CN114773660A - Porous ultrahigh molecular weight fluorinated polyolefin hollow microsphere and preparation method thereof - Google Patents
Porous ultrahigh molecular weight fluorinated polyolefin hollow microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a porous ultrahigh molecular weight fluorinated polyolefin hollow microsphere and a preparation method thereof, and the preparation method comprises the following steps: (1) vacuumizing the reaction kettle, filling nitrogen, and adding a metal nano catalyst and a reactant according to a certain mass ratio; (2) heating the reaction kettle to 30-60 ℃, stirring at a rotating speed of 500-1500 r/min, and adding a pore-foaming agent; (3) maintaining the rotating speed at 500-1500 r/min, and filling fluorine-containing monomer to reach the polymerization pressure; (4) and centrifuging, washing and drying the polymerization product. The molecular weight of the obtained polyfluoroolefin hollow microspheres is 1.5-3.0 times of that of a polymer obtained by common free radical polymerization, the molecular weight distribution is narrow, the size of the microspheres is 10-200 mu m, and the pore size is 5-20 mu m. The obtained product has high porosity and is applied to lithium battery binders, diaphragms and high-efficiency catalyst carriers. The method has the advantages of mild reaction conditions, low cost, environmental friendliness and excellent industrial prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to porous ultrahigh molecular weight fluorinated polyolefin hollow microspheres and a preparation method thereof.
Background
The fluorine-containing polymer has good heat resistance, cold resistance, electrical insulation, chemical corrosion resistance and mechanical property, and is an excellent high-temperature resistant material and an insulating material. The fluoropolymer has wide application in the fields of construction, chemical industry, electronics, automobiles and the like. Among them, the special molecular structure of polyvinylidene fluoride makes it have properties which are both superior to those of fluorine resin and general-purpose resin, such as: excellent chemical resistance, high temperature resistance, weather resistance, UV resistance, dielectric property and the like. The excellent characteristics of the polyfluoroolefin enable the polyfluoroolefin to be widely applied to the fields of lithium batteries, chemical engineering corrosion prevention, piezoelectric materials, building coatings, oil and gas pipelines, medicines and the like.
With the shortage of energy and the increasing demand for environmental protection, the application of polyvinylidene fluoride in lithium batteries is rapidly increasing. In the end of 2020, the domestic lithium-grade polyvinylidene fluoride needs 1 ten thousand tons, and the estimated total domestic lithium-grade polyvinylidene fluoride demand in 2025 years is about 5 ten thousand tons. Currently, lithium-grade polyvinylidene fluoride raw materials are mainly supplied by foreign enterprises, such as Suwei in the United states, Wu Yu in Japan, and Akema in France. The viscosity of the obtained polymer solution can not reach the same level abroad due to the low molecular weight of the domestic polyvinylidene fluoride, and the mechanical properties such as toughness, impact resistance and the like of the polymer can not reach the level required by a lithium battery.
The synthesis of polyfluoroolefins includes solution polymerization, suspension polymerization and emulsion polymerization. Common in industry are suspension and emulsion polymerization: the emulsion polymerization has high polymerization rate, can obtain polyfluoroolefins with higher molecular weight, but has complex post-treatment and higher production cost, is difficult to remove the emulsifier, and has the damage to the electrical properties of the polyfluoroolefins. The suspension polymerization post-treatment is simple, the production cost is low, but the traditional production process has a long period and low production efficiency, and the molecular weight of the obtained polymer is low. In a certain range, the solution viscosity, the mechanical strength and other properties of the polymer are increased along with the increase of the molecular weight of the polymer, so that the prepared ultra-high molecular weight polyfluoroolefin can meet the requirement on the high performance of the lithium-grade polyfluoroolefin.
Disclosure of Invention
Aiming at the problems, the invention provides a porous ultrahigh molecular weight fluorinated olefin microsphere and a preparation method thereof, which solve the technical problems that the viscosity of the obtained polymer solution cannot meet the requirements of lithium batteries and the like due to longer period, lower production efficiency and lower molecular weight of the obtained polymer in the existing fluorinated olefin production process.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of porous ultrahigh molecular weight fluorinated polyolefin hollow microspheres adopts a metal nanoparticle catalytic polymerization reaction system, the polymerization mode is suspension polymerization, and the preparation method specifically comprises the following steps:
(1) vacuumizing the reaction kettle, filling nitrogen, replacing air in the reaction kettle, adding a second monomer, a catalyst, an initiator, a dispersing agent and deionized water according to a certain mass ratio, and closing the reaction kettle;
(2) heating the reaction kettle to 30-60 ℃, maintaining the stirring speed at 500-1500 r/min, adding a pore-foaming agent according to a certain mass ratio, and stirring uniformly;
(3) keeping the temperature of the reaction kettle at 30-60 ℃, maintaining the stirring speed at 500-1500 r/min, filling a first monomer to reach the polymerization reaction pressure, wherein the reaction pressure of the vinylidene fluoride is 2.8-5.0 MPa, supplementing the first monomer when the reaction pressure is reduced, maintaining the reaction pressure, maintaining the reaction temperature at 30-60 ℃, and the reaction duration time at 5-15 h;
(4) and after the reaction is finished, centrifuging, washing and drying the polymerization product to obtain the porous ultrahigh molecular weight fluorine-containing olefin hollow microsphere.
As a further technical scheme, the mass ratio in the step (1) is as follows: a second monomer: the catalyst is composed of an initiator, a dispersant and deionized water, wherein the ratio of the deionized water to the dispersant is 5-20: 0.0001-0.01: 0.1-1.0: 300-800; in the step (2), the mass ratio of the added pore-foaming agent is as follows: a second monomer: the pore-forming agent is 5-20: 0.1-1.0.
As a further technical scheme, in the step (1), the second monomer is one or more of tetrafluoroethylene, hexafluorobutyl methacrylate, perfluorohexene and perfluoroheptene; the first monomer in the step (3) is one of vinylidene fluoride, perfluoroethylene propylene and vinyl fluoride.
As a further technical scheme, the initiator in the step (1) is ethyl 2-bromoisobutyrate or ethyl 2-bromopropionate.
As a further technical scheme, in the step (1), the catalyst is a metal nanoparticle, and the metal nanoparticle is one of gold nanoparticle, silver nanoparticle, platinum nanoparticle, copper nanoparticle, nickel nanoparticle, iron nanoparticle, palladium nanoparticle and ruthenium nanoparticle.
As a further technical scheme, the metal nanoparticles are spherical, and the diameter of the metal nanoparticles is 2-100 nm.
As a further technical scheme, in the step (2), the pore-forming agent is one or two of n-pentane, n-hexane and petroleum ether; the dispersing agent in the step (1) is polyvinyl alcohol.
The invention also provides the porous ultrahigh molecular weight fluorinated polyolefin hollow microsphere prepared by the preparation method.
As a further technical scheme, the molecular weight of the porous ultra-high molecular weight fluorinated olefin hollow microsphere is 1.5-3.0 times of that of a polymer obtained by common polymerization, the molecular weight distribution is 2.0-5.0, the microsphere size is 10-200 mu m, and the pore size is 5-20 mu m.
Compared with the prior art, the invention has the following beneficial effects:
the porous fluorine-containing olefin hollow microsphere with ultrahigh molecular weight is prepared by a metal nanoparticle catalytic polymerization reaction system and a suspension polymerization mode, and the obtained polymer has a porous structure and ultrahigh molecular weight, has excellent solution viscosity and mechanical properties, and meets the requirements of the fluorine-containing olefin for lithium batteries. The size of the prepared microspheres is 10-200 mu m, and the size of the aperture is 5-20 mu m. The obtained product has adjustable porosity (30-80%), adjustable specific surface area and can be applied to lithium battery binders, diaphragms and efficient catalyst carriers. The method has mild reaction conditions, low production cost and environmental friendliness, conforms to the carbon neutralization development concept and has excellent industrial prospect.
Drawings
FIG. 1 is a schematic diagram of a porous UHMWPE hollow microsphere prepared in example 1 of the present invention;
FIG. 2 is a GPC chart of the porous UHMWPE hollow microsphere prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to a preparation method of porous fluorine-containing polyolefin microspheres with ultrahigh molecular weight, which adopts a metal nanoparticle catalytic polymerization reaction system, adopts suspension polymerization as a polymerization mode, and comprises the following steps:
(1) vacuumizing a reaction kettle, filling nitrogen, replacing air in the reaction kettle, adding a second monomer, a catalyst, an initiator, a dispersing agent and deionized water according to a certain mass ratio, and closing the reaction kettle, wherein the second monomer: the catalyst is composed of an initiator, a dispersant and deionized water, wherein the ratio of the deionized water is 5-20: 0.0001-0.01: 0.1-1.0: 300-800;
(2) heating the reaction kettle to 30-60 ℃, maintaining the stirring speed at 500-1500 r/min, adding a pore-foaming agent according to a certain mass ratio, and stirring uniformly, wherein the second monomer: pore-forming agent = 5-20: 0.1-1.0;
(3) keeping the temperature of the reaction kettle at 30-60 ℃, maintaining the stirring speed at 500-1500 r/min, filling a first monomer to reach the polymerization reaction pressure, supplementing the first monomer when the reaction pressure is reduced, maintaining the reaction pressure, maintaining the reaction temperature at 30-60 ℃, and keeping the reaction duration for 5-15 h;
(4) and after the reaction is finished, centrifuging, washing and drying the polymerization product to obtain the porous ultrahigh molecular weight fluorinated polyolefin hollow microsphere.
Wherein, in the step (1), the second monomer is one or more of tetrafluoroethylene, hexafluorobutyl methacrylate, perfluorohexene and perfluoroheptene, and mainly has the functions of modification, flexibility increase, molecular weight improvement and various mechanical properties improvement; the catalyst in the step (1) is a metal nanoparticle, the metal nanoparticle is one of gold nanoparticle, silver nanoparticle, platinum nanoparticle, copper nanoparticle, nickel nanoparticle, iron nanoparticle, palladium nanoparticle and ruthenium nanoparticle, the metal nanoparticle is spherical, and the diameter of the metal nanoparticle is 2-100 nm; the initiator in the step (1) is 2-bromoisobutyric acid ethyl ester or 2-bromopropionic acid ethyl ester; the dispersing agent is polyvinyl alcohol; in the step (2), the pore-foaming agent is one or two of n-pentane, n-hexane and petroleum ether; the first monomer in the step (3) is vinylidene fluoride, perfluoroethylene propylene or vinyl fluoride.
The specific preparation examples are as follows:
example 1:
firstly, closing the reaction kettle, vacuumizing the reaction kettle, then filling nitrogen in the reaction kettle in a vacuum state, and replacing air in the reaction kettle. Into a stainless steel autoclave equipped with stirring, 600 g of deionized water, 10 g of hexafluorobutyl methacrylate, 0.001 g of silver nanoparticles (spherical), 0.8 g of ethyl 2-bromoisobutyrate, 0.3 g of polyvinyl alcohol, 0.3 g of n-pentane were charged via the apparatus charging device.
Maintaining the temperature of the reaction kettle at 50 ℃, maintaining the stirring speed at 500 r/min, charging vinylidene fluoride to increase the pressure of the reaction kettle to 3.5 MPa, supplementing the vinylidene fluoride monomer when the pressure is reduced, maintaining the reaction pressure at 3.5 MPa, maintaining the polymerization temperature at 50 ℃, and maintaining the polymerization reaction time at 10 h. And after the reaction is finished, stopping stirring, and centrifuging, washing and drying the polymerization product to obtain the porous ultra-high molecular weight polyvinylidene fluoride hollow microspheres.
Particle size and pore size measurement of microspheres: and (3) observing the dried polyfluoroolefin hollow microspheres by using a Scanning Electron Microscope (SEM).
And (3) testing the molecular weight: and (3) taking a certain amount of product, dissolving the product in a DMF solvent, measuring a polymer chromatogram by Gel Permeation Chromatography (GPC), and analyzing and calculating the molecular weight of the polymer microsphere.
The molecular weight of the obtained polyvinylidene fluoride hollow microspheres is 125 ten thousand, the molecular weight distribution is 3.5, the size of the microspheres is 40-150 mu m, the size of the pore size is 5-20 mu m, and the product yield is = 92.5%.
Example 2:
firstly, closing the reaction kettle, vacuumizing the reaction kettle, then filling nitrogen in the reaction kettle in a vacuum state, and replacing air in the reaction kettle. In a stainless steel autoclave equipped with stirring, 800 g of deionized water, 5 g of hexafluorobutyl methacrylate, 0.0001 g of silver nanoparticles (spherical), 0.1 g of ethyl 2-bromoisobutyrate, 0.1 g of polyvinyl alcohol, 0.1 g of n-pentane were charged through the apparatus charging device.
And (3) maintaining the temperature of the reaction kettle at 30 ℃, maintaining the stirring speed at 800 r/min, charging vinylidene fluoride to increase the pressure of the reaction kettle to 2.8 MPa, replenishing vinylidene fluoride monomer when the pressure is reduced, maintaining the reaction pressure at 2.8 MPa, maintaining the polymerization temperature at 30 ℃, and keeping the polymerization reaction time at 15 h. And after the reaction is finished, stopping stirring, and centrifuging, washing and drying the polymerization product to obtain the porous ultra-high molecular weight polyvinylidene fluoride hollow microspheres.
The test procedure of example 1 was repeated. The molecular weight of the obtained polyvinylidene fluoride hollow microspheres is 104 ten thousand, the molecular weight distribution is 2.0, the size of the microspheres is 20-110 mu m, the size of the pore diameter is 5-20 mu m, and the product yield is = 68.5%.
Example 3:
firstly, closing the reaction kettle, vacuumizing the reaction kettle, then filling nitrogen in the reaction kettle in a vacuum state, and replacing air in the reaction kettle. Into a stainless steel autoclave equipped with stirring, through the apparatus charging device, 300 g of deionized water, 20g of hexafluorobutyl methacrylate, 0.01 g of platinum nanoparticles (columnar), 1.0 g of ethyl 2-bromoisobutyrate, 1.0 g of polyvinyl alcohol, 1.0 g of n-pentane were charged.
Maintaining the temperature of the reaction kettle at 60 ℃, maintaining the stirring speed at 1500 r/min, charging vinylidene fluoride to increase the pressure of the reaction kettle to 5.0 MPa, supplementing the vinylidene fluoride monomer when the pressure is reduced, maintaining the reaction pressure at 5.0 MPa, maintaining the polymerization temperature at 60 ℃, and maintaining the polymerization reaction time for 5 hours. And after the reaction is finished, stopping stirring, and centrifuging, washing and drying the polymerization product to obtain the porous ultra-high molecular weight polyvinylidene fluoride hollow microspheres.
The test procedure of example 1 was repeated. The molecular weight of the obtained polyvinylidene fluoride hollow microspheres is 118 ten thousand, the molecular weight distribution is 5.0, the size of the microspheres is 50-110 mu m, the size of the pore size is 5-20 mu m, and the product yield is = 98.5%.
Example 4:
firstly, closing the reaction kettle, vacuumizing the reaction kettle, and then filling nitrogen in the reaction kettle in a vacuum state to replace air in the reaction kettle. In a stainless steel autoclave equipped with stirring, 600 g of deionized water, 10 g of hexafluorobutyl methacrylate, 0.001 g of copper nanoparticles (spherical), 0.8 g of ethyl 2-bromoisobutyrate, 0.3 g of polyvinyl alcohol, 1.0 g of n-pentane were charged via the apparatus charging device.
And (3) maintaining the temperature of the reaction kettle at 50 ℃, maintaining the stirring speed at 800 r/min, filling vinylidene fluoride to increase the pressure of the reaction kettle to 3.5 MPa, replenishing vinylidene fluoride monomer when the pressure is reduced, maintaining the reaction pressure at 3.5 MPa, maintaining the polymerization temperature at 50 ℃, and performing polymerization for 10 hours. And after the reaction is finished, stopping stirring, and centrifuging, washing and drying the polymerization product to obtain the porous ultra-high molecular weight polyvinylidene fluoride hollow microspheres.
The test procedure of example 1 was repeated. The molecular weight of the obtained polyvinylidene fluoride hollow microspheres is 108 ten thousand, the molecular weight distribution is 2.8, the size of the microspheres is 30-110 mu m, the size of the pore size is 5-20 mu m, and the product yield is = 82.3%.
Example 5:
firstly, closing the reaction kettle, vacuumizing the reaction kettle, then filling nitrogen in the reaction kettle in a vacuum state, and replacing air in the reaction kettle. In a stainless steel autoclave equipped with stirring, 600 g of deionized water, 10 g of chlorotrifluoroethylene, 0.001 g of silver nanoparticles (spherical), 0.8 g of ethyl 2-bromoisobutyrate, 0.3 g of polyvinyl alcohol, 1.0 g of n-pentane were added via the apparatus feed.
And (3) maintaining the temperature of the reaction kettle at 50 ℃, maintaining the stirring speed at 800 r/min, filling vinylidene fluoride to increase the pressure of the reaction kettle to 3.5 MPa, replenishing vinylidene fluoride monomer when the pressure is reduced, maintaining the reaction pressure at 3.5 MPa, maintaining the polymerization temperature at 50 ℃, and performing polymerization for 10 hours. And after the reaction is finished, stopping stirring, and centrifuging, washing and drying the polymerization product to obtain the porous ultra-high molecular weight polyvinylidene fluoride hollow microspheres.
The test procedure of example 1 was repeated. The molecular weight of the obtained polyvinylidene fluoride hollow microspheres is 123 ten thousand, the molecular weight distribution is 3.6, the size of the microspheres is 40-115 mu m, the pore size is 5-20 mu m, and the product yield is = 85.4%.
Example 6:
firstly, closing the reaction kettle, vacuumizing the reaction kettle, and then filling nitrogen in the reaction kettle in a vacuum state to replace air in the reaction kettle. In a stainless steel autoclave equipped with stirring, 600 g of deionized water, 10 g of perfluorohexene, 0.001 g of nickel nanoparticles (spherical), 0.8 g of ethyl 2-bromoisobutyrate, 0.3 g of polyvinyl alcohol, 1.0 g of n-pentane were charged via the apparatus charging device.
And (3) maintaining the temperature of the reaction kettle at 50 ℃, maintaining the stirring speed at 800 r/min, filling vinylidene fluoride to increase the pressure of the reaction kettle to 3.5 MPa, replenishing vinylidene fluoride monomer when the pressure is reduced, maintaining the reaction pressure at 3.5 MPa, maintaining the polymerization temperature at 50 ℃, and performing polymerization for 10 hours. And after the reaction is finished, stopping stirring, and centrifuging, washing and drying the polymerization product to obtain the porous ultra-high molecular weight polyvinylidene fluoride hollow microspheres.
The test procedure of example 1 was repeated. The molecular weight of the obtained polyvinylidene fluoride hollow microspheres is 128 ten thousand, the molecular weight distribution is 2.9, the size of the microspheres is 10-100 mu m, the size of the pore size is 5-20 mu m, and the product yield is = 90.3%.
Example 7:
firstly, closing the reaction kettle, vacuumizing the reaction kettle, then filling nitrogen in the reaction kettle in a vacuum state, and replacing air in the reaction kettle. In a stainless steel autoclave equipped with stirring, 600 g of deionized water, 10 g of hexafluorobutyl methacrylate, 0.001 g of silver nanoparticles (spherical), 0.8 g of ethyl 2-bromopropionate, 0.3 g of polyvinyl alcohol, 1.0 g of n-pentane were added via the apparatus charging device.
Maintaining the temperature of the reaction kettle at 50 ℃, maintaining the stirring speed at 800 r/min, charging vinylidene fluoride to increase the pressure of the reaction kettle to 3.5 MPa, supplementing the vinylidene fluoride monomer when the pressure is reduced, maintaining the reaction pressure at 3.5 MPa, maintaining the polymerization temperature at 50 ℃, and maintaining the polymerization reaction time at 10 h. And after the reaction is finished, stopping stirring, and centrifuging, washing and drying the polymerization product to obtain the porous ultra-high molecular weight polyvinylidene fluoride hollow microspheres.
The test procedure of example 1 was repeated. The molecular weight of the obtained polyvinylidene fluoride hollow microspheres is 130 ten thousand, the molecular weight distribution is 3.7, the size of the microspheres is 30-120 mu m, the pore size is 5-20 mu m, and the product yield is = 93.5%.
Example 8:
firstly, closing the reaction kettle, vacuumizing the reaction kettle, then filling nitrogen in the reaction kettle in a vacuum state, and replacing air in the reaction kettle. In a stainless steel autoclave equipped with stirring, 600 g of deionized water, 10 g of perfluoroheptene, 0.001 g of palladium nanoparticles (spherical), 0.8 g of ethyl 2-bromoisobutyrate, 0.3 g of polyvinyl alcohol, 1.0 g of n-pentane were charged via the apparatus charging device.
And (3) maintaining the temperature of the reaction kettle at 50 ℃, maintaining the stirring speed at 1000 r/min, filling vinylidene fluoride to increase the pressure of the reaction kettle to 3.5 MPa, replenishing vinylidene fluoride monomer when the pressure is reduced, maintaining the reaction pressure at 3.5 MPa, maintaining the polymerization temperature at 50 ℃, and performing polymerization for 10 hours. And after the reaction is finished, stopping stirring, and centrifuging, washing and drying the polymerization product to obtain the porous ultra-high molecular weight polyvinylidene fluoride hollow microspheres.
The test procedure of example 1 was repeated. The molecular weight of the obtained polyvinylidene fluoride hollow microspheres is 125 ten thousand, the molecular weight distribution is 3.2, the size of the microspheres is 40-200 mu m, the pore size is 5-20 mu m, and the product yield is = 90.4%.
Example 9:
firstly, closing the reaction kettle, vacuumizing the reaction kettle, and then filling nitrogen in the reaction kettle in a vacuum state to replace air in the reaction kettle. In a stainless steel autoclave equipped with stirring, 600 g of deionized water, 10 g of hexafluoropropylene, 0.001 g of palladium nanoparticles (spherical), 0.8 g of ethyl 2-bromoisobutyrate, 0.3 g of polyvinyl alcohol, 1.0 g of n-pentane were added via the equipment addition.
And (3) maintaining the temperature of the reaction kettle at 50 ℃, maintaining the stirring speed at 800 r/min, charging tetrafluoroethylene and hexafluoropropylene to increase the pressure of the kettle to 2.0 MPa, supplementing tetrafluoroethylene and hexafluoropropylene monomers when the pressure is reduced, maintaining the reaction pressure at 2.0 MPa, maintaining the polymerization temperature at 50 ℃, and maintaining the polymerization reaction time at 10 h. And after the reaction is finished, stopping stirring, and centrifuging, washing and drying the polymerization product to obtain the porous ultra-high molecular weight perfluoroethylene propylene hollow microsphere.
The test procedure of example 1 was repeated. The molecular weight of the obtained fluorinated ethylene propylene hollow microsphere is 35 ten thousand, the molecular weight distribution is 4.3, the microsphere size is 40-200 mu m, the pore size is 5-20 mu m, and the product yield is = 85.4%.
Example 10:
firstly, closing the reaction kettle, vacuumizing the reaction kettle, and then filling nitrogen in the reaction kettle in a vacuum state to replace air in the reaction kettle. Into a stainless steel autoclave equipped with stirring, through the apparatus charging device, 600 g of deionized water, 0.001 g of palladium nanoparticles (spherical), 0.8 g of ethyl 2-bromoisobutyrate, 0.3 g of polyvinyl alcohol, 1.0 g of n-pentane were charged.
Maintaining the temperature of the reaction kettle at 50 ℃, maintaining the stirring speed at 800 r/min, filling vinyl fluoride to increase the pressure of the kettle to 2.5 MPa, supplementing vinyl fluoride monomer when the pressure is reduced, maintaining the reaction pressure at 2.5 MPa, maintaining the polymerization temperature at 50 ℃, and maintaining the polymerization reaction time at 10 h. And after the reaction is finished, stopping stirring, and centrifuging, washing and drying the polymerization product to obtain the porous ultrahigh molecular weight polyvinyl fluoride hollow microspheres.
The test procedure of example 1 was repeated. The molecular weight of the obtained polyvinyl fluoride hollow microspheres is 30 ten thousand, the molecular weight distribution is 4.5, the size of the microspheres is 40-200 mu m, the pore size is 5-20 mu m, and the product yield is = 85.4%.
The first monomer of the present invention may also be other fluorine-containing olefins, and is also suitable for the process of the present invention to prepare the porous ultrahigh molecular weight fluorine-containing olefin hollow microsphere.
In conclusion, the invention provides the preparation method of the porous ultrahigh molecular weight fluorinated olefin hollow microsphere with mild reaction conditions, environmental friendliness and simple process. The ultra-high molecular weight polyfluoroolefin hollow microsphere is synthesized by metal nanoparticle catalytic polymerization reaction, wherein the molecular weight of polyvinylidene fluoride is up to more than one million, and the solution viscosity and the mechanical property are remarkably improved, so that the problem of shortage of the existing domestic lithium battery grade high-performance polyfluoroolefin is solved. The size of the prepared microspheres is 10-200 mu m, and the size of the aperture is 5-20 mu m. The obtained product has high porosity and large specific surface area, and can be applied to lithium battery binders, diaphragms and high-efficiency catalyst carriers. The polymerization method has low cost, is environment-friendly and conforms to the carbon neutralization development concept.
Claims (10)
1. A preparation method of porous ultra-high molecular weight fluorinated olefin hollow microspheres is characterized in that a metal nanoparticle catalytic polymerization reaction system is adopted, the polymerization mode is suspension polymerization, and the preparation method specifically comprises the following steps:
(1) vacuumizing the reaction kettle, filling nitrogen, replacing air in the reaction kettle, adding a second monomer, a catalyst, an initiator, a dispersing agent and deionized water according to a certain mass ratio, and closing the reaction kettle;
(2) heating the reaction kettle to 30-60 ℃, maintaining the stirring speed at 500-1500 r/min, adding a pore-foaming agent according to a certain mass ratio, and uniformly stirring;
(3) keeping the temperature of the reaction kettle at 30-60 ℃, maintaining the stirring speed at 500-1500 r/min, filling a first monomer to reach the polymerization reaction pressure, supplementing the first monomer when the reaction pressure is reduced, maintaining the reaction pressure, maintaining the reaction temperature at 30-60 ℃, and keeping the reaction duration for 5-15 h;
(4) and after the reaction is finished, centrifuging, washing and drying the polymerization product to obtain the porous ultrahigh molecular weight fluorine-containing olefin hollow microsphere.
2. The preparation method of the porous ultra-high molecular weight fluorinated olefin hollow microsphere according to claim 1, wherein the mass ratio in the step (1) is as follows: a second monomer: the catalyst is composed of an initiator, a dispersant and deionized water, wherein the ratio of the deionized water is 5-20: 0.0001-0.01: 0.1-1.0: 300-800; in the step (2), the mass ratio of the added pore-foaming agent is as follows: a second monomer: the pore-forming agent is 5-20: 0.1-1.0.
3. The method for preparing the porous hollow microsphere of the fluorinated polyolefin with the ultrahigh molecular weight according to claim 1, wherein the second monomer in the step (1) is one or more of tetrafluoroethylene, hexafluorobutyl methacrylate, perfluorohexene and perfluoroheptene; the first monomer in the step (3) is fluorine-containing olefin.
4. The method for preparing the porous hollow microsphere of the fluorinated polyolefin with the ultrahigh molecular weight according to claim 3, wherein the fluorinated olefin is one of vinylidene fluoride, perfluoroethylene propylene and vinyl fluoride.
5. The method for preparing the porous ultra-high molecular weight fluorinated olefin hollow microsphere according to claim 1, wherein in the step (1), the initiator is ethyl 2-bromoisobutyrate or ethyl 2-bromopropionate; the dispersing agent in the step (1) is polyvinyl alcohol.
6. The method for preparing porous hollow microspheres of ultra-high molecular weight fluorinated olefin according to claim 1, wherein the catalyst in step (1) is a metal nanoparticle, and the metal nanoparticle is one of gold nanoparticle, silver nanoparticle, platinum nanoparticle, copper nanoparticle, nickel nanoparticle, iron nanoparticle, palladium nanoparticle and ruthenium nanoparticle.
7. The preparation method of the porous ultra-high molecular weight fluorinated polyolefin hollow microsphere according to claim 6, wherein the metal nanoparticles are spherical and have a diameter of 2-100 nm.
8. The preparation method of the porous ultra-high molecular weight fluorinated olefin hollow microsphere according to claim 1, wherein in the step (2), the pore-forming agent is one or two of n-pentane, n-hexane and petroleum ether.
9. A porous hollow microsphere of fluorinated polyolefin with ultrahigh molecular weight, which is characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. The porous ultra-high molecular weight fluorinated olefin hollow microsphere according to claim 9, characterized in that the molecular weight of the porous ultra-high molecular weight fluorinated olefin hollow microsphere is 1.5-3.0 times that of a polymer obtained by common polymerization, the molecular weight distribution is 2.0-5.0, the microsphere size is 10-200 μm, and the pore size is 5-20 μm.
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| CN101735374A (en) * | 2009-12-15 | 2010-06-16 | 上海三爱富新材料股份有限公司 | Preparation method of vinylidene fluoride copolymer resin |
| CN104497190A (en) * | 2014-12-29 | 2015-04-08 | 浙江孚诺林化工新材料有限公司 | Preparation method of vinylidene fluoride polymer of lithium ion battery electrode material binder |
| CN105924657A (en) * | 2016-06-03 | 2016-09-07 | 广东工业大学 | Preparation method of electrostatic spray nano microsphere with porous structure |
| CN108409894A (en) * | 2017-02-09 | 2018-08-17 | 浙江工业大学 | The method that transition metal nanoparticles are catalyzed polymerization of vinyl monomer reaction |
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| CN101735374A (en) * | 2009-12-15 | 2010-06-16 | 上海三爱富新材料股份有限公司 | Preparation method of vinylidene fluoride copolymer resin |
| CN104497190A (en) * | 2014-12-29 | 2015-04-08 | 浙江孚诺林化工新材料有限公司 | Preparation method of vinylidene fluoride polymer of lithium ion battery electrode material binder |
| CN105924657A (en) * | 2016-06-03 | 2016-09-07 | 广东工业大学 | Preparation method of electrostatic spray nano microsphere with porous structure |
| CN108409894A (en) * | 2017-02-09 | 2018-08-17 | 浙江工业大学 | The method that transition metal nanoparticles are catalyzed polymerization of vinyl monomer reaction |
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| CN115594931A (en) * | 2022-12-13 | 2023-01-13 | 四川省众望科希盟科技有限公司（Cn） | Aerospace and aviation conductive expanded polytetrafluoroethylene sealing material |
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