CN110577611B - Preparation method of vinylidene fluoride polymer aqueous dispersion liquid for coating - Google Patents
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- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
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- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract
A preparation method of vinylidene fluoride polymer aqueous dispersion liquid for coating belongs to the technical field of fluorine chemical coating. The method comprises three stages: the first stage, adding deionized water, an initiator, a dispersant, a stabilizer, a chain transfer agent and a polymerization monomer into a high-pressure reaction kettle to carry out emulsion polymerization reaction to obtain vinylidene fluoride polymer mother liquor; in the second stage, adding a surfactant into the vinylidene fluoride polymer mother liquor, and heating to 3-5 ℃ below the cloud point of the surfactant; adding surfactant and electrolyte again, heating to 1-10 deg.C above the surfactant cloud point, standing at constant temperature for 6-24 hr; and in the third stage, separating supernatant of the vinylidene fluoride polymer emulsion, adding a pH regulator and a stabilizer into the lower-layer emulsion, and then passing the emulsion through a 400-mesh filter screen to obtain a final product. The preparation method of the vinylidene fluoride polymer aqueous dispersion liquid for the coating has the advantages of environmental protection, high solid content and stable storage.
Description
Technical Field
The invention belongs to the technical field of fluorine chemical coatings, and particularly relates to a preparation method of a vinylidene fluoride polymer aqueous dispersion liquid for a coating.
Background
The coating industry in china has experienced rapid growth over the past fifty years and china has become the second largest world for coating production and consumption. Fluorocarbon coatings based on polyvinylidene fluoride (PVDF) resin are widely used in the fields of construction, industrial corrosion prevention and the like due to excellent weather resistance, chemical resistance, stain resistance and easy maintenance.
At present, most PVDF fluorocarbon resin manufacturers use perfluoro organic surfactants (PFOCs including PFOA, PFOS and other PFCs) to produce PVDF resin. The perfluorinated organic substances have toxicity, durability, biological accumulation and long-distance migration characteristics, are determined as carcinogenic substances and are widely present in various biospheres of the earth. In addition, a large amount of latent solvent is required to be added in the processing process of the PVDF fluorocarbon resin, and the latent solvent is volatilized by heating to cause the emission of a large amount of Volatile Organic Compounds (VOC), thereby causing serious pollution to the environment. With the restrictions of environmental protection regulations on VOC emission and the low-carbon requirements of energy conservation and consumption reduction, a new generation of PFCs-free production technology and an environment-friendly aqueous PVDF fluorocarbon coating are a new development trend.
At present, the international aqueous fluorine-containing polymer concentrated solution mainly comprises two major types of tetrafluoroethylene and perfluoroethylene propylene, and the solid content is about 60 percent generally; the vinylidene fluoride-based aqueous concentrated solution has not been commercialized, but the solid content can not meet the requirement, if the solid content is lower than 55%, the performance of the product can not meet the requirement of fluorocarbon coating, and the use value is lost.
Patent CN 106749798B discloses a preparation method of a coating type polyvinylidene fluoride polymer. Although the method adopts the substitutes of PFCs as the emulsifier, the produced product is also oil-soluble PVDF fluorocarbon resin, and can cause environmental pollution.
Patent CN 1612911B discloses a concentrated fluoropolymer dispersion. The monomer is non-meltable tetrafluoroethylene, which is not suitable for serving as fluorocarbon coating.
Patent CN 102161769B discloses an aqueous fluoropolymer dispersion emulsion and its stabilizing method. The fluorine-containing resin used in the method is mainly tetrafluoroethylene, and PFOA, a large amount of anionic and cationic surfactants are used in the emulsion polymerization process. The product can not be used for fluorocarbon coating, and is not environment-friendly.
Patent CN 101104697B discloses a method for producing an aqueous fluororesin dispersion. The fluorine resin is tetrafluoroethylene, and the defect that PFOA anionic fluorinated surfactant is used in the polymerization process also exists.
Patent CN 104119544B discloses a preparation method of a polyperfluorinated ethylene propylene concentrated dispersion liquid. The fluorine-containing resin used in the method mainly comprises tetrafluoroethylene and hexafluoropropylene; PFOA is used in the emulsion polymerization process; vacuum heating is adopted in the concentration process. The product is mainly used for coating and dipping and is not suitable for the coating industry.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to design and provide a technical scheme of a preparation method of a PFCs-free vinylidene fluoride polymer aqueous dispersion liquid for a coating, and the aqueous dispersion liquid prepared by the method has high solid content, is clean and environment-friendly, does not cause environmental pollution, and is suitable for the coating industry.
The preparation method of the vinylidene fluoride polymer aqueous dispersion liquid for the coating is characterized by comprising the following steps:
1) The first stage is as follows: adding deionized water, an initiator, a dispersant, a stabilizer, a chain transfer agent and a polymerization monomer into a high-pressure reaction kettle to carry out emulsion polymerization reaction to obtain vinylidene fluoride polymer mother liquor;
2) In the second stage, adding 0.2-1.0% of surfactant into vinylidene fluoride polymer mother liquor, stirring at a low speed, and heating to 3-5 ℃ below the cloud point of the surfactant at a speed of 0.75-1.35 ℃/min; adding 3-8% of surfactant and 0.02-0.08% of electrolyte again, rapidly stirring, heating to 1-10 deg.C above the cloud point of surfactant at a rate of 0.15-0.35 deg.C/min, stopping stirring, standing at constant temperature for 1-4 hr, stopping heating, and cooling to room temperature;
3) And the third stage, separating the supernatant of the vinylidene fluoride polymer emulsion, adding a pH regulator and a stabilizer into the lower layer emulsion, and passing the emulsion through a filter screen of 300-500 meshes to obtain the aqueous dispersion of the vinylidene fluoride polymer for the coating.
The preparation method of the vinylidene fluoride polymer aqueous dispersion liquid for the coating is characterized in that in the first stage of the step 1): the polymerization monomer consists of vinylidene fluoride and other fluorine-containing monomers, and the other fluorine-containing monomers are one or a mixture of more than one of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene and perfluoroalkyl vinyl ether; the weight ratio of the vinylidene fluoride to other fluorine-containing monomers is 95:5 to 100:0, preferably in a weight ratio of 96.5: 3.5-98.5: 1.5.
the preparation method of the vinylidene fluoride polymer aqueous dispersion liquid for the coating is characterized in that in the first stage of the step 1): the initiator is organic peroxide, the dispersing agent is fluoroether sulfonate, the stabilizing agent is paraffin, and the chain transfer agent is diethyl malonate, ethyl acetate or diethyl carbonate.
The preparation method of the vinylidene fluoride polymer aqueous dispersion liquid for the coating is characterized in that in the first stage of the step 1): the weight ratio of the deionized water, the initiator, the dispersant, the stabilizer, the chain transfer agent and the polymerization monomer is 100: 1.5 multiplied by 10 -3 ～3.5×10 -2 ∶0.08～0.35∶0.03～0.12∶5.7×10 -3 ～7.2×10 -2 20 to 35 percent; the weight ratio is preferably 100: 2.0X 10 -3 ～3.0×10 -2 ∶0.15～0.30∶0.05～0.10∶6.0×10 -3 ～7.0×10 -2 22-32; the weight ratio is more preferably 100: 2.2X 10 -3 ～2.8×10 -2 ∶0.18～0.27∶0.07～0.09∶6.2×10 -3 ～6.8×10 -2 ∶25～30。
The preparation method of the vinylidene fluoride polymer aqueous dispersion liquid for the coating is characterized in that in the first stage of the step 1): the solid content of the vinylidene fluoride polymer emulsion mother liquor is 22-28%, preferably 25-27%.
The preparation method of the vinylidene fluoride polymer aqueous dispersion liquid for the coating is characterized in that in the second stage of the step 2): the amount of the surfactant added is 2 to 8wt%, preferably 4 to 6wt%, with respect to 100 parts by weight of the vinylidene fluoride polymer emulsion mother liquor.
The preparation method of the vinylidene fluoride polymer aqueous dispersion liquid for the coating is characterized in that in the second stage of the step 2): the surfactant is a nonionic surfactant, specifically is a condensate of alkylphenol or fatty alcohol and ethylene oxide, and the cloud point temperature of the surfactant is 60-85 ℃; the slow stirring speed is 10-30 rpm, preferably 15-20 rpm; heating to 4 deg.C below the cloud point of surfactant at a rate of 0.8-1.3 deg.C/min, preferably 1.0-1.1 deg.C/min; the rapid stirring speed is 200-400 rpm, preferably 250-320 rpm, the temperature is raised to 5-8 ℃ above the cloud point of the surfactant at 0.2-0.3 ℃/min, preferably 0.25-0.28 ℃/min, and the mixture is kept still for 2-3h at constant temperature.
The preparation method of the vinylidene fluoride polymer aqueous dispersion liquid for the coating is characterized in that in the second stage of the step 2): the electrolyte is one or more of ammonium carbonate, ammonium sulfate and a hydrogen salt thereof, and is prepared into an aqueous solution with the weight percent of 1-5 percent when added, preferably 2-3 percent.
The preparation method of the vinylidene fluoride polymer aqueous dispersion liquid for the coating is characterized in that in the third stage of the step 3): the pH regulator is ammonia water or ammonium bicarbonate, and the pH value is regulated to 6-9, preferably 7-8.
The preparation method of the vinylidene fluoride polymer aqueous dispersion liquid for the coating is characterized in that in the third stage of the step 3): in the third stage, the stabilizer is fatty alcohol-polyoxyethylene ether with high cloud point, the cloud point is more than 100 ℃, and the adding amount is 0.25-0.75 wt% of the mass of the emulsion, preferably 0.3-0.7 wt% of the mass of the emulsion, and more preferably 0.34-0.5 wt%.
The vinylidene fluoride polymer prepared by the invention has the relative molecular weight of 400-550KDa and the specific gravity of 1.280-1.360 g/cm 3 The aqueous dispersion has the advantages of 55-63 wt% of solid content, 7-8 of pH value, 50-1500 mpas of viscosity and 4-7 wt% of nonionic surfactant, and is environment-friendly, high in solid content and stable in storage.
The preparation method of the PFCs-free vinylidene fluoride polymer aqueous dispersion for the coating has the advantages that the aqueous dispersion prepared by the method is high in solid content, clean and environment-friendly, does not cause environmental pollution, and is suitable for the coating industry.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Example 1
6200g of deionized water, 6.2g of fluoroether sulfonate and 2.9g of paraffin are added into a 10L stainless steel reaction kettle, and nitrogen is used for purging and replacing to ensure that the oxygen content in the kettle is lower than 15ppm; heating the reaction kettle, introducing vinylidene fluoride monomer, and increasing the pressure to 80 ℃ and 4.5MPa; setting up stirringAt the speed of 80r/min, 0.68g of diisopropyl peroxydicarbonate is rapidly injected into the reaction kettle by a metering pump to initiate the reaction, and the pressure in the kettle is maintained to be stable by replenishing vinylidene fluoride monomer; after 30min, 0.92g of diisopropyl peroxydicarbonate and 1.4g of diethyl malonate are slowly added; and finishing the reaction after 3 hours, and recovering unreacted monomers to obtain 8150g of vinylidene fluoride polymer mother liquor in total. Adding 33.6g of isomeric tridecanol polyoxyethylene ether E-1308 into the vinylidene fluoride polymer mother liquor, stirring at a low speed of 20rpm, and heating to 73 ℃ at a speed of 0.8 ℃/min; and adding 350g of isomeric tridecanol polyoxyethylene ether E-1308 and 165g of 2% ammonium bicarbonate aqueous solution again, rapidly stirring at the rotation speed of 280rpm, heating to 80 ℃ at the speed of 0.2 ℃/min, stopping stirring, standing at the constant temperature for 2h, and cooling to room temperature. Separating supernatant of the vinylidene fluoride polymer emulsion, adding ammonia water into the lower layer emulsion to adjust the pH value to 8, adding 12.4g of lauryl alcohol polyoxyethylene ether, fully stirring, and then passing the emulsion through a 400-mesh filter screen to obtain 3850g of aqueous dispersion of the vinylidene fluoride polymer for the coating. The solid residue after filtration was found to be 3.1g, and the specific gravity of the emulsion was 1.307g/cm 3 The solid content is 56.5wt%, the viscosity is 115mpas, the content of the nonionic surfactant is 4.6wt%, and the emulsion has no layering phenomenon after being parked for 15 days.
Example 2
5800g of deionized water, 4.8g of fluoroether sulfonate and 2.7g of paraffin are added into a 10L stainless steel reaction kettle, and nitrogen is used for purging and replacement to ensure that the oxygen content in the kettle is lower than 15ppm; heating the reaction kettle, introducing vinylidene fluoride monomer, and increasing the pressure to 85 ℃ and 4.4MPa; setting the stirring speed to be 75r/min, quickly injecting 0.82g of tert-butyl peroxypivalate into the reaction kettle by using a metering pump to initiate a reaction, and supplementing vinylidene fluoride and hexafluoropropylene with the weight ratio of 96:4, maintaining the pressure in the kettle to be stable; after 30min, slowly adding 1.03g of tert-butyl peroxypivalate and 2.1g of ethyl acetate; and finishing the reaction after 3.2 hours, and recovering unreacted monomers to obtain 8020g of vinylidene fluoride polymer mother liquor in total. Adding 44.6g of nonylphenol polyoxyethylene ether TX-10 into the vinylidene fluoride polymer mother liquor, stirring at a slow speed of 15rpm and at a speed of 1.0 ℃/minWarming to 57 ℃; and adding 304g of nonylphenol polyoxyethylene ether TX-10 and 180g of aqueous solution of 4% ammonium sulfate and ammonium bisulfate (1:1) again, rapidly stirring at the rotation speed of 330rpm, heating to 68 ℃ at the speed of 0.3 ℃/min, stopping stirring, standing at the constant temperature for 3 hours, and cooling to room temperature. Separating supernatant of the vinylidene fluoride polymer emulsion, adding ammonia water into the lower layer emulsion to adjust the pH value to 8, adding 15.4g of tetradecanol polyoxyethylene ether, fully stirring, and passing the emulsion through a 400-mesh filter screen to obtain 3570g of aqueous vinylidene fluoride polymer dispersion for the coating. After test filtration, the solid residue was 2.2g, and the specific gravity of the emulsion was 1.344g/cm 3 The solid content is 61.5wt%, the viscosity is 480mpas, the content of the nonionic surfactant is 5.2wt%, and the emulsion has no layering phenomenon after being parked for 15 days.
Example 3
6000g of deionized water, 5.5g of fluoroether sulfonate and 1.4g of paraffin are added into a 10L stainless steel reaction kettle, and nitrogen is used for purging and replacing to ensure that the oxygen content in the kettle is lower than 15ppm; heating the reaction kettle, introducing the vinylidene fluoride monomer, and increasing the pressure to 78 ℃ and 4.0MPa; setting the stirring speed to be 90r/min, rapidly injecting 0.59g of tert-butyl peroxyisobutyrate into the reaction kettle by using a metering pump to initiate reaction, and supplementing vinylidene fluoride and hexafluoropropylene with the weight ratio of 99:1, maintaining the pressure in the kettle to be stable; after 45min, slowly adding 1.79g of tert-butyl peroxyisobutyrate and 3.3g of diethyl carbonate; and finishing the reaction after 3.8 hours, and recovering unreacted monomers to obtain 7740g of vinylidene fluoride polymer mother liquor in total. Adding 52.5g of isomeric dodecyl alcohol polyoxyethylene ether E-08 into the vinylidene fluoride polymer mother liquor, stirring at a slow speed of 15rpm, and heating to 57 ℃ at a speed of 1.0 ℃/min; and adding 300g of isomeric dodecyl polyoxyethylene ether E-08, 214g of 3.2 percent aqueous solution of ammonium carbonate and ammonium bicarbonate (1:1), quickly stirring at the rotation speed of 380rpm, heating to 67 ℃ at the speed of 0.28 ℃/min, stopping stirring, standing at the constant temperature for 2.8 hours, and cooling to the room temperature. Separating supernatant of vinylidene fluoride polymer emulsion, adding ammonia water into lower layer emulsion to adjust pH to 7, adding 18.8g of fatty alcohol-polyoxyethylene ether O-20, stirring fully, and passing emulsion through a 400-mesh filter screen to obtain 2990g of emulsion for coatingAqueous vinylidene fluoride polymer dispersions. After test filtration, the solid residue was 1.6g, and the specific gravity of the emulsion was 1.317g/cm 3 The solid content is 57.9wt%, the viscosity is 208mpas, the content of the nonionic surfactant is 4.9wt%, and the emulsion has no layering phenomenon after standing for 15 days.
Comparative example 1
The procedure is analogous to example 1, except that the isomeric tridecanol polyoxyethylene ether is initially charged at 0, and again at 383.6g, and is heated directly to 80 ℃ at 280rpm,0.2 ℃/min. 4670g of an aqueous dispersion of a vinylidene fluoride polymer used for a coating material was finally obtained. After testing and filtration, the solid residue is 24.8g, and the specific gravity of the emulsion is 1.165g/cm 3 The solid content is 40.2wt%, the viscosity is 90mpas, the content of the nonionic surfactant is 4.6wt%, and the emulsion has no layering phenomenon after being parked for 15 days.
Comparative example 2
Similar to the production method of example 2, except that the first addition amount of nonylphenol polyoxyethylene ether TX-10 was 348.6g, the second addition amount was 0g, and the temperature was directly raised to 80 ℃ at a rate of 1.0 ℃/min. 4620g of aqueous dispersion of vinylidene fluoride polymer for coating are finally obtained. The solid residue obtained after filtration was measured to be 19.5g, and the specific gravity of the emulsion was 1.237g/cm 3 The solid content is 46.4wt%, the viscosity is 475mpas, the content of the nonionic surfactant is 5.0wt%, the emulsion has obvious demixing phenomenon after being parked for 15 days, and the volume of the water phase accounts for 15% of the total volume.
Comparative example 3
The production process was similar to that of example 3 except that the amount of the aqueous solution of ammonium carbonate and ammonium bicarbonate (1:1) added was 850g, and the final temperature rise was 60 ℃. Finally, 5125g of an aqueous dispersion of vinylidene fluoride polymer for coating was obtained. The solid residue after filtration was found to be 3.7g, and the specific gravity of the emulsion was found to be 1.128g/cm 3 The emulsion has a solid content of 33.2wt%, a viscosity of 66mpas and a nonionic surfactant content of 4.4wt%, and the emulsion has obvious demixing phenomenon after standing for 15 days, and the volume of the water phase accounts for 10% of the total volume.
Comparative example 4
LikeThe production method of example 3 was followed, except that the surfactant used was castor oil polyoxyethylene ether, to finally obtain 5546g of an aqueous dispersion of a vinylidene fluoride polymer for a coating material. After test filtration, the solid residue was 6.4g, and the specific gravity of the emulsion was 1.121g/cm 3 The solid content is 30.1wt%, the viscosity is 75mpas, the content of the nonionic surfactant is 4.1wt%, and the emulsion has no obvious layering phenomenon after being parked for 15 days.
Comparative example 5
The production process was similar to that of example 3 except that fluoroether sulfonate was added in an amount of 7.7g, and 2.59g of t-butyl peroxyisobutyrate and 3.4g of diethyl carbonate were slowly added after 45min; and finishing the reaction after 4.9 hours, and recovering unreacted monomers to obtain 8630g of vinylidene fluoride polymer mother liquor in total. 5058g of vinylidene fluoride polymer aqueous dispersion for coating was finally obtained. The solid residue after filtration was found to be 42.7g, and the specific gravity of the emulsion was found to be 1.259g/cm 3 The emulsion has a solid content of 49.9wt%, a viscosity of 174mpas and a nonionic surfactant content of 4.6wt%, and the emulsion has obvious demixing phenomenon after standing for 15 days, and the volume of the water phase accounts for 8% of the total volume.
The relevant test data are tabulated below:
TABLE 1 aqueous Dispersion Performance test of vinylidene fluoride polymers
| Item | Solids content/% | Specific gravity/g/cm 3 | Viscosity/mpas | Surfactant content/%) | Solid residue/g | Stability of |
| Example 1 | 56.5 | 1.307 | 115 | 4.6 | 3.1 | Without delamination |
| Example 2 | 61.5 | 1.344 | 480 | 5.2 | 2.2 | Without delamination |
| Example 3 | 57.9 | 1.317 | 208 | 4.9 | 1.6 | Without delamination |
| Comparative example 1 | 40.2 | 1.165 | 90 | 4.6 | 24.8 | Without delamination |
| Comparative example 2 | 46.4 | 1.237 | 475 | 5.0 | 19.5 | 15% demixing |
| Comparative example 3 | 33.2 | 1.128 | 66 | 4.4 | 3.7 | 10% demixing |
| Comparative example 4 | 30.1 | 1.121 | 75 | 4.1 | 6.4 | Without delamination |
| Comparative example 5 | 49.9 | 1.259 | 174 | 4.6 | 42.7 | 8% inLayer(s) |
Table 1 shows that the vinylidene fluoride polymer aqueous dispersion prepared by the method has the outstanding advantages of high solid content and stable storage.
The above technical solutions and examples describe the present invention in detail, but do not limit the scope of the present invention. It should be understood that any obvious alterations or substitutions to the present invention by those skilled in the art based on the teachings herein should also be considered to fall within the scope of the present invention.
Claims (16)
1. A preparation method of vinylidene fluoride polymer aqueous dispersion liquid for paint is characterized by comprising the following steps:
the first stage is as follows: adding deionized water, an initiator, a dispersant, a stabilizer, a chain transfer agent and a polymerization monomer into a high-pressure reaction kettle to carry out emulsion polymerization reaction to obtain vinylidene fluoride polymer mother liquor;
in the second stage, adding 0.2-1.0% of surfactant into vinylidene fluoride polymer mother liquor, stirring at a low speed, and heating to 3-5 ℃ below the cloud point of the surfactant at a speed of 0.75-1.35 ℃/min; adding 3-8% of surfactant and 0.02-0.08% of electrolyte again, stirring rapidly, heating to 1-10 deg.C above the cloud point of surfactant at 0.15-0.35 deg.C/min, stopping stirring, standing at constant temperature for 1-4 hr, stopping heating, and cooling to room temperature;
the surfactant is a nonionic surfactant, specifically is a condensate of alkylphenol or fatty alcohol and ethylene oxide, and the cloud point temperature of the surfactant is 60-85 ℃; the slow stirring speed is 10-30 rpm, and the fast stirring speed is 200-400 rpm;
and the third stage, separating the supernatant of the vinylidene fluoride polymer emulsion, adding a pH regulator and a stabilizer into the lower layer emulsion, and passing the emulsion through a filter screen of 300-500 meshes to obtain the aqueous dispersion of the vinylidene fluoride polymer for the coating.
2. The method according to claim 1, wherein in the first stage: the polymerization monomer consists of vinylidene fluoride and other fluorine-containing monomers, and the other fluorine-containing monomers are one or a mixture of more than one of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene and perfluoroalkyl vinyl ether; the weight ratio of the vinylidene fluoride to other fluorine-containing monomers is 95:5 to 100:0.
3. the method of claim 1, wherein in the first stage: the polymerization monomer consists of vinylidene fluoride and other fluorine-containing monomers, and the other fluorine-containing monomers are one or a mixture of more than one of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene and perfluoroalkyl vinyl ether; the weight ratio of the vinylidene fluoride to other fluorine-containing monomers is 96.5: 3.5-98.5: 1.5.
4. the method according to claim 1, wherein in the first stage: the initiator is organic peroxide, the dispersing agent is fluoroether sulfonate, the stabilizing agent is paraffin, and the chain transfer agent is diethyl malonate, ethyl acetate or diethyl carbonate.
5. The method of claim 1, wherein in the first stage: the weight ratio of the deionized water, the initiator, the dispersant, the stabilizer, the chain transfer agent and the polymerization monomer is 100: 1.5 multiplied by 10 -3 ～3.5×10 -2 ∶0.08～0.35∶0.03～0.12∶5.7×10 -3 ～7.2×10 -2 ∶20～35。
6. The method of claim 1, wherein in the first stage: the weight ratio of the deionized water, the initiator, the dispersant, the stabilizer, the chain transfer agent and the polymerization monomer is 100: 2.2X 10 -3 ～2.8×10 -2 ∶0.18～0.27∶0.07～0.09∶6.2×10 -3 ～6.8×10 -2 ∶25～30。
7. The method of claim 1, wherein in the first stage: the solid content of the vinylidene fluoride polymer emulsion mother liquor is 22-28%.
8. The method of claim 1, wherein in the first stage: the solid content of the vinylidene fluoride polymer emulsion mother liquor is 25-27%.
9. The method according to claim 1, wherein in the second stage: the addition amount of the surfactant is 2-8 wt% corresponding to 100 parts by weight of the vinylidene fluoride polymer emulsion mother liquor.
10. The method according to claim 1, wherein in the second stage: the addition amount of the surfactant is 4-6 wt% corresponding to 100 parts by weight of the vinylidene fluoride polymer emulsion mother liquor.
11. The method according to claim 1, wherein in the second stage: the slow stirring speed is 15-20 rpm; heating to 4 ℃ below the cloud point of the surfactant at the speed of 0.8-1.3 ℃/min; the rapid stirring speed is 250-320 rpm, the temperature is raised to 5-8 ℃ above the cloud point of the surfactant at 0.2-0.3 ℃/min, and the mixture is kept at a constant temperature for 2-3h.
12. The method according to claim 1, wherein in the second stage: the electrolyte is one or more of ammonium carbonate, ammonium sulfate and hydrogen salt thereof, and is prepared into 1-5 wt% aqueous solution when added.
13. The method according to claim 1, wherein in the second stage: the electrolyte is one or more of ammonium carbonate, ammonium sulfate and hydrogen salt thereof, and is prepared into 2-3 wt% aqueous solution when added.
14. The method of claim 1, wherein in the third stage: the pH regulator is ammonia water or ammonium bicarbonate, and the pH value is regulated to 6-9.
15. The method of claim 1, wherein in the third stage: the stabilizer is fatty alcohol-polyoxyethylene ether with high cloud point, the cloud point is more than 100 ℃, and the adding amount is 0.25-0.75 wt% of the mass of the emulsion.
16. The method of claim 1, wherein in the third stage: the stabilizer is fatty alcohol-polyoxyethylene ether with high cloud point, the cloud point is more than 100 ℃, and the adding amount is 0.34-0.5 wt% of the mass of the emulsion.
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| ITMI20032050A1 (en) * | 2003-10-21 | 2005-04-22 | Solvay Solexis Spa | PROCESS FOR THE PREPARATION OF FLUOROPOLYMER DISPERSERS. |
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| US3704272A (en) * | 1970-09-15 | 1972-11-28 | Du Pont | Concentration of polytetrafluoroethylene aqueous dispersion |
| CN1612911A (en) * | 2002-01-04 | 2005-05-04 | 纳幕尔杜邦公司 | Concentrated fluoroploymer dispersions |
| CN101155857A (en) * | 2005-04-13 | 2008-04-02 | 大金工业株式会社 | Process for producing aqueous fluoropolymer dispersion |
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