CN116082556A - Modification method of polyvinylidene fluoride - Google Patents
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- CN116082556A CN116082556A CN202310371762.1A CN202310371762A CN116082556A CN 116082556 A CN116082556 A CN 116082556A CN 202310371762 A CN202310371762 A CN 202310371762A CN 116082556 A CN116082556 A CN 116082556A
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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
- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
- C08F214/225—Vinylidene fluoride with non-fluorinated comonomers
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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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A modification method of polyvinylidene fluoride, which belongs to the technical field of polyvinylidene fluoride synthesis. The method is characterized by comprising the following steps of: adding potassium hydroxide, hydrogen peroxide, a dispersing agent and water into a reaction kettle, uniformly stirring, and adding vinylidene fluoride into the reaction kettle for short-time reaction; stirring is maintained, butadiene and styrene monomers are added into a reaction kettle, and the temperature is raised for copolymerization; and replenishing vinylidene fluoride, potassium hydroxide and hydrogen peroxide into the reaction kettle until the reaction is terminated. The invention uses ternary random copolymerization method to toughen, does not need to add auxiliary agents with complex components, does not introduce impurities such as metal ions, can keep other performances of PVDF materials while toughen, and can effectively widen the application field of PVDF.
Description
Technical Field
A modification method of polyvinylidene fluoride, which belongs to the technical field of polyvinylidene fluoride synthesis.
Background
Polyvinylidene fluoride (PVDF) can be used to produce insulating sheaths for pipes, plates, films, substrates, and cables. PVDF has very high mechanical strength, wear resistance, weather resistance, good thermal stability and outstanding corrosion resistance. PVDF can also be injection molded or welded, and is widely used in chemical industry, semiconductor industry, pharmaceutical industry and national defense industry; such as in the manufacture of lithium ion batteries. In addition, PVDF can be made into cross-linked closed cell foams, which are increasingly used in the aerospace field.
However, the existing polyvinylidene fluoride has the defect of insufficient toughness, and limits the application environment of the high-quality material. In order to solve this problem, various improvements have been made, for example, chinese patent CN115028945a discloses a method for synthesizing polyvinylidene fluoride, in which, in order to improve the high temperature resistance and toughness of polyvinylidene fluoride, the following steps are adopted: and adding additives such as a stabilizer, an auxiliary agent, a plasticizer, an antioxidant and the like into the synthesized polyvinylidene fluoride solution under the nitrogen atmosphere. However, this method results in a PVDF-based composition. The weather resistance, corrosion resistance and other properties of the PVDF material can be affected, and more importantly, impurities such as metal ions and the like are introduced, so that the application field of PVDF can be limited.
Disclosure of Invention
The invention aims to solve the technical problems that: overcomes the defects of the prior art and provides a modification method of polyvinylidene fluoride with improved toughness through monomer copolymerization.
The technical scheme adopted for solving the technical problems is as follows: the modification method of polyvinylidene fluoride is characterized by comprising the following steps:
1) Adding potassium hydroxide, hydrogen peroxide, a dispersing agent and water into a reaction kettle, uniformly stirring, adding vinylidene fluoride into the reaction kettle, stirring, controlling the reaction temperature to be 10-40 ℃ and the reaction time to be 5-10 min; in the step 1), the mass ratio of vinylidene fluoride, potassium hydroxide, hydrogen peroxide, a dispersing agent and water is 30-40:0.5-2:0.1-1:2-7:100;
2) Stirring is kept, butadiene and styrene monomers are added into a reaction kettle, the temperature is raised, the reaction temperature is controlled to be 60-80 ℃, and the reaction time is controlled to be 60-180 min; the mass ratio of the butadiene and the styrene added in the step 2) to the water in the step 1) is 3-7:8-14:100;
3) Replenishing vinylidene fluoride, potassium hydroxide and hydrogen peroxide into a reaction kettle, cooling to a reaction temperature of 10-40 ℃ until the reaction is terminated, and washing and filtering to obtain toughened polyvinylidene fluoride; the mass ratio of the vinylidene fluoride, the potassium hydroxide, the hydrogen peroxide and the water in the step 1) which are supplemented in the step 3) is 3-7:3-8:2-6:100.
In the invention, the self-polymerization of vinylidene fluoride is used for initiating copolymerization, the vinylidene fluoride is fully dispersed in a reaction system in the presence of a dispersing agent, the technological conditions are controlled to ensure that the self-polymerization of the vinylidene fluoride generates short chains, then the butadiene and styrene monomers for modification are added, the technological conditions are changed for ternary random copolymerization, and finally the vinylidene fluoride is used for end capping to keep the performances of mechanical strength, wear resistance, thermal stability, corrosion resistance and the like of PVDF. Polymerization of butadiene and styrene monomers not only in the backbone, but also can result in self-polymerizing or copolymerized short chain branches, thereby improving PVDF toughness.
Preferably, in the modification method of polyvinylidene fluoride, the reaction temperature in the step 1) is 20-30 ℃ and the reaction time is 6-8 min. The reaction temperature and the reaction time in the step 1) directly influence the length of the self-polymerization short chain, the toughness of the product is influenced if the length is too long, and a good end-capping effect cannot be achieved if the length is too short, so that the effect of keeping the original characteristics of PVDF is not achieved. Under the preferable reaction conditions, the toughness and other properties of the prepared product can be kept in a better state.
Preferably, in the above-mentioned method for modifying polyvinylidene fluoride, the mass ratio of the vinylidene fluoride, potassium hydroxide, hydrogen peroxide, dispersant and water in the step 1) is 34 to 37:1 to 1.5:0.3 to 0.6:4 to 6:100. The initial concentration of vinylidene fluoride and the catalytic system can also affect the length of the self-polymerizing short chains, and the polymerization rate can be controlled at the preferred initial concentration to produce products with excellent toughness and other PVDF inherent properties.
More preferably, in the above-mentioned method for modifying polyvinylidene fluoride, the mass ratio of vinylidene fluoride, potassium hydroxide, hydrogen peroxide, dispersant and water in step 1) is 35:1.2:0.4:5:100. More preferred initial concentrations in combination with other preferred process conditions can achieve optimal conditions for the products of the invention.
Preferably, in the modification method of polyvinylidene fluoride, the reaction temperature in the step 2) is 67-75 ℃ and the reaction time is 80-100 min. The reaction temperature and time in the step 2) are main factors for determining the copolymerization state of the main chain, and the preferable process conditions can ensure random copolymerization on the main chain, reduce self-polymerization chain segments on the main chain, control the length of the branched chain and finally better ensure the toughness of the product.
Preferably, in the modification method of polyvinylidene fluoride, the mass ratio of the butadiene and the styrene added in the step 2) to the water in the step 1) is 4 to 5:9 to 11:100. The addition of butadiene and styrene monomers, which are mainly used for modifying the molecular chains of PVDF, cannot be added too much, and should not exceed 30% of the total mass of the comonomer as much as possible. The ratio between butadiene and styrene monomers is controlled, and the length and density of the branched chain can be controlled, so that the toughness of PVDF can be improved and the original characteristics of PVDF can be maintained.
Preferably, in the modification method of polyvinylidene fluoride, the reaction temperature in the step 3) is 15-25 ℃. In the step 3), the end capping is mainly carried out by using the polyvinylidene fluoride, so that the stability of the reaction is mainly ensured, and the generation and the maintenance of independent polyvinylidene fluoride short chains are avoided as much as possible; the preferred reaction conditions can better achieve this goal, thereby ensuring the overall performance of the product PVDF.
Preferably, in the modification method of polyvinylidene fluoride, the mass ratio of the vinylidene fluoride, potassium hydroxide, hydrogen peroxide and water in the step 3) to the water in the step 1) is 4.5-5.5:4.5-6:3.5-4.5:100. The catalytic environment is required to be further adjusted when the monomer is supplemented, and the concentration of the optimized supplementary material can promote the vinylidene fluoride to be mainly subjected to end-capped chain extension polymerization, so that new short chains generated by self-polymerization are reduced, and the overall performance of the PVDF product is improved.
Preferably, in the modification method of polyvinylidene fluoride, the dispersant in the step 1) is stearamide or/and vinyl bis-stearamide. The selection of the dispersant directly affects the state of the initial dispersion polymerization system, and the preferred dispersant can better disperse vinylidene fluoride, can generate short chains with more uniform chain length, and reduces the generation of long chains at the moment. Thereby better ensuring various performances of the product.
More preferably, in the modification method of polyvinylidene fluoride, the dispersant in the step 1) is a dispersant prepared by compounding stearamide and vinyl bis-stearamide according to a mass ratio of 10:1-4. The invention also provides a compound dispersing agent with the best dispersibility on vinylidene fluoride in the polymerization system, and the product with the best performance can be obtained by matching other preferable process conditions.
The content of hetero chains generated by self-polymerization or copolymerization of butadiene and styrene monomers in the copolymerization toughened polyvinylidene fluoride prepared by the invention is less than 5%.
Compared with the prior art, the modification method of polyvinylidene fluoride has the following beneficial effects: in the invention, the self-polymerization of vinylidene fluoride is used for initiating copolymerization, the vinylidene fluoride is fully dispersed in a reaction system in the presence of a dispersing agent, the technological conditions are controlled to ensure that the self-polymerization of the vinylidene fluoride generates short chains, then the butadiene and styrene monomers for modification are added, the technological conditions are changed for ternary random copolymerization, and finally the vinylidene fluoride is used for end capping to keep the performances of mechanical strength, wear resistance, thermal stability, corrosion resistance and the like of PVDF. Polymerization of butadiene and styrene monomers in the backbone also produces self-polymerizing or copolymerized short chain branches, thereby improving PVDF toughness. According to the toughening method disclosed by the invention, no auxiliary agent with complex components is required to be added, impurities such as metal ions are not introduced, other performances of the PVDF material can be maintained while toughening, and the application field of the PVDF can be effectively widened.
Detailed Description
The present invention will be specifically described below by way of examples. All materials are commercially available, unless otherwise indicated.
Example 1
1) Adding a dispersing agent and water which are compounded by potassium hydroxide, hydrogen peroxide, stearamide and vinyl bis-stearamide according to the mass ratio of 10:2.5 into a reaction kettle, uniformly stirring, adding vinylidene fluoride into the reaction kettle, rapidly stirring at 120r/min, and controlling the reaction temperature at 25 ℃ and the reaction time at 7min; in the step 1), the mass ratio of the vinylidene fluoride, the potassium hydroxide, the hydrogen peroxide, the dispersing agent and the water is 35:1.2:0.4:5:100;
2) Stirring is maintained, butadiene and styrene monomers are added into a reaction kettle, the temperature is raised, the reaction temperature is controlled at 70 ℃, and the reaction time is controlled at 90 minutes; the mass ratio of the butadiene and the styrene added in the step 2) to the water in the step 1) is 5:10:100;
3) Replenishing vinylidene fluoride, potassium hydroxide and hydrogen peroxide into a reaction kettle, cooling to a reaction temperature of 20 ℃ until the reaction is terminated, and then washing and filtering to obtain toughened polyvinylidene fluoride; the mass ratio of the vinylidene fluoride, the potassium hydroxide, the hydrogen peroxide and the water in the step 1) which are supplemented in the step 3) is 5:5:4:100.
Example 2
1) Adding a dispersing agent and water which are compounded by potassium hydroxide, hydrogen peroxide, stearamide and vinyl bis-stearamide according to the mass ratio of 10:1 into a reaction kettle, uniformly stirring, adding vinylidene fluoride into the reaction kettle, rapidly stirring at 120r/min, and controlling the reaction temperature at 20 ℃ and the reaction time at 8min; in the step 1), the mass ratio of the vinylidene fluoride, the potassium hydroxide, the hydrogen peroxide, the dispersing agent and the water is 34:1.5:0.3:6:100;
2) Stirring is kept, butadiene and styrene monomers are added into a reaction kettle, the temperature is raised, the reaction temperature is controlled at 75 ℃, and the reaction time is controlled at 80 minutes; the mass ratio of the butadiene and the styrene added in the step 2) to the water in the step 1) is 5:9:100;
3) Replenishing vinylidene fluoride, potassium hydroxide and hydrogen peroxide into a reaction kettle, cooling to a reaction temperature of 25 ℃ until the reaction is terminated, and then washing and filtering to obtain toughened polyvinylidene fluoride; the mass ratio of the vinylidene fluoride, the potassium hydroxide, the hydrogen peroxide and the water in the step 1) which are supplemented in the step 3) is 4.5:6:3.5:100.
Example 3
1) Adding a dispersing agent and water which are compounded by potassium hydroxide, hydrogen peroxide, stearamide and vinyl bis-stearamide according to the mass ratio of 10:4 into a reaction kettle, uniformly stirring, adding vinylidene fluoride into the reaction kettle, rapidly stirring at 120r/min, and controlling the reaction temperature at 30 ℃ and the reaction time at 6min; in the step 1), the mass ratio of the vinylidene fluoride, the potassium hydroxide, the hydrogen peroxide, the dispersing agent and the water is 37:1:0.6:4:100;
2) Stirring is maintained, butadiene and styrene monomers are added into a reaction kettle, the temperature is raised, the reaction temperature is controlled at 67 ℃, and the reaction time is controlled at 100min; the mass ratio of the butadiene and the styrene added in the step 2) to the water in the step 1) is 4:11:100;
3) Replenishing vinylidene fluoride, potassium hydroxide and hydrogen peroxide into a reaction kettle, cooling to a reaction temperature of 15 ℃ until the reaction is terminated, and then washing and filtering to obtain toughened polyvinylidene fluoride; the mass ratio of the vinylidene fluoride, the potassium hydroxide, the hydrogen peroxide and the water in the step 1) which are supplemented in the step 3) is 5.5:4.5:4.5:100.
Example 4
1) Adding potassium hydroxide, hydrogen peroxide, stearamide and water into a reaction kettle, uniformly stirring, adding vinylidene fluoride into the reaction kettle, rapidly stirring at 120r/min, and controlling the reaction temperature at 25 ℃ and the reaction time at 7min; in the step 1), the mass ratio of vinylidene fluoride, potassium hydroxide, hydrogen peroxide, stearamide and water is 35:1.2:0.4:5:100;
2) Stirring is maintained, butadiene and styrene monomers are added into a reaction kettle, the temperature is raised, the reaction temperature is controlled at 70 ℃, and the reaction time is controlled at 90 minutes; the mass ratio of the butadiene and the styrene added in the step 2) to the water in the step 1) is 5:10:100;
3) Replenishing vinylidene fluoride, potassium hydroxide and hydrogen peroxide into a reaction kettle, cooling to a reaction temperature of 20 ℃ until the reaction is terminated, and then washing and filtering to obtain toughened polyvinylidene fluoride; the mass ratio of the vinylidene fluoride, the potassium hydroxide, the hydrogen peroxide and the water in the step 1) which are supplemented in the step 3) is 5:5:4:100.
Example 5
1) Adding a dispersing agent and water which are compounded by potassium hydroxide, hydrogen peroxide, stearamide and vinyl bis-stearamide according to the mass ratio of 10:2.5 into a reaction kettle, uniformly stirring, adding vinylidene fluoride into the reaction kettle, rapidly stirring at 120r/min, and controlling the reaction temperature at 10 ℃ and the reaction time at 10min; in the step 1), the mass ratio of the vinylidene fluoride, the potassium hydroxide, the hydrogen peroxide, the dispersing agent and the water is 30:2:0.1:7:100;
2) Stirring is kept, butadiene and styrene monomers are added into a reaction kettle, the temperature is raised, the reaction temperature is controlled at 60 ℃, and the reaction time is controlled at 180 minutes; the mass ratio of the butadiene and the styrene added in the step 2) to the water in the step 1) is 3:14:100;
3) Replenishing vinylidene fluoride, potassium hydroxide and hydrogen peroxide into a reaction kettle, cooling to a reaction temperature of 40 ℃ until the reaction is terminated, and then washing and filtering to obtain toughened polyvinylidene fluoride; the mass ratio of the vinylidene fluoride, the potassium hydroxide, the hydrogen peroxide and the water in the step 1) which are supplemented in the step 3) is 3:8:2:100.
Example 6
1) Adding potassium hydroxide, hydrogen peroxide, vinyl bis-stearamide and water into a reaction kettle, uniformly stirring, adding vinylidene fluoride into the reaction kettle, rapidly stirring at 120r/min, and controlling the reaction temperature at 40 ℃ and the reaction time at 5min; in the step 1), the mass ratio of the vinylidene fluoride, the potassium hydroxide, the hydrogen peroxide, the vinyl bis-stearamide and the water is 40:0.5:1:2:100;
2) Stirring is kept, butadiene and styrene monomers are added into a reaction kettle, the temperature is raised, the reaction temperature is controlled at 80 ℃, and the reaction time is controlled at 60 minutes; the mass ratio of the butadiene and the styrene added in the step 2) to the water in the step 1) is 7:8:100;
3) Replenishing vinylidene fluoride, potassium hydroxide and hydrogen peroxide into a reaction kettle, cooling to a reaction temperature of 10 ℃ until the reaction is terminated, and then washing and filtering to obtain toughened polyvinylidene fluoride; the mass ratio of the vinylidene fluoride, the potassium hydroxide, the hydrogen peroxide and the water in the step 1) which are supplemented in the step 3) is 7:3:6:100.
Comparative example 1
1) Adding potassium hydroxide, hydrogen peroxide and water into a reaction kettle, uniformly stirring, adding vinylidene fluoride into the reaction kettle, rapidly stirring at 120r/min, and controlling the reaction temperature at 25 ℃ and the reaction time at 7min; in the step 1), the mass ratio of vinylidene fluoride, potassium hydroxide, hydrogen peroxide and water is 35:1.2:0.4:100;
2) Stirring is maintained, butadiene and styrene monomers are added into a reaction kettle, the temperature is raised, the reaction temperature is controlled at 70 ℃, and the reaction time is controlled at 90 minutes; the mass ratio of the butadiene and the styrene added in the step 2) to the water in the step 1) is 5:10:100;
3) Replenishing vinylidene fluoride, potassium hydroxide and hydrogen peroxide into a reaction kettle, cooling to a reaction temperature of 20 ℃ until the reaction is terminated, and then washing and filtering to obtain toughened polyvinylidene fluoride; the mass ratio of the vinylidene fluoride, the potassium hydroxide, the hydrogen peroxide and the water in the step 1) which are supplemented in the step 3) is 5:5:4:100.
Comparative example 2
1) Adding a dispersing agent and water which are compounded by potassium hydroxide, hydrogen peroxide, stearamide and vinyl bis-stearamide according to the mass ratio of 10:2.5 into a reaction kettle, uniformly stirring, adding vinylidene fluoride into the reaction kettle, rapidly stirring at 120r/min, and controlling the reaction temperature at 25 ℃ and the reaction time at 7min; in the step 1), the mass ratio of the vinylidene fluoride, the potassium hydroxide, the hydrogen peroxide, the dispersing agent and the water is 20:1.2:0.4:5:100;
2) Stirring is maintained, butadiene and styrene monomers are added into a reaction kettle, the temperature is raised, the reaction temperature is controlled at 70 ℃, and the reaction time is controlled at 90 minutes; the mass ratio of the butadiene and the styrene added in the step 2) to the water in the step 1) is 15:10:100;
3) Replenishing vinylidene fluoride, potassium hydroxide and hydrogen peroxide into a reaction kettle, cooling to a reaction temperature of 20 ℃ until the reaction is terminated, and then washing and filtering to obtain toughened polyvinylidene fluoride; the mass ratio of the vinylidene fluoride, the potassium hydroxide, the hydrogen peroxide and the water in the step 1) which are supplemented in the step 3) is 5:5:4:100.
The polymers obtained in each example and comparative example were made into film samples by a film drawing process, and performance tests were performed according to the corresponding national standards, and the test results are shown in table 1. Wherein the acid corrosion resistance is the highest use temperature in sulfuric acid with the concentration of 60 percent. Abrasion was measured according to DIN53516 standard test method.
TABLE 1
| Tensile yield strength MPa | Elongation at break% | Impact strength (cantilever, notched) J/M | Abrasion mm3 | Pyrolysis temperature (DEG C) | Acid corrosion resistance (DEG C) | |
| Example 1 | 46 | 312 | 273 | 46 | 438 | 107 |
| Example 2 | 46 | 310 | 271 | 49 | 427 | 102 |
| Examples3 | 45 | 303 | 264 | 45 | 423 | 104 |
| Example 4 | 42 | 296 | 251 | 64 | 388 | 102 |
| Example 5 | 44 | 298 | 260 | 79 | 382 | 99 |
| Example 6 | 37 | 267 | 233 | 53 | 391 | 103 |
| Comparative example 1 | 21 | 79 | 198 | 128 | - | - |
| Comparative example 2 | 16 | 157 | 167 | 153 | - | - |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method for modifying polyvinylidene fluoride, which is characterized by comprising the following steps:
1) Adding potassium hydroxide, hydrogen peroxide, a dispersing agent and water into a reaction kettle, uniformly stirring, adding vinylidene fluoride into the reaction kettle, stirring, controlling the reaction temperature to be 10-40 ℃ and the reaction time to be 5-10 min; in the step 1), the mass ratio of vinylidene fluoride, potassium hydroxide, hydrogen peroxide, a dispersing agent and water is 30-40:0.5-2:0.1-1:2-7:100;
2) Adding butadiene and styrene monomers into a reaction kettle while stirring, heating, controlling the reaction temperature to be 60-80 ℃ and the reaction time to be 60-180 min; the mass ratio of the butadiene and the styrene added in the step 2) to the water in the step 1) is 3-7:8-14:100;
3) Replenishing vinylidene fluoride, potassium hydroxide and hydrogen peroxide into a reaction kettle, cooling to a reaction temperature of 10-40 ℃ until the reaction is terminated, and washing and filtering to obtain toughened polyvinylidene fluoride; the mass ratio of the vinylidene fluoride, the potassium hydroxide, the hydrogen peroxide and the water in the step 1) which are supplemented in the step 3) is 3-7:3-8:2-6:100.
2. The method for modifying polyvinylidene fluoride according to claim 1, wherein: the reaction temperature in the step 1) is 20-30 ℃ and the reaction time is 6-8 min.
3. The method for modifying polyvinylidene fluoride according to claim 1, wherein: the mass ratio of the vinylidene fluoride, the potassium hydroxide, the hydrogen peroxide, the dispersing agent and the water in the step 1) is 34-37:1-1.5:0.3-0.6:4-6:100.
4. The method for modifying polyvinylidene fluoride according to claim 1, wherein: the mass ratio of vinylidene fluoride, potassium hydroxide, hydrogen peroxide, dispersant and water in the step 1) is 35:1.2:0.4:5:100.
5. The method for modifying polyvinylidene fluoride according to claim 1, wherein: the reaction temperature in the step 2) is 67-75 ℃ and the reaction time is 80-100 min.
6. The method for modifying polyvinylidene fluoride according to claim 1, wherein: the mass ratio of the butadiene and the styrene added in the step 2) to the water in the step 1) is 4-5:9-11:100.
7. The method for modifying polyvinylidene fluoride according to claim 1, wherein: the reaction temperature in the step 3) is 15-25 ℃.
8. The method for modifying polyvinylidene fluoride according to claim 1, wherein: the mass ratio of the vinylidene fluoride, the potassium hydroxide, the hydrogen peroxide and the water in the step 1) which are supplemented in the step 3) is 4.5-5.5:4.5-6:3.5-4.5:100.
9. The method for modifying polyvinylidene fluoride according to claim 1, wherein: the dispersing agent in the step 1) is stearamide or/and vinyl bis-stearamide.
10. The method for modifying polyvinylidene fluoride according to claim 1, wherein: the dispersing agent in the step 1) is a dispersing agent formed by compounding stearamide and vinyl bis-stearamide according to a mass ratio of 10:1-4.
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| JPH05194668A (en) * | 1991-07-05 | 1993-08-03 | Japan Synthetic Rubber Co Ltd | Vinylidene fluoride-fluorine-containing (meth)acrylic acid ester copolymer, its production and coating composition using the same |
| CN102702404A (en) * | 2012-06-12 | 2012-10-03 | 辽宁富朗科技有限公司 | Preparation method of polyvinylidene fluoride material |
| CN103204961A (en) * | 2013-04-18 | 2013-07-17 | 山东东岳高分子材料有限公司 | Method for preparing fluorine-containing polymer by using mixed fluorine-containing surfactant |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05194668A (en) * | 1991-07-05 | 1993-08-03 | Japan Synthetic Rubber Co Ltd | Vinylidene fluoride-fluorine-containing (meth)acrylic acid ester copolymer, its production and coating composition using the same |
| CN102702404A (en) * | 2012-06-12 | 2012-10-03 | 辽宁富朗科技有限公司 | Preparation method of polyvinylidene fluoride material |
| CN103204961A (en) * | 2013-04-18 | 2013-07-17 | 山东东岳高分子材料有限公司 | Method for preparing fluorine-containing polymer by using mixed fluorine-containing surfactant |
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