing for a period of time, adding the rest of the emulsion, the rest of the polymerizable quaternary ammonium salt emulsifier shown in the structural formula (B) and the rest of the initiator into a polymerization kettle, and continuing to perform polymerization reaction until the reaction is finished to obtain the cationic fluorine-containing soap-free emulsion.
In the preparation method of the cationic fluorine-containing soap-free emulsion provided by the invention, the used initiator can be an initiator commonly used in the field.
Preferably, the initiator is selected from the group consisting of potassium persulfate, ammonium persulfate, potassium persulfate-sodium bisulfite, azobisisobutylamidine hydrochloride.
As the amount of the initiator, those which are conventional in the art can be used. Preferably, the mass ratio of the used amount of the added initiator to the total added monomers is 1: 100-500.
As for the addition mode of the initiator, the initiator can be directly added, or the initiator can be prepared into an aqueous solution to be added. Preferably, the initiator is added in a manner that the initiator is prepared into an aqueous solution and added into the reaction system. The mass concentration of the aqueous initiator solution may be such that the reaction proceeds smoothly. Preferably, the mass concentration of the initiator aqueous solution is 10-30%.
The polymerizable quaternary ammonium salt emulsifier B of the polymerized monomer is used as an emulsifier in addition to the polymerized monomer. When the emulsifier is used as the emulsifier, the dosage of the polymerizable quaternary ammonium salt emulsifier shown in the structural formula (B) meets the requirement of smooth reaction, and the required cationic fluorine-containing soap-free emulsion is prepared.
The preparation method of the cation type fluorine-containing soap-free emulsion provided by the invention is characterized in that a polymerizable quaternary ammonium salt type emulsifier shown in a structural formula (B) is added in the step of preparing the emulsion. The addition mode of the polymerizable quaternary ammonium salt emulsifier shown in the structural formula (B) can be only directly added, or the polymerizable quaternary ammonium salt emulsifier shown in the structural formula (B) can be prepared into an aqueous solution and added. Preferably, the polymerizable quaternary ammonium salt emulsifier shown in the structural formula (B) is added into the reaction system after being prepared into an aqueous solution. The mass concentration of the aqueous solution of the polymerizable quaternary ammonium salt emulsifier represented by the structural formula (B) is sufficient to allow the reaction to proceed smoothly. Preferably, the mass concentration of the polymerizable quaternary ammonium salt emulsifier aqueous solution shown in the structural formula (B) is 40-60%.
The cationic fluorine-containing soap-free emulsion is obtained by two-step feeding soap-free emulsion polymerization, wherein a majority of emulsion monomers are added into a polymerization kettle for polymerization reaction in the presence of an initiator, and after polymerization for a period of time, the second feeding is carried out, and the rest of emulsion monomers, the rest of polymerizable quaternary ammonium salt type emulsifier and the rest of initiator are added into the polymerization kettle for continuous polymerization. For emulsion polymerization, the polymerization rate and reaction heat release in the early stage of polymerization are relatively stable, and the particle size singleness of the emulsion particles is relatively good, but in the later stage of polymerization, the viscosity is higher and higher along with the increase of the polymer concentration in the emulsion particles, the polymerization reaction can generate a self-acceleration phenomenon, so that the reaction heat release is increased, the stability of the emulsion particles in a system is reduced, the emulsion particles collide and coalesce, and finally the particle size of the emulsion particles is widened. According to the invention, by controlling the adding proportion of the emulsion and the polymerizable quaternary ammonium salt type emulsifier B in the two-step feeding, the concentration of the emulsifier on the surface of the emulsion particle at the later stage of polymerization is ensured, the collision and coalescence probability of the emulsion particle is reduced, the emulsion particle with narrow particle size distribution can be prepared, and the stability of the emulsion particle in a polymerization system is improved.
The solid content of the cationic fluorine-containing soap-free emulsion prepared by the invention can reach 45-52%.
The invention also provides the application of the cationic fluorine-containing soap-free emulsion, which is suitable for neutralizing negative charges on the surface of a material, eliminating electrostatic repulsion or improving the surface performance of the material.
The cationic fluorine-containing soap-free emulsion provided by the invention is particularly suitable for surface antistatic coating in paint dyeing and antistatic materials in the field of fabric finishing.
Compared with the prior art, the cationic fluorine-containing soap-free emulsion provided by the invention has the following advantages:
(1) the prepared emulsion has high solid content and good stability, and the water resistance of the emulsion after film forming is excellent;
(2) the structure of the water-soluble polymerizable macromonomer A contains polyethylene glycol repeated structural units, a hydrophilic shell layer can be formed by good water solubility of the water-soluble polymerizable macromonomer A, and the stability of emulsion particle particles is greatly improved through the synergistic effect of the steric hindrance effect and the electrostatic effect of the polymerizable quaternary ammonium salt emulsifier B;
(3) the emulsion particle with narrow particle size distribution can be prepared by a two-step feeding soap-free emulsion polymerization method, and the stability of the fluorine-containing soap-free emulsion in the polymerization process is improved.
The emulsion prepared by the embodiment of the invention has the following index testing method:
(1) the solid content and the emulsion stability are tested according to a conventional emulsion test method;
(2) the particle size distribution of the emulsion particles is tested by a dynamic laser light scattering instrument, and the smaller the value of the poly-dispersion index (PDI), the narrower the particle size distribution;
(3) the water resistance of the latex film is characterized by water absorption;
(4) water absorption of the latex film: coating the cationic fluorine-containing soap-free emulsion on a polytetrafluoroethylene board, drying the polytetrafluoroethylene board in a ventilated kitchen under natural conditions to form a film, soaking the dried film in deionized water for 7 days, taking out the film, quickly absorbing the surface moisture of the film by using filter paper, weighing the film to obtain the mass, and obtaining the weight gain ratio which is the water absorption rate.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1
Preparing 8g of azodiisobutyl amidine hydrochloride into an initiator aqueous solution with the mass concentration of 20% for later use, preparing 40g of (methyl) acryloyloxyethyl trimethyl ammonium chloride into an aqueous solution with the mass concentration of 50% for later use, adding 400g of isobutyl vinyl ether, 320g of cyclohexyl vinyl ether, 40g of ethoxyethyl vinyl ether (m is 6-8), 64g of (methyl) acryloyloxyethyl trimethyl ammonium chloride solution and 1400g of deionized water into a mixing container, emulsifying for 10min by using a high-speed shearing emulsifying machine to prepare an emulsion, then adding the emulsion accounting for 90% of the total weight of the emulsion into a polymerization kettle, cooling a polymerization kettle jacket by introducing frozen saline water, cooling the temperature to be lower than 5 ℃, vacuumizing the reaction kettle, replacing with nitrogen, adding 800g of chlorotrifluoroethylene into the reaction kettle after the replacement is qualified, starting the reaction kettle, stirring and heating the reaction kettle, after the reaction temperature is stabilized at 60 ℃, adding an initiator aqueous solution accounting for 55 percent of the total weight into a polymerization kettle through a metering pump, polymerizing for 3 hours, adding the rest of emulsion, the rest of (methyl) acryloyloxyethyl trimethyl ammonium chloride solution and the rest of the initiator aqueous solution into the reaction kettle through a metering device, continuing polymerizing for 6 hours after the addition is finished within 20 minutes, cooling the polymerization kettle after the polymerization is finished, recovering unreacted chlorotrifluoroethylene monomer, discharging materials and filtering to obtain the cationic fluorine-containing soap-free emulsion.
Example 2
Preparing 2g of azodiisobutyl amidine hydrochloride into an initiator aqueous solution with the mass concentration of 20% for later use, preparing 16g of (methyl) acryloyloxyethyl N-isopropyl dimethyl ammonium chloride into an aqueous solution with the mass concentration of 50% for later use, adding 350g of isobutyl vinyl ether, 290g of cyclohexyl vinyl ether, 16g of ethoxyethyl (methyl) vinyl ether (m is 10-12), 22g of (methyl) acryloyloxyethyl N-isopropyl dimethyl ammonium chloride solution and 1300g of deionized water into a mixing container, emulsifying for 10min by using a high-speed shearing emulsifying machine to prepare an emulsion, then adding the emulsion accounting for 80% of the total weight of the emulsion into a polymerization kettle, cooling a polymerization kettle jacket by using frozen saline water, vacuumizing the reaction kettle until the temperature is reduced to below 5 ℃, replacing nitrogen, adding 800g of chlorotrifluoroethylene into the reaction kettle after the replacement is qualified, and then starting the reaction kettle to stir and heating the reaction kettle, adding an initiator aqueous solution accounting for 55 percent of the total weight into the polymerization kettle through a metering pump after the reaction temperature is stabilized at 55 ℃, after 4 hours of polymerization, adding the rest of the emulsion, the rest of the (methyl) acryloyloxyethyl N-isopropyl dimethyl ammonium chloride solution and the rest of the initiator aqueous solution into the reaction kettle through a metering device, continuing to polymerize for 6 hours after the addition is finished within 20 minutes, cooling the polymerization kettle after the polymerization is finished, recovering unreacted chlorotrifluoroethylene monomer, discharging the material and filtering to obtain the cationic fluorine-containing soap-free emulsion.
Example 3
Preparing 4g of azodiisobutyl amidine hydrochloride into an initiator aqueous solution with the mass concentration of 20% for later use, preparing 42g of (methyl) acryloyloxyethyl N-N-octyl dimethyl ammonium chloride into an aqueous solution with the mass concentration of 50% for later use, adding 600g of isobutyl vinyl ether, 420g of cyclohexyl vinyl ether, 10g of ethoxyethyl (ethyl) vinyl ether (m is 16-20), 32g of (methyl) acryloyloxyethyl N-octyl dimethyl ammonium chloride solution and 1600g of deionized water into a mixing container, emulsifying for 10min by using a high-speed shearing emulsifying machine to prepare an emulsion, then adding the emulsion accounting for 86% of the total weight of the emulsion into a polymerization kettle, cooling a polymerization kettle jacket by using frozen saline water, vacuumizing the reaction kettle until the temperature is reduced to below 5 ℃, replacing nitrogen, adding 900g of chlorotrifluoroethylene into the reaction kettle after the replacement is qualified, and then starting the reaction kettle to stir and heating the reaction kettle, adding an initiator aqueous solution accounting for 60 percent of the total weight into the polymerization kettle through a metering pump after the reaction temperature is stabilized at 65 ℃, after 4 hours of polymerization, adding the rest of the emulsion, the rest of the (methyl) acryloyloxyethyl N-N-octyldimethylammonium chloride solution and the rest of the initiator aqueous solution into the reaction kettle through a metering device, continuing to polymerize for 8 hours after the addition is finished within 20 minutes, cooling the polymerization kettle after the polymerization is finished, recovering unreacted chlorotrifluoroethylene monomer, discharging the material and filtering to obtain the cationic fluorine-containing soap-free emulsion.
Example 4
Preparing 5g of azodiisobutyl amidine hydrochloride into an initiator aqueous solution with the mass concentration of 20% for later use, preparing 8g of (methyl) acryloyloxyethyl N-N-propyl dimethyl ammonium chloride into an aqueous solution with the mass concentration of 50% for later use, adding 420g of isobutyl vinyl ether, 360g of cyclohexyl vinyl ether, 16g of ethoxyethyl (N-propyl) vinyl ether (m is 14-16), 12g of (methyl) acryloyloxyethyl N-N-propyl dimethyl ammonium chloride solution and 1700g of deionized water into a mixing container, emulsifying for 10min by using a high-speed shearing emulsifying machine to prepare an emulsion, then adding the emulsion accounting for 85% of the total weight of the emulsion into a polymerization kettle, cooling a polymerization kettle jacket by using frozen saline water, vacuumizing the reaction kettle until the temperature is reduced to below 5 ℃, replacing nitrogen, adding 800g of chlorotrifluoroethylene into the reaction kettle after the replacement is qualified, and then starting the reaction kettle to stir and heating the reaction kettle, adding an initiator aqueous solution accounting for 60 percent of the total weight into the polymerization kettle through a metering pump after the reaction temperature is stabilized at 62 ℃, after 3 hours of polymerization, adding the rest of the emulsion, the rest of the (methyl) acryloyloxyethyl N-N-propyldimethyl ammonium chloride solution and the rest of the initiator aqueous solution into the reaction kettle through a metering device, continuing to polymerize for 5 hours after the addition is finished within 20 minutes, cooling the polymerization kettle after the polymerization is finished, recovering unreacted chlorotrifluoroethylene monomer, discharging the material and filtering to obtain the cationic fluorine-containing soap-free emulsion.
Example 5
Preparing 4g of azodiisobutyl amidine hydrochloride into an initiator aqueous solution with the mass concentration of 20% for later use, preparing 8g of (methyl) acryloyloxyethyl N-ethyl dimethyl ammonium chloride into an aqueous solution with the mass concentration of 50% for later use, adding 320g of isopropyl vinyl ether, 340g of cyclohexyl vinyl ether, 8g of allyl polyethylene glycol (N is 6-8), 12g of (methyl) acryloyloxyethyl N-ethyl dimethyl ammonium chloride solution and 1300g of deionized water into a mixing container, emulsifying for 10min by using a high-speed shearing emulsifying machine to prepare an emulsion, then adding the emulsion accounting for 90% of the total weight of the emulsion into a polymerization kettle, cooling a polymerization kettle jacket by using frozen saline water, cooling the temperature to below 5 ℃, vacuumizing the reaction kettle, replacing nitrogen, adding 800g of chlorotrifluoroethylene into the reaction kettle after the replacement is qualified, starting the reaction kettle, stirring and heating the reaction kettle, after the reaction temperature is stabilized at 65 ℃, adding an initiator aqueous solution accounting for 55 percent of the total weight into the polymerization kettle through a metering pump, polymerizing for 3.5 hours, adding the rest of the emulsion, the rest of the (methyl) acryloyloxyethyl N-ethyl dimethyl ammonium chloride solution and the rest of the initiator aqueous solution into the reaction kettle through a metering device, continuing polymerizing for 4 hours after the addition is finished within 20 minutes, cooling the polymerization kettle and recovering unreacted chlorotrifluoroethylene monomer after the polymerization is finished, discharging the materials and filtering to obtain the cationic fluorine-containing soap-free emulsion.
Example 6
Preparing 6.5g of azodiisobutyl amidine hydrochloride into an initiator aqueous solution with the mass concentration of 20% for later use, preparing 32g of (methyl) acryloyloxyethyl N-N-butyl dimethyl ammonium chloride into an aqueous solution with the mass concentration of 50% for later use, adding 320g of ethyl vinyl ether, 340g of cyclohexyl vinyl ether, 24g of methylallyl polyethylene glycol (N ═ 16-20), 46g of (methyl) acryloyloxyethyl N-N-butyl dimethyl ammonium chloride solution and 1200g of deionized water into a mixing container, emulsifying for 10min by using a high-speed shearing emulsifying machine to prepare an emulsion, then adding the emulsion accounting for 80% of the total weight of the emulsion into a polymerization kettle, cooling a polymerization kettle jacket by using frozen saline water, vacuumizing the reaction kettle until the temperature is lower than 5 ℃, replacing nitrogen, adding 800g of chlorotrifluoroethylene into the reaction kettle after the replacement is qualified, starting the reaction kettle, stirring and heating the reaction kettle, after the reaction temperature is stabilized at 57 ℃, adding an initiator aqueous solution accounting for 50 percent of the total weight into the polymerization kettle through a metering pump, after 4 hours of polymerization, adding the rest of the emulsion, the rest of the (meth) acryloyloxyethyl N-N-butyl dimethyl ammonium chloride solution and the rest of the initiator aqueous solution into the reaction kettle through a metering device, continuing to polymerize for 7.5 hours after the addition is finished within 20 minutes, cooling the polymerization kettle after the polymerization is finished, recovering unreacted chlorotrifluoroethylene monomer, discharging the materials and filtering to obtain the cationic fluorine-containing soap-free emulsion.
Example 7
Preparing 6g of azodiisobutyl amidine hydrochloride into an initiator aqueous solution with the mass concentration of 20% for later use, preparing 36g of (methyl) acryloyloxyethyl N-tert-butyl dimethyl ammonium chloride into an aqueous solution with the mass concentration of 50% for later use, adding 520g of ethyl vinyl ether, 150g of isopropyl vinyl ether, 30g of ethyl allyl polyethylene glycol (N is 10-12), 52g of (methyl) acryloyloxyethyl N-tert-butyl dimethyl ammonium chloride and 1400g of deionized water into a mixing container, emulsifying for 10min by using a high-speed shearing emulsifying machine to prepare an emulsion, then adding the emulsion accounting for 88% of the total weight of the emulsion into a polymerization kettle, cooling a polymerization kettle jacket by using frozen saline water, cooling the temperature to below 5 ℃, vacuumizing the reaction kettle, replacing nitrogen, adding 800g of chlorotrifluoroethylene into the reaction kettle after replacement is qualified, starting the reaction kettle, stirring and heating the reaction kettle, after the reaction temperature is stabilized at 60 ℃, adding an initiator aqueous solution accounting for 50 percent of the total weight into the polymerization kettle through a metering pump, after 4 hours of polymerization, adding the rest of the emulsion, the rest of the (meth) acryloyloxyethyl N-tert-butyl dimethyl ammonium chloride solution and the rest of the initiator aqueous solution into the reaction kettle through a metering device, after 20 minutes of addition, continuing to polymerize for 6 hours, after the polymerization is finished, cooling the polymerization kettle, recovering unreacted chlorotrifluoroethylene monomer, discharging the materials and filtering to obtain the cationic fluorine-containing soap-free emulsion.
Example 8
Preparing 6g of azodiisobutyl amidine hydrochloride into an initiator aqueous solution with the mass concentration of 20% for later use, preparing 20g of (methyl) acryloyloxyethyl N-N-hexyl dimethyl ammonium chloride into an aqueous solution with the mass concentration of 50% for later use, adding 460g of ethyl vinyl ether, 200g of cyclohexyl vinyl ether, 20g of isopropyl allyl polyethylene glycol (N ═ 14-16), 30g of (methyl) acryloyloxyethyl N-N-hexyl dimethyl ammonium chloride solution and 1350g of deionized water into a mixing container, emulsifying for 10min by using a high-speed shearing emulsifying machine to prepare an emulsion, then adding the emulsion accounting for 85% of the total weight of the emulsion into a polymerization kettle, cooling a polymerization kettle jacket by using frozen saline water, vacuumizing the reaction kettle until the temperature is reduced to below 5 ℃, replacing the reaction kettle by nitrogen, adding 800g of chlorotrifluoroethylene into the reaction kettle after the replacement is qualified, starting the reaction kettle, stirring and heating the reaction kettle, after the reaction temperature is stabilized at 56 ℃, adding an initiator aqueous solution accounting for 55 percent of the total weight into the polymerization kettle through a metering pump, after polymerizing for 3 hours, adding the rest of the emulsion, the rest of the (methyl) acryloyloxyethyl N-N-hexyldimethylammonium chloride solution and the rest of the initiator aqueous solution into the reaction kettle through a metering device, after the addition is finished within 20 minutes, continuing polymerizing for 6 hours, after the polymerization is finished, cooling the polymerization kettle, recovering unreacted chlorotrifluoroethylene monomer, discharging the materials and filtering to obtain the cationic fluorine-containing soap-free emulsion.
Comparative example 1
Preparing 8g of azodiisobutyl amidine hydrochloride into an initiator aqueous solution with the mass concentration of 20% for later use, preparing 40g of (methyl) acryloyloxyethyl trimethyl ammonium chloride into an aqueous solution with the mass concentration of 50% for later use, adding 400g of isobutyl vinyl ether, 320g of cyclohexyl vinyl ether, all methacryloyloxyethyl trimethyl ammonium chloride solutions and 1400g of deionized water into a mixing container, emulsifying for 10min by using a high-speed shearing emulsifying machine to prepare an emulsion, transferring the emulsion into a polymerization kettle, cooling a polymerization kettle jacket by introducing frozen saline water, vacuumizing the reaction kettle, replacing with nitrogen when the temperature is reduced to below 5 ℃, adding 800g of chlorotrifluoroethylene into the reaction kettle after the replacement is qualified, starting the reaction kettle, stirring and heating the reaction kettle, adding the initiator aqueous solution into the polymerization kettle by using a metering pump after the reaction temperature is stabilized at 60 ℃, polymerizing for 9h, after the polymerization is finished, cooling the polymerization kettle, recovering unreacted chlorotrifluoroethylene monomer, discharging the materials and filtering to obtain the cationic fluorine-containing soap-free emulsion.
Comparative example 2
Preparing 8g of azodiisobutyl amidine hydrochloride into an initiator aqueous solution with the mass concentration of 20% for later use, preparing 40g of (methyl) acryloyloxyethyl trimethyl ammonium chloride into an aqueous solution with the mass concentration of 50% for later use, adding 400g of isobutyl vinyl ether, 320g of cyclohexyl vinyl ether, all methacryloyloxyethyl trimethyl ammonium chloride solutions, 25g of fatty alcohol polyoxyethylene ether-9 and 1400g of deionized water into a mixing container, emulsifying for 10min by using a high-speed shearing emulsifying machine to prepare an emulsion, transferring the emulsion into a polymerization kettle, cooling a jacket of the polymerization kettle by introducing frozen saline, vacuumizing the reaction kettle, replacing nitrogen, adding 800g of chlorotrifluoroethylene into the reaction kettle after the replacement is qualified, starting the reaction kettle to stir and heat the reaction kettle, and after the reaction temperature is stabilized at 60 ℃, adding an initiator aqueous solution into a polymerization kettle through a metering pump, polymerizing for 9 hours, cooling the polymerization kettle after polymerization is finished, recovering unreacted chlorotrifluoroethylene monomer, discharging materials and filtering to obtain the cationic fluorine-containing emulsion.
TABLE 1 basic Properties of cationic fluorine-containing soap-free emulsions
Figure BDA0001697646130000101
As can be seen from table 1: (1) although the emulsion prepared by the comparative example 1 does not have the emulsifier added during the preparation process, so that the emulsifier does not migrate during the use process, and the emulsion film prepared by the emulsion has low water absorption and good water resistance, the emulsion prepared by the emulsion has poor stability compared with the emulsion prepared by each example because the water-soluble macromonomer A is not introduced during the polymerization process; (2) in the polymerization process of comparative example 2, the fatty alcohol-polyoxyethylene ether-9 is used to replace the water-soluble macromonomer A, and the prepared emulsion has good stability, but the added fatty alcohol-polyoxyethylene ether-9 emulsifier can migrate from the inside of the emulsion film to the surface, so that the prepared emulsion film has high water absorption rate and poor water resistance.
The cation fluorine-containing soap-free emulsion prepared by the invention has good stability, and the emulsion film prepared by the cation fluorine-containing soap-free emulsion has low water absorption and excellent water resistance.

Claims (11)

1. The cation type fluorine-containing soap-free emulsion is characterized in that:
the polymerization monomers of the emulsion comprise chlorotrifluoroethylene, a water-soluble polymerizable macromonomer A, a polymerizable quaternary ammonium salt type emulsifier B and alkyl vinyl ether;
the water-soluble polymerizable macromonomer A is selected from a monomer represented by the following structural formula (A1) and/or a monomer represented by the structural formula (A2):
Figure FDA0001697646120000011
wherein: r1And R2Independently selected from hydrogen, C1-C6 alkyl, m and n are independently selected from integers of 6-20;
the polymerizable quaternary ammonium salt type emulsifier B is selected from monomers shown in the following structural formula (B):
Figure FDA0001697646120000012
wherein: r is selected from C1-C8 alkyl;
the emulsion is obtained by an emulsion polymerization method in the presence of a polymerizable quaternary ammonium salt emulsifier represented by a structural formula (B).
2. The cationic fluorochemical soap-free emulsion of claim 1 wherein:
in the monomer shown in the structural formula (A1) and the monomer shown in the structural formula (A2), R1And R2Independently selected from hydrogen, methyl, ethyl, n-propyl, n-butyl, isoamyl, cyclohexyl, m and n are independently selected from integers of 8-16;
in the polymerizable quaternary ammonium salt emulsifier shown in the structural formula (B), R is selected from methyl, ethyl, tert-butyl and n-octyl;
the alkyl vinyl ether is selected from at least one of ethyl vinyl ether, n-hexyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether and isobutyl vinyl ether.
3. The cationic fluorochemical soap-free emulsion of claim 2 wherein:
in the monomer shown in the structural formula (A1) and the monomer shown in the structural formula (A2), R1And R2Independently selected from hydrogen and ethyl, m and n are independently selected from integers of 10-12;
in the polymerizable quaternary ammonium salt emulsifier shown in the structural formula (B), R is selected from methyl and n-octyl;
the alkyl vinyl ether is selected from at least one of cyclohexyl vinyl ether and isobutyl vinyl ether.
4. The cationic fluorochemical soap-free emulsion of claim 1 wherein:
the mass ratio of the chlorotrifluoroethylene to the water-soluble polymerizable macromonomer A to the polymerizable quaternary ammonium salt emulsifier B to the alkyl vinyl ether is 1: 0.01-0.05: 0.8-1.2.
5. The cationic fluorochemical soap-free emulsion of claim 4 wherein:
the mass ratio of the chlorotrifluoroethylene to the water-soluble polymerizable macromonomer A to the polymerizable quaternary ammonium salt emulsifier B to the alkyl vinyl ether is 1: 0.01-0.02: 0.02-0.03: 0.9-1.0.
6. A method of preparing the cationic fluorine-containing soap-free emulsion of claim 1, wherein the method comprises:
(1) preparing an emulsion: emulsifying a polymerizable quaternary ammonium salt emulsifier represented by a structural formula (B), alkyl vinyl ether, a water-soluble polymerizable macromonomer A and deionized water which account for 70-80% of the total weight of the emulsifier in a high-speed shearing emulsifying machine to prepare an emulsion;
(2) preparing an emulsion:
a) adding the emulsion accounting for 80-90% of the total weight of the emulsion into a polymerization kettle, and reducing the temperature in the polymerization kettle to be below 5 ℃;
b) adding chlorotrifluoroethylene gas into a polymerization kettle, heating to raise the temperature in the polymerization kettle to 55-65 ℃, adding an initiator accounting for 50-60% of the total weight of the initiator, and starting a polymerization reaction;
c) and B) after polymerizing for a period of time, adding the rest of the emulsion, the rest of the polymerizable quaternary ammonium salt emulsifier shown in the structural formula (B) and the rest of the initiator into a polymerization kettle, and continuing to perform polymerization reaction until the reaction is finished to obtain the cationic fluorine-containing soap-free emulsion.
7. The method of claim 6, wherein the cationic fluorine-containing soap-free emulsion comprises: the initiator is an initiator aqueous solution with the mass concentration of 10-30%, and the polymerizable quaternary ammonium salt emulsifier shown in the structural formula (B) is an emulsifier aqueous solution with the mass concentration of 40-60%.
8. The method for preparing cationic fluorine-containing soap-free emulsion according to claim 6, wherein the initiator is selected from potassium persulfate, ammonium persulfate, potassium persulfate-sodium bisulfite and azodiisobutyl amidine hydrochloride, and the mass ratio of the initiator to the total input monomers is 1: 100-500.
9. The cationic fluorine-containing soap-free emulsion according to claim 1, wherein the cationic fluorine-containing soap-free emulsion has an emulsion solid content of 45 to 52%.
10. Use of the cationic fluorine-containing soap-free emulsion according to claim 1 for neutralizing negative charges on the surface of a material, eliminating electrostatic repulsion, or improving the surface properties of a material.
11. Use of a cationic fluorine-containing soap-free emulsion according to claim 10, characterized in that the cationic fluorine-containing soap-free emulsion is used for coating dyeing in the field of fabric finishing and surface antistatic coating in antistatic materials.
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