CN114031704B - Vinylidene fluoride polymer and preparation method and application thereof - Google Patents
Vinylidene fluoride polymer and preparation method and application thereof Download PDFInfo
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- CN114031704B CN114031704B CN202111545659.1A CN202111545659A CN114031704B CN 114031704 B CN114031704 B CN 114031704B CN 202111545659 A CN202111545659 A CN 202111545659A CN 114031704 B CN114031704 B CN 114031704B
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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
- 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
- C08F114/18—Monomers containing fluorine
- C08F114/22—Vinylidene fluoride
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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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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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
The invention relates to the technical field of polymers, in particular to a vinylidene fluoride polymer, and also relates to a preparation method and application thereof. The polyvinylidene fluoride polymer with the core-shell structure can improve the performances such as peel strength and the like when used in a lithium battery binder, particularly the low-temperature cycle performance of the battery, has obvious improvement effect and has very wide application prospect.
Description
Technical Field
The invention relates to the technical field of polymers, in particular to a vinylidene fluoride polymer, and also relates to a preparation method and application thereof.
Background
Polyvinylidene fluoride Poly (vinylidene fluoride), abbreviated as PVDF in English, mainly refers to vinylidene fluoride homopolymer or copolymer of vinylidene fluoride and other small amount of fluorine-containing vinyl monomers, has the characteristics of both fluororesin and general resin, has special performances such as piezoelectric property, dielectric property, thermoelectric property and the like besides good chemical corrosion resistance, high temperature resistance, oxidation resistance, weather resistance and ray radiation resistance, is a second-place product with high yield in fluorine-containing plastics, and has the global annual capacity of over 5.3 ten thousand tons.
PVDF applications are mainly focused in petrochemical, electronics, electrical and fluorocarbon coatings, and are one of the best materials for pumps, valves, pipes, plumbing fittings, storage tanks and heat exchangers for petrochemical plant fluid handling systems as a whole or lining due to its good chemical resistance, processability, and fatigue and creep resistance. PVDF has good chemical stability and electrical insulation performance, so that the manufactured equipment can meet the TOCS and flame retardant requirements, and is widely applied to the storage and transportation of high-purity chemicals in the semiconductor industry. PVDF is one of the main raw materials of fluorocarbon coatings, the fluorocarbon coatings prepared by taking PVDF as the raw material have been developed to the sixth generation, and since PVDF resin has super-strong weather resistance, the PVDF resin can be used outdoors for a long time without maintenance, and the PVDF resin is widely applied to power stations, airports, expressways, high-rise buildings and the like. In addition, the PVDF resin can be blended and modified with other resins, such as PVDF and ABS resin to obtain a composite material, and the composite material is widely applied to buildings, automobile decorations, home appliance shells and the like.
Porous membranes, gels, diaphragms and the like made of PVDF resin are applied to lithium secondary batteries, and the application is one of markets with the fastest growing demand of PVDF at present. PVDF resins are also described as a binder for batteries, but have a varying binding effect and a large influence on battery performance, particularly low-temperature cycle performance.
Disclosure of Invention
In order to solve the above problems, the present application provides a polyvinylidene fluoride polymer, and particularly, an application of the polyvinylidene fluoride polymer in a lithium battery binder.
The invention is realized by the following measures:
a polyvinylidene fluoride polymer is prepared by homopolymerizing polyvinylidene fluoride in a deionized water environment under the participation of an emulsifier, an initiator and a chain transfer agent and under a certain temperature and pressure.
The polyvinylidene fluoride homopolymerization process of the polyvinylidene fluoride polymer is as follows: 10-20% of vinylidene fluoride reacts to obtain a polymer core, and then the rest of vinylidene fluoride is added to react to obtain the polyvinylidene fluoride polymer.
The polyvinylidene fluoride polymer is characterized in that the emulsifier is an anionic fluorocarbon emulsifier, a fluorine-containing surfactant or an amphoteric fluorocarbon surfactant, and the using amount of the emulsifier is 0.1-0.35% of the mass of the vinylidene fluoride.
The polyvinylidene fluoride polymer is characterized in that the initiator is tert-butyl peroxypivalate, diethyl peroxydicarbonate, di-tert-butyl peroxide, diisopropyl peroxydicarbonate or di-n-propyl peroxydicarbonate, and the using amount of the initiator is 0.05-0.18% of the mass of the vinylidene fluoride.
The polyvinylidene fluoride polymer is characterized in that the chain transfer agent is more than one of diethyl carbonate, ethyl acetate, diethyl malonate, isopropanol and propane, and the dosage of the chain transfer agent is 0.06-0.2% of the mass of the polyvinylidene fluoride.
The usage amount of the polyvinylidene fluoride polymer and the deionized water is 300-400% of the mass of the polyvinylidene fluoride.
The polymerization temperature of the polyvinylidene fluoride polymer is 85-95 ℃, the polymerization pressure is 4.5-6.5Mpa, the polymerization stirring speed is 80-100 r/min, and the reaction time is 3.5-4.5 hours.
In the polyvinylidene fluoride polymer, the initiator is added with 25-45% of the total mass before reaction, and after a polymer core is obtained, the rest initiator is uniformly added until the reaction is finished.
The polyvinylidene fluoride polymer is added with 35-55% of the total mass of the chain transfer agent before reaction, and after a polymer core is obtained and the reaction is finished, the residual chain transfer agent is uniformly added.
The polyvinylidene fluoride polymer is applied to a lithium battery binder.
The invention has the beneficial effects that:
the polyvinylidene fluoride polymer with the core-shell structure can improve the performances such as peel strength and the like when used in a lithium battery binder, particularly the low-temperature cycle performance of the battery, has obvious improvement effect and has very wide application prospect.
Detailed Description
For a better understanding of the present invention, reference is made to the following examples.
A polyvinylidene fluoride polymer is prepared by homopolymerizing polyvinylidene fluoride in a deionized water environment under the participation of an emulsifier, an initiator and a chain transfer agent and under a certain temperature and pressure.
The polyvinylidene fluoride homopolymerization process of the polyvinylidene fluoride polymer is as follows: and (3) reacting 10-20% of vinylidene fluoride to obtain a polymer core, and then adding the rest vinylidene fluoride to react to obtain the polyvinylidene fluoride polymer.
The polyvinylidene fluoride polymer is characterized in that the emulsifier is an anionic fluorocarbon emulsifier, a fluorine-containing surfactant or an amphoteric fluorocarbon surfactant.
The initiator of the polyvinylidene fluoride polymer is tert-butyl peroxypivalate, diethyl peroxydicarbonate, di-tert-butyl peroxide, diisopropyl peroxydicarbonate or di-n-propyl peroxydicarbonate.
The polyvinylidene fluoride polymer is characterized in that the chain transfer agent is more than one of diethyl carbonate, ethyl acetate, diethyl malonate, isopropanol and propane.
The post-treatment process of the polyvinylidene fluoride polymer emulsion comprises the following steps: degassing the polyvinylidene fluoride polymer emulsion, recovering unreacted monomers, cooling, washing the emulsion with deionized water until the conductivity of the washing liquid is reduced to less than or equal to 3us/cm, carrying out flash evaporation drying, crushing and packaging to obtain the finished product.
The conductivity of the used deionized water is less than or equal to 0.8us/cm.
In order to prevent sticking, an anti-sticking agent, preferably paraffin wax is added into the reaction, and the dosage of the anti-sticking agent is 0.05 to 1.5 percent of that of the vinylidene fluoride.
The basic indexes of the prepared polyvinylidene fluoride polymer are shown in the following table 1. The index detection method is shown in the content of the last part of the specification.
TABLE 1 polyvinylidene fluoride Polymer Performance indices
Example 1:
(1) Vacuumizing a closed polymerization reaction kettle, introducing nitrogen to remove oxygen, and then adding deionized water, an emulsifier, kettle adhesion preventing agent paraffin, an initiator, a chain transfer agent and vinylidene fluoride, wherein the using amount of the deionized water is 300% of the mass of the vinylidene fluoride, the using amount of the emulsifier is 0.35% of the mass of the vinylidene fluoride, the using amount of the kettle adhesion preventing agent paraffin is 0.05% of the mass of the vinylidene fluoride, the using amount of the initiator is 0.18% of the mass of the vinylidene fluoride, and the using amount of the chain transfer agent is 0.06% of the mass of the vinylidene fluoride;
(2) Raising the temperature of the reaction kettle to 100 ℃, controlling the reaction pressure to be 4mpa and the rotating speed to be 120r/min, adding an initiator, and reacting for 2 hours to prepare polyvinylidene fluoride emulsion;
(3) Degassing the polymer emulsion, recovering unreacted monomers, cooling, washing the emulsion with deionized water until the conductivity of the washing liquid is reduced to less than or equal to 3us/cm, carrying out flash evaporation drying, crushing and packaging to obtain the finished product.
Example 2:
(1) Vacuumizing a closed polymerization reaction kettle, introducing nitrogen to remove oxygen, and then adding deionized water, an emulsifier, kettle adhesion preventing agent paraffin, an initiator, a chain transfer agent and vinylidene fluoride, wherein the using amount of the deionized water is 400% of the mass of the vinylidene fluoride, the using amount of the emulsifier is 0.1% of the mass of the vinylidene fluoride, the using amount of the kettle adhesion preventing agent paraffin is 1.5% of the mass of the vinylidene fluoride, the using amount of the initiator is 0.05% of the mass of the vinylidene fluoride, and the using amount of the chain transfer agent is 0.2% of the mass of the vinylidene fluoride;
(2) Raising the temperature of the reaction kettle to 70 ℃, controlling the reaction pressure to be 6.5mpa and the rotating speed to be 70r/min, adding an initiator, and reacting for 5 hours to prepare polyvinylidene fluoride emulsion;
(3) Degassing the polymer emulsion, recovering unreacted monomers, cooling, washing the emulsion with deionized water until the conductivity of a washing liquid is reduced to be less than or equal to 3us/cm, carrying out flash evaporation drying, crushing and packaging to obtain a finished product.
Example 3:
(1) Vacuumizing a closed polymerization reaction kettle, introducing nitrogen to remove oxygen, and then adding deionized water, an emulsifier, kettle adhesion preventing agent paraffin, an initiator, a chain transfer agent and vinylidene fluoride, wherein the using amount of the deionized water is 350% of the mass of the vinylidene fluoride, the using amount of the emulsifier is 0.22% of the mass of the vinylidene fluoride, the using amount of the kettle adhesion preventing agent paraffin is 1% of the mass of the vinylidene fluoride, the using amount of the initiator is 0.11% of the mass of the vinylidene fluoride, and the using amount of the chain transfer agent is 0.13% of the mass of the vinylidene fluoride;
(2) Raising the temperature of the reaction kettle to 85 ℃, controlling the reaction pressure to be 5.5Mpa and the rotating speed to be 90 r/min, adding an initiator, and reacting for 3.5 hours to prepare polyvinylidene fluoride emulsion;
(3) Degassing the polymer emulsion, recovering unreacted monomers, cooling, washing the emulsion with deionized water until the conductivity of the washing liquid is reduced to less than or equal to 3us/cm, carrying out flash evaporation drying, crushing and packaging to obtain the finished product.
Example 4:
compared with the example 3, 10% of vinylidene fluoride reacts to obtain a polymer core, and the rest of vinylidene fluoride is added to react to obtain the polyvinylidene fluoride polymer.
Example 5:
compared with the example 3, 20% of vinylidene fluoride reacts to obtain a polymer core, and the rest of vinylidene fluoride is added to react to obtain the polyvinylidene fluoride polymer.
Example 6:
compared with the example 3, 15% of vinylidene fluoride reacts to obtain a polymer core, and the rest of vinylidene fluoride is added to react to obtain the polyvinylidene fluoride polymer.
Example 7:
compared with example 6, the initiator was added in an amount of 25% of the total mass before the reaction to obtain a polymer core, and the remaining initiator was added uniformly until the reaction was completed.
Example 8:
compared with example 6, the initiator was added in an amount of 45% of the total mass before the reaction to obtain a polymer core, and the remaining initiator was added uniformly until the reaction was completed.
Example 9:
compared with example 6, the initiator was added in an amount of 35% of the total mass before the reaction to obtain a polymer core, and the remaining initiator was added uniformly until the reaction was completed.
Battery performance testing
1. The test method comprises the following steps:
and respectively mixing the silicon-carbon negative electrode material with a conductive agent sp and the polyvinylidene fluoride finished product prepared in each embodiment according to the mass ratio of 91: 5: 4, dissolving the mixture with NMP, and uniformly coating the mixture on a copper current collector to obtain the negative electrode plate for the experimental battery. And mixing the NCM622 ternary material, sp and the polyvinylidene fluoride finished product according to the mass ratio of 93: 4: 3, dissolving the mixture by using NMP, and uniformly coating the mixture on an aluminum current collector to obtain the positive plate for the experimental battery. After punching, the battery case, the positive plate, the negative plate and the 20-micron ceramic diaphragm are dried in vacuum at 95 ℃ for 24 hours, and then a 1Ah soft package battery is formed in a glove box filled with argon, and after injection and sealing, an electrochemical test is carried out (according to GB/T31467.1-2015).
2. Test results
Index detection method
1. Determination of rotational viscosity
(1) The viscometer and electronic scale are turned on in advance.
(2) Weighing 10.0g of sample by using a beaker according to the specification
(3) Transferring 100ml of pyrrolidone reagent by a transfer pipette into a beaker filled with a sample, and stirring uniformly in the clockwise direction
(4) The mixture was stirred by a sand mill, and after the sample was completely dissolved, the mixture was transferred to a 100ml beaker.
(5) The horizontal bead of the rotational viscometer is adjusted to be horizontal.
(6) Selecting a rotor, putting the rotor into a sample beaker in a rotating mode, checking whether bubbles are not formed at the bottom of the rotor and in the beaker, putting the beaker into a constant-temperature water bath, fastening, adjusting a viscometer up and down to enable the scale lines of the rotor to be in the same level with the upper plane of the sample
(7) And selecting a corresponding rotor number on a display screen, selecting a rotating speed according to the range of the viscosity, pressing a confirmation key, and starting a key test.
(8) And reading after the data are stable.
Parallel determination 3 times, taking the average as the final value
2. Measurement of Mw and Mn
(1) The measuring instrument:
an Agilent chromatograph; a differential detector, a chromatographic column;
(3) Making a test sample:
weighing the sample, dissolving in DMF, placing in a dryer, and standing for more than 12 h.
(4) The determination step comprises:
1) Starting the computer; starting the instrument, and sequentially turning on four power switches; opening 'online software' on a computer desktop; and opening an instrument 'opening' button on the software, starting heating the column incubator and the reference pool, and waiting for the 'pump' and the 'column incubator' to display 'idle' in the reference pool to represent that the instrument is ready.
2) Cleaning a pump head: selecting control at the blank position of the pump, selecting single cleaning at the cleaning component of the pump sealing gasket, and determining the point within the default time of 1 min; cleaning once after starting up each time;
3) Exhausting: opening an exhaust valve of the instrument; the method of right clicking a point at the blank of the pump is adopted, the lower right corner of the point is determined, the flow speed is adjusted to be 0 after 5 minutes of exhaust, and the exhaust valve is screwed down rightwards after the flow speed is reduced to be 0;
4) The downloading method comprises the following steps: opening a 'method' interface, clicking a second small icon to 'open an acquisition method', selecting 'PVDF acquisition method is new', clicking to open, then clicking a right second small icon 'to send the current method to an instrument', and completing downloading of the method; and returning to the 'state' interface, and flushing the reference cell after the flow rate of the quaternary pump is increased to 1 ml/min.
5) Sample introduction: opening a single sample interface, inputting a sample name and a result name, turning a knob from INJET to LOAD before sample injection, cleaning a micro injector and a sample injector by using the sample, clicking to run after cleaning is finished, turning the knob to INJET after the left side is not ready and the sample is injected into the sample injector at a constant speed after the sample is absorbed, and pulling out the injector to finish the sample injection.
3. Determination of D50
1) Measuring instrument and tool
Laser particle analyzer, electronic balance, beaker, absolute ethyl alcohol, measuring cylinder, lens wiping paper.
2) Preparation before testing
(1) And turning on a power switch and analysis software of the particle analyzer.
(2) Checking whether the cleaning agent bottle has cleaning agent
(3) Checking whether the drainage bucket and the water inlet bucket are full or not.
3) And testing of
(1) Clicking 'online' on analysis software, changing the color of 'online' into green, and successfully connecting the instrument.
(2) And setting a test data storage file. Using the new file, click "File" - "File identification" to enter the file name.
(3) And inputting sample information.
(4) 70mg (+ -2 mg) of the sample was weighed into a 3ml absolute ethanol beaker and stirred well with a spoon.
(5) Clicking 'running SOP' on software;
(6) The sample is added according to the prompt, and after the concentration bar becomes green and stable, click to determine.
(7) When the light shading degree is determined to be between 15 and 20, clicking to determine, and starting to dispersedly store the sample.
(8) The icon changes from green to gray and the test ends.
4) Data storage
And double clicking the data bar to be viewed, and switching to a report page.
5) Data analysis
The data to be averaged is selected and analyzed by clicking-averaging to obtain the average of several tests.
4. Determination of dissolution
Accurately weighing a proper amount of sample, placing into a dry beaker, sucking a proper amount of pyrrolidone (analytically pure) solvent by a pipette, injecting into the beaker, placing into a magnetic stirrer for stirring, stirring by a glass rod every 10min, and stirring for 30 min. Under natural light, the solution should be clear, transparent, not turbid and free of impurities when the solution is inspected by eye observation.
5. Measurement of yellowing resistance
Zeroing and calibrating the electronic scale, weighing 5 +/-0.1 g of sample by using a tinfoil box, sintering in a high-temperature oven for 65min, taking out and cooling to room temperature, observing the sample by using eyes, wherein the color of the sample is lighter than or equal to that of a standard sample.
6. Measurement of high-temperature discoloration resistance
After analyzing the yellowing resistance measurement, the sample was observed with the eyes, and the color of the sample was white, which was acceptable.
7. Determination of melting Point
(1) And (3) detecting an instrument:
DSC 4000 melting point tester
(2) The determination step comprises:
1) Starting mechanical refrigeration, and after waiting for 10min, starting refrigeration by the refrigerator.
2) The nitrogen cylinder was opened and the gas pressure was adjusted to about 0.25mpa.
3) And starting the computer, starting the melting point tester, and waiting for the tester to enter a ready state.
4) Clicking computer desktop DSC 4000 software, and clicking an icon to perform online.
(3) Production of test specimens
1) 5-10 mg of the sample is weighed and pressed into a ball box.
2) After the instrument is ready (curve stabilized), the sample is placed.
3) After the start temperature stabilizes, the start program button may be clicked for testing.
(4) Data processing after test completion
1) Clicking first a data graph to be processed
2) Click on the calculate (Calc) menu, select Peak Area (Peak Area)
3) Pressing the mouse, selecting the temperature start and end points,
start of tick (Onset), click count.
4) Melting points are shown as peaks.
8. Measurement of peeling Strength
(1) A detection instrument:
KT-PSA-1056 peeling force tester, 3M double-sided adhesive tape and stainless steel plate
(1) The method comprises the following operation steps:
1) The pole piece slitting size is as follows: 19mm 70mm;
2) The fixed pressure-sensitive 3M-VHB double faced adhesive tape is pasted on the surface of the electrode, and the other surface is pasted on a stainless steel plate;
3) The test was carried out by fixing a stainless steel plate and a current collector on two clamps of a peel force tester, and then carrying out a 180-degree peel test at a speed of 10mm/min under a load of 10N, and the force detected when the aluminum current collector was completely peeled off was the peel strength.
9. Measurement of Capacity Retention after 300 cycles
(1) The measurement conditions were as follows:
the battery cycle life test should be carried out under the condition of the environmental temperature of 20 +/-5 ℃, and the cycle life is 300 times.
(2) The method comprises the following operation steps:
charging by using 1C5A under the condition that the ambient temperature is 20 +/-5 ℃, changing constant voltage charging when the battery terminal voltage reaches the charging limiting voltage until the charging current is less than or equal to 20mA, stopping charging, standing for 0.5-1 h, then discharging by using 1C5A current to the termination voltage, standing for 0.5-1 h after discharging is finished, then performing the next charging and discharging cycle, and calculating the capacity retention rate after 300 cycles.
10. Determination of Pole piece State after 300 cycles
And (4) observing the state of the pole piece after analyzing the capacity retention rate after 300 cycles, wherein no powder represents that the pole piece is qualified.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the embodiments, and any other changes, modifications, combinations, substitutions and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.
Claims (6)
1. The application of the polyvinylidene fluoride polymer in the lithium battery binder is characterized in that the polyvinylidene fluoride polymer is obtained by the following steps: in a deionized water environment, under the participation of an emulsifier, an initiator and a chain transfer agent, and under a certain temperature and pressure, the vinylidene fluoride homopolymerization is obtained, and the method is characterized in that the vinylidene fluoride homopolymerization process is as follows: reacting 15% of vinylidene fluoride to obtain a polymer core, and adding the rest vinylidene fluoride to react to obtain a polyvinylidene fluoride polymer;
the initiator is tert-butyl peroxypivalate, diethyl peroxydicarbonate, di-tert-butyl peroxide, diisopropyl peroxydicarbonate or di-n-propyl peroxydicarbonate, and the using amount of the initiator is 0.05-0.18% of the mass of the vinylidene fluoride;
the initiator is added with 25% -45% of the total mass before reaction, and after a polymer core is obtained, the rest initiator is uniformly added until the reaction is finished.
2. The use according to claim 1, characterized in that the emulsifier is an anionic fluorocarbon emulsifier, a fluorosurfactant or an amphoteric fluorocarbon surfactant in an amount of 0.1-0.35% by mass of vinylidene fluoride.
3. The method of claim 1, wherein the chain transfer agent is one or more of diethyl carbonate, ethyl acetate, diethyl malonate, isopropanol and propane, and the amount of the chain transfer agent is 0.06-0.2% of the mass of the vinylidene fluoride.
4. The use according to claim 1, characterized in that the amount of deionized water is 300-400% by mass of vinylidene fluoride.
5. The process of claim 1, wherein the polymerization temperature is 70-120 ℃, the polymerization pressure is 4-6.5MPa, the rotation speed of the polymerization stirrer is 70-100 rpm, and the reaction time is 2-5 hours.
6. The use according to claim 1, characterized in that 35% -55% of the total mass of chain transfer agent is added before the reaction, and after the polymer core is obtained and the reaction is over, the remaining chain transfer agent is added uniformly.
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