CN112778679A - High-strength and high-thermal-stability poly (4-methyl-1-pentene) microporous membrane and preparation method thereof - Google Patents

High-strength and high-thermal-stability poly (4-methyl-1-pentene) microporous membrane and preparation method thereof Download PDF

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CN112778679A
CN112778679A CN202011639374.XA CN202011639374A CN112778679A CN 112778679 A CN112778679 A CN 112778679A CN 202011639374 A CN202011639374 A CN 202011639374A CN 112778679 A CN112778679 A CN 112778679A
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夏超华
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Suzhou Xinguangyi Electronics Co ltd
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Abstract

The invention discloses a high-strength and high-thermal-stability poly (4-methyl-1-pentene) microporous membrane which is characterized by being prepared from the following raw materials in parts by weight: 60-70 parts of poly-4-methyl-1-pentene, 3-5 parts of acrylic acid modified fluconazole, 8-15 parts of 4-chloromethyl styrene modified 4-fluorophenyl methyl imino diacetate and 15-25 parts of high-density polyethylene. The invention also discloses a preparation method of the poly 4-methyl-1-pentene microporous membrane with high strength and high thermal stability. The high-strength and high-thermal-stability poly 4-methyl-1-pentene microporous membrane disclosed by the invention is excellent in mechanical property, thermal stability, chemical stability and electrochemical stability, can keep high wettability to an electrolyte in a repeated charging and discharging process, and is suitable for a lithium battery diaphragm.

Description

High-strength and high-thermal-stability poly (4-methyl-1-pentene) microporous membrane and preparation method thereof
Technical Field
The invention relates to the technical field of membrane materials, in particular to a poly 4-methyl-1-pentene microporous membrane with high strength and high thermal stability and a preparation method thereof.
Background
With the progress of information, material and energy technology, the technology of secondary lithium batteries and related materials thereof have also been rapidly developed. The diaphragm is a layer of diaphragm material between the positive electrode and the negative electrode of the lithium battery, is a very critical part in the battery, and has direct influence on the safety and the cost of the battery. The function of the separator is to separate the anode and the cathode in the battery to avoid short circuit, to enable ions to smoothly migrate between the two electrodes through the separator to form current, and to close an ion channel when the battery works abnormally, and to cut off the current to ensure the safety of the battery.
At present, a separator of a lithium ion battery prepared by a thermal separation method is mainly made of polyethylene, and has good chemical stability and excellent physical properties, but a commercial polyethylene separator has a melting point below 150 ℃, and has poor high-temperature and thermal shrinkage properties, and in the use process of the lithium ion battery, due to some reasons, the separator is punctured and perforated, or due to the temperature rise of the battery under the action of the inside or the outside, the separator is thermally shrunk or melted, and the positive electrode and the negative electrode of the lithium battery are in direct contact, so that the short circuit and even the explosion of the lithium battery are caused, and the safe use of the lithium battery is limited. Therefore, an ideal lithium battery separator needs to have not only excellent mechanical properties and ionic conductivity, but also good thermal stability, chemical stability and electrochemical stability, and to maintain high wettability to an electrolyte during repeated charging and discharging. The performance of the lithium battery diaphragm directly influences the battery capacity, the cycle service life and the safety performance of the lithium battery. Therefore, development of a lithium battery separator having excellent overall performance is imperative.
Poly-4-methyl-1-pentene (PMP) has been widely used in the fields of chemical industry, environmental protection, medical treatment and the like as a gas separation membrane with excellent performance due to the advantages of good heat resistance, high mechanical strength and large gas transmission capacity, and is expected to become a material for a high-temperature-resistant lithium battery diaphragm as a membrane with shape retention at high temperature. For example, chinese patent application No. 201080027091.8 mentions that polymethylpentene (PMP) is used to increase the membrane rupture temperature of the membrane in order to improve the safety of the battery. Although improved, polymeric microporous membranes with higher rupture temperatures are desired.
Disclosure of Invention
The invention mainly aims to provide a poly 4-methyl-1-pentene microporous membrane which has excellent mechanical and mechanical properties, good thermal stability, chemical stability and electrochemical stability, can keep high wettability to electrolyte in the repeated charge and discharge process, and is suitable for a lithium battery diaphragm and high in strength and high thermal stability. Meanwhile, the invention also provides a preparation method of the poly 4-methyl-1-pentene microporous membrane with high strength and high thermal stability, and the preparation method is simple and easy to implement, high in preparation efficiency and finished product qualification rate, and suitable for continuous large-scale production.
In order to achieve the above purpose, the invention provides a poly 4-methyl-1-pentene microporous membrane with high strength and high thermal stability, which is characterized by being prepared from the following raw materials in parts by weight: 60-70 parts of poly-4-methyl-1-pentene, 3-5 parts of acrylic acid modified fluconazole, 8-15 parts of 4-chloromethyl styrene modified 4-fluorophenyl methyl imino diacetate and 15-25 parts of high-density polyethylene.
Preferably, the preparation method of the acrylic acid modified fluconazole comprises the following steps: adding acrylic acid, fluconazole, 4-dimethylaminopyridine and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into an organic solvent, carrying out reflux stirring reaction for 4-6 hours at the temperature of 30-50 ℃, then carrying out rotary evaporation to remove the solvent, washing for 3-6 times by using water, and then carrying out rotary evaporation to remove water to obtain the acrylic acid modified fluconazole.
Preferably, the molar ratio of the acrylic acid to the fluconazole to the 4-dimethylaminopyridine to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the organic solvent is 1:1 (0.4-0.6) to 1 (8-15).
Preferably, the organic solvent is at least one of methanol, ethanol and isopropanol.
Preferably, the preparation method of the 4-chloromethyl styrene modified 4-fluorophenyl methyl imino diacetate comprises the following steps: adding 4-chloromethylstyrene, 4-fluorophenylboronic acid methyl imino diacetate and an alkaline catalyst into acetonitrile, stirring and reacting for 5-8 hours at 30-40 ℃, filtering to remove insoluble substances, and performing rotary evaporation to remove acetonitrile to obtain the 4-chloromethylstyrene modified 4-fluorophenylboronic acid methyl imino diacetate.
Preferably, the molar ratio of the 4-chloromethyl styrene to the 4-fluorophenylboronic acid methyl imino diacetate to the basic catalyst to the acetonitrile is 1:1 (0.8-1.2) to (8-14).
Preferably, the alkaline catalyst is at least one of sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate.
Preferably, the poly-4-methyl-1-pentene is
Figure BDA0002877891120000031
MX004 poly-4-methyl-1-pentene.
Preferably, the high density polyethylene is a 3300F grade high density polyethylene.
Another object of the present invention is to provide a method for preparing the poly-4-methyl-1-pentene microporous membrane with high strength and high thermal stability, which comprises the following steps: the preparation method comprises the steps of uniformly mixing the raw materials in parts by weight to obtain a mixture, adding the mixture into a double-screw extruder for melt extrusion, performing casting film forming, sequentially performing biaxial tension, heat setting, radiation grafting crosslinking, washing with ethanol, and drying to obtain the high-strength and high-thermal-stability poly 4-methyl-1-pentene microporous film.
Preferably, the melt extrusion temperature is 300-350 ℃; the magnification of the biaxial stretching is (5-8) × (10-15).
Preferably, the heat setting temperature is 120-150 ℃, and the setting time is 5-10 min.
Preferably, the radiation grafting crosslinking is carried out in a nitrogen atmosphere, and the radiation energy of the radiation grafting crosslinking is 5MeV-15MeV, and the radiation dose is 80KGy-200 KGy.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) the preparation method of the poly 4-methyl-1-pentene microporous membrane with high strength and high thermal stability, disclosed by the invention, is simple and feasible, has high preparation efficiency and finished product qualification rate, and is suitable for continuous large-scale production.
(2) The invention discloses a high-strength and high-thermal-stability poly 4-methyl-1-pentene microporous membrane, which overcomes the defects that a commercial polyethylene membrane has a melting point below 150 ℃, has poor high temperature and thermal shrinkage performance, is punctured and perforated due to some reasons in the use process of a lithium ion battery, or is punctured and perforated due to the increase of the temperature of the battery under the action of the inside or the outside, the membrane is thermally shrunk or melted, and the positive and negative electrodes of the lithium battery are in direct contact, so that the short circuit and even explosion of the lithium battery are caused, and the safe use of the lithium battery is limited, and the prepared high-strength and high-thermal-stability poly 4-methyl-1-pentene microporous membrane has excellent mechanical property, thermal stability, chemical stability and electrochemical stability through the synergistic action of all components, and can keep high wettability to electrolyte in the repeated charging and discharging processes, is suitable for the lithium battery diaphragm.
(3) The invention discloses a poly 4-methyl-1-pentene microporous membrane with high strength and high thermal stability, wherein the added acrylic acid modified fluconazole is formed by esterification reaction of acrylic acid and hydroxyl on the fluconazole, the fluconazole with low price is used, a new using way is provided for medical waste, waste can be changed into valuable, the azole group and the fluorophenyl group on the membrane can endow the membrane with excellent mechanical property and high temperature resistance, so that the membrane has excellent performance stability, a 4-dimethylaminopyridine/1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride catalytic system is used in the esterification process, the reaction condition is mild, the olefinic bond can be effectively protected from polymerization, and the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride can be removed by washing, 4-dimethylamino pyridine can be partially left in the product, and after the final film forming, the product is washed and removed by ethanol, so that a microporous structure can be endowed to the film, the problem that the film is difficult to separate and purify is effectively solved, and the film plays a role of a pore-forming agent.
(4) According to the poly 4-methyl-1-pentene microporous membrane with high strength and high thermal stability, 4-chloromethyl styrene is added to modify 4-fluorophenyl methyl imino diacetate, the chlorine radical on the 4-chloromethyl styrene and the nitrogen on the 4-fluorophenyl methyl imino diacetate are subjected to quaternization, and the introduced fluorobenzene borate structure can further improve the comprehensive performance of the membrane and has a better improvement effect on the strength and the thermal stability of the membrane.
(5) According to the high-strength high-thermal-stability poly 4-methyl-1-pentene microporous membrane disclosed by the invention, vinyl on acrylic acid modified fluconazole and 4-chloromethyl styrene modified 4-fluorophenyl boric acid methyl imino diacetate is connected to a poly 4-methyl-1-pentene molecular chain in a chemical bond form through radiation grafting in the membrane forming process to form a three-dimensional network structure, so that the comprehensive performance and the performance stability are better.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
In the embodiment of the invention, the raw materials are all purchased commercially; the poly-4-methyl-1-pentene is
Figure BDA0002877891120000051
MX004 poly-4-methyl-1-pentene; the high density polyethylene is a high density polyethylene having a grade of 3300F.
Example 1
The high-strength and high-thermal-stability poly (4-methyl-1-pentene) microporous membrane is characterized by being prepared from the following raw materials in parts by weight: 60 parts of poly-4-methyl-1-pentene, 3 parts of acrylic acid modified fluconazole, 8 parts of 4-chloromethyl styrene modified 4-fluorophenyl methyl imino diacetate and 15 parts of high-density polyethylene.
The preparation method of the acrylic acid modified fluconazole comprises the following steps: adding acrylic acid, fluconazole, 4-dimethylaminopyridine and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into an organic solvent, refluxing and stirring at 30 ℃ for reaction for 4 hours, then performing rotary evaporation to remove the solvent, washing with water for 3 times, and then performing rotary evaporation to remove water to obtain acrylic acid modified fluconazole; the molar ratio of the acrylic acid to the fluconazole to the organic solvent to the 4-dimethylaminopyridine to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is 1:1:0.4:1: 8; the organic solvent is methanol.
The preparation method of the 4-chloromethyl styrene modified 4-fluorophenyl methyl imino diacetate comprises the following steps: adding 4-chloromethylstyrene, 4-fluorophenylboronic acid methyl imino diacetate and an alkaline catalyst into acetonitrile, stirring and reacting for 5 hours at 30 ℃, filtering to remove insoluble substances, and performing rotary evaporation to remove the acetonitrile to obtain 4-chloromethylstyrene modified 4-fluorophenylboronic acid methyl imino diacetate; the molar ratio of the 4-chloromethyl styrene to the 4-fluorophenylboronic acid methyl imino diacetate to the basic catalyst to the acetonitrile is 1:1:0.8: 8; the alkaline catalyst is sodium hydroxide.
The preparation method of the poly 4-methyl-1-pentene microporous membrane with high strength and high thermal stability is characterized by comprising the following steps: uniformly mixing the raw materials in parts by weight to obtain a mixture, adding the mixture into a double-screw extruder for melt extrusion, performing casting film forming, sequentially performing biaxial tension, heat setting, radiation grafting crosslinking, washing with ethanol, and drying to obtain a high-strength and high-heat-stability poly 4-methyl-1-pentene microporous film; the melt extrusion temperature is 300 ℃; the magnification of the biaxial stretching is 5 multiplied by 10; the heat setting temperature is 120 ℃, and the setting time is 5 min. The radiation grafting crosslinking is carried out in nitrogen atmosphere, the radiation energy of the radiation grafting crosslinking is 5MeV, and the radiation dose is 80 KGy.
Example 2
The high-strength and high-thermal-stability poly (4-methyl-1-pentene) microporous membrane is characterized by being prepared from the following raw materials in parts by weight: 63 parts of poly-4-methyl-1-pentene, 3.5 parts of acrylic acid modified fluconazole, 10 parts of 4-chloromethyl styrene modified 4-fluorophenyl methyl imino diacetate and 17 parts of high-density polyethylene.
The preparation method of the acrylic acid modified fluconazole comprises the following steps: adding acrylic acid, fluconazole, 4-dimethylaminopyridine and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into an organic solvent, carrying out reflux stirring reaction for 4.5 hours at the temperature of 35 ℃, then carrying out rotary evaporation to remove the solvent, washing for 4 times with water, and then carrying out rotary evaporation to remove water to obtain acrylic acid modified fluconazole; the molar ratio of the acrylic acid to the fluconazole to the organic solvent to the 4-dimethylaminopyridine to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is 1:1:0.45:1: 10; the organic solvent is ethanol.
The preparation method of the 4-chloromethyl styrene modified 4-fluorophenyl methyl imino diacetate comprises the following steps: adding 4-chloromethylstyrene, 4-fluorophenylboronic acid methyl imino diacetate and an alkaline catalyst into acetonitrile, stirring and reacting for 6 hours at 32 ℃, filtering to remove insoluble substances, and performing rotary evaporation to remove the acetonitrile to obtain 4-chloromethylstyrene modified 4-fluorophenylboronic acid methyl imino diacetate; the molar ratio of the 4-chloromethyl styrene to the 4-fluorophenylboronic acid methyl imino diacetate to the basic catalyst to the acetonitrile is 1:1:0.9: 10; the alkaline catalyst is sodium carbonate.
The preparation method of the poly 4-methyl-1-pentene microporous membrane with high strength and high thermal stability is characterized by comprising the following steps: uniformly mixing the raw materials in parts by weight to obtain a mixture, adding the mixture into a double-screw extruder for melt extrusion, performing casting film forming, sequentially performing biaxial tension, heat setting, radiation grafting crosslinking, washing with ethanol, and drying to obtain a high-strength and high-heat-stability poly 4-methyl-1-pentene microporous film; the melt extrusion temperature is 320 ℃; the magnification of the biaxial stretching is 6 multiplied by 12; the heat setting temperature is 130 ℃, and the setting time is 7 min; the radiation grafting crosslinking is carried out in nitrogen atmosphere, the radiation energy of the radiation grafting crosslinking is 8MeV, and the radiation dose is 120 KGy.
Example 3
The high-strength and high-thermal-stability poly (4-methyl-1-pentene) microporous membrane is characterized by being prepared from the following raw materials in parts by weight: 65 parts of poly-4-methyl-1-pentene, 4 parts of acrylic acid modified fluconazole, 12 parts of 4-chloromethyl styrene modified 4-fluorophenyl methyl imino diacetate and 20 parts of high-density polyethylene.
The preparation method of the acrylic acid modified fluconazole comprises the following steps: adding acrylic acid, fluconazole, 4-dimethylaminopyridine and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into an organic solvent, refluxing and stirring at 40 ℃ for reaction for 5 hours, then performing rotary evaporation to remove the solvent, washing with water for 5 times, and then performing rotary evaporation to remove water to obtain acrylic acid modified fluconazole; the molar ratio of the acrylic acid to the fluconazole to the organic solvent to the 4-dimethylaminopyridine to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is 1:1:0.5:1: 12; the organic solvent is isopropanol.
The preparation method of the 4-chloromethyl styrene modified 4-fluorophenyl methyl imino diacetate comprises the following steps: adding 4-chloromethylstyrene, 4-fluorophenylboronic acid methyl imino diacetate and an alkaline catalyst into acetonitrile, stirring and reacting for 6.5 hours at 35 ℃, filtering to remove insoluble substances, and performing rotary evaporation to remove the acetonitrile to obtain 4-chloromethylstyrene modified 4-fluorophenylboronic acid methyl imino diacetate; the molar ratio of the 4-chloromethyl styrene to the 4-fluorophenylboronic acid methyl imino diacetate to the basic catalyst to the acetonitrile is 1:1:1: 11; the alkaline catalyst is potassium hydroxide.
The preparation method of the poly 4-methyl-1-pentene microporous membrane with high strength and high thermal stability is characterized by comprising the following steps: uniformly mixing the raw materials in parts by weight to obtain a mixture, adding the mixture into a double-screw extruder for melt extrusion, performing casting film forming, sequentially performing biaxial tension, heat setting, radiation grafting crosslinking, washing with ethanol, and drying to obtain a high-strength and high-heat-stability poly 4-methyl-1-pentene microporous film; the melt extrusion temperature is 335 ℃; the magnification of the biaxial stretching is 7 multiplied by 13; the heat setting temperature is 145 ℃, and the setting time is 9 min; the radiation grafting crosslinking is carried out in nitrogen atmosphere, the radiation energy of the radiation grafting crosslinking is 13MeV, and the radiation dose is 180 KGy.
Example 4
The high-strength and high-thermal-stability poly (4-methyl-1-pentene) microporous membrane is characterized by being prepared from the following raw materials in parts by weight: 68 parts of poly-4-methyl-1-pentene, 4.5 parts of acrylic acid modified fluconazole, 8-15 parts of 4-chloromethyl styrene modified 4-fluorophenyl methyl imino diacetate and 23 parts of high-density polyethylene.
The preparation method of the acrylic acid modified fluconazole comprises the following steps: adding acrylic acid, fluconazole, 4-dimethylaminopyridine and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into an organic solvent, carrying out reflux stirring reaction at 48 ℃ for 5.5 hours, then carrying out rotary evaporation to remove the solvent, washing with water for 6 times, and then carrying out rotary evaporation to remove water to obtain acrylic acid modified fluconazole; the molar ratio of the acrylic acid to the fluconazole to the organic solvent to the 4-dimethylaminopyridine to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is 1:1:0.55:1: 14; the organic solvent is formed by mixing methanol, ethanol and isopropanol according to the mass ratio of 1:3: 2.
The preparation method of the 4-chloromethyl styrene modified 4-fluorophenyl methyl imino diacetate comprises the following steps: adding 4-chloromethylstyrene, 4-fluorophenylboronic acid methyl imino diacetate and an alkaline catalyst into acetonitrile, stirring and reacting for 7.5 hours at 38 ℃, filtering to remove insoluble substances, and performing rotary evaporation to remove the acetonitrile to obtain 4-chloromethylstyrene modified 4-fluorophenylboronic acid methyl imino diacetate; the molar ratio of the 4-chloromethyl styrene to the 4-fluorophenylboronic acid methyl imino diacetate to the basic catalyst to the acetonitrile is 1:1:1.1: 13; the alkaline catalyst is prepared by mixing sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate according to the mass ratio of 1:3:2: 3.
The preparation method of the poly 4-methyl-1-pentene microporous membrane with high strength and high thermal stability is characterized by comprising the following steps: uniformly mixing the raw materials in parts by weight to obtain a mixture, adding the mixture into a double-screw extruder for melt extrusion, performing casting film forming, sequentially performing biaxial tension, heat setting, radiation grafting crosslinking, washing with ethanol, and drying to obtain a high-strength and high-heat-stability poly 4-methyl-1-pentene microporous film; the melt extrusion temperature is 340 ℃; the magnification of the biaxial stretching is 7 multiplied by 14; the heat setting temperature is 145 ℃, and the setting time is 9 min; the radiation grafting crosslinking is carried out in nitrogen atmosphere, the radiation energy of the radiation grafting crosslinking is 13MeV, and the radiation dose is 180 KGy.
Example 5
The high-strength and high-thermal-stability poly (4-methyl-1-pentene) microporous membrane is characterized by being prepared from the following raw materials in parts by weight: 70 parts of poly-4-methyl-1-pentene, 5 parts of acrylic acid modified fluconazole, 15 parts of 4-chloromethyl styrene modified 4-fluorophenyl methyl imino diacetate and 25 parts of high-density polyethylene.
The preparation method of the acrylic acid modified fluconazole comprises the following steps: adding acrylic acid, fluconazole, 4-dimethylaminopyridine and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into an organic solvent, refluxing and stirring at 50 ℃ for reaction for 6 hours, then performing rotary evaporation to remove the solvent, washing with water for 6 times, and then performing rotary evaporation to remove water to obtain acrylic acid modified fluconazole; the molar ratio of the acrylic acid to the fluconazole to the organic solvent to the 4-dimethylaminopyridine to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is 1:1:0.6:1: 15; the organic solvent is methanol.
The preparation method of the 4-chloromethyl styrene modified 4-fluorophenyl methyl imino diacetate comprises the following steps: adding 4-chloromethylstyrene, 4-fluorophenylboronic acid methyl imino diacetate and an alkaline catalyst into acetonitrile, stirring and reacting for 5-8 hours at 30-40 ℃, filtering to remove insoluble substances, and performing rotary evaporation to remove acetonitrile to obtain 4-chloromethylstyrene modified 4-fluorophenylboronic acid methyl imino diacetate; the molar ratio of the 4-chloromethyl styrene to the 4-fluorophenylboronic acid methyl imino diacetate to the basic catalyst to the acetonitrile is 1:1:1.2: 14; the alkaline catalyst is sodium hydroxide.
The preparation method of the poly 4-methyl-1-pentene microporous membrane with high strength and high thermal stability is characterized by comprising the following steps: uniformly mixing the raw materials in parts by weight to obtain a mixture, adding the mixture into a double-screw extruder for melt extrusion, performing casting film forming, sequentially performing biaxial tension, heat setting, radiation grafting crosslinking, washing with ethanol, and drying to obtain a high-strength and high-heat-stability poly 4-methyl-1-pentene microporous film; the melt extrusion temperature is 350 ℃; the magnification of the biaxial stretching is 8 multiplied by 15; the heat setting temperature is 150 ℃, and the setting time is 10 min; the radiation grafting crosslinking is carried out in nitrogen atmosphere, the radiation energy of the radiation grafting crosslinking is 15MeV, and the radiation dose is 200 KGy.
Comparative example 1
The invention provides a high-strength and high-thermal-stability poly (4-methyl-1-pentene) microporous membrane, the formula and the preparation method of which are similar to those of example 1, except that acrylic acid is not added to modify fluconazole.
Comparative example 2
The invention provides a high-strength and high-thermal-stability poly (4-methyl-1-pentene) microporous membrane, the formula and the preparation method are similar to those of example 1, except that 4-chloromethyl styrene modified 4-fluorophenyl methyl imino diacetate is not added.
Comparative example 3
The invention provides a high-strength and high-thermal-stability poly (4-methyl-1-pentene) microporous membrane, the formula and the preparation method of which are similar to those of example 1, except that high-density polyethylene is not added.
In order to further illustrate the beneficial technical effects of the embodiments of the present invention, the high-strength and high-thermal stability poly-4-methyl-1-pentene microporous membrane of each example is subjected to a relevant performance test according to the current relevant national standard of China, and the test results are shown in table 1.
TABLE 1
Figure BDA0002877891120000111
As can be seen from Table 1, the high-strength and high-thermal stability microporous poly-4-methyl-1-pentene film disclosed in the examples of the present invention has excellent mechanical properties, liquid retention properties and thermal stability, which are the result of the synergistic effect of the raw materials.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. The high-strength and high-thermal-stability poly (4-methyl-1-pentene) microporous membrane is characterized by being prepared from the following raw materials in parts by weight: 60-70 parts of poly-4-methyl-1-pentene, 3-5 parts of acrylic acid modified fluconazole, 8-15 parts of 4-chloromethyl styrene modified 4-fluorophenyl methyl imino diacetate and 15-25 parts of high-density polyethylene.
2. The high strength, high thermal stability poly 4-methyl-1-pentene microporous membrane of claim 1, wherein said acrylic modified fluconazole prepared by said process comprises the steps of: adding acrylic acid, fluconazole, 4-dimethylaminopyridine and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into an organic solvent, carrying out reflux stirring reaction for 4-6 hours at the temperature of 30-50 ℃, then carrying out rotary evaporation to remove the solvent, washing for 3-6 times by using water, and then carrying out rotary evaporation to remove water to obtain the acrylic acid modified fluconazole.
3. The high strength, high thermal stability poly 4-methyl-1-pentene microporous membrane of claim 2, wherein the molar ratio of acrylic acid, fluconazole, 4-dimethylaminopyridine, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, organic solvent is 1:1 (0.4-0.6) to 1 (8-15).
4. The high strength, high thermal stability poly 4-methyl-1-pentene microporous membrane of claim 2, wherein said organic solvent is at least one of methanol, ethanol, isopropanol.
5. The microporous high-strength and high-thermal-stability poly (4-methyl-1-pentene) membrane according to claim 1, wherein the preparation method of the 4-chloromethylstyrene modified methyl imino diacetate 4-fluorophenylborate comprises the following steps: adding 4-chloromethylstyrene, 4-fluorophenylboronic acid methyl imino diacetate and an alkaline catalyst into acetonitrile, stirring and reacting for 5-8 hours at 30-40 ℃, filtering to remove insoluble substances, and performing rotary evaporation to remove acetonitrile to obtain the 4-chloromethylstyrene modified 4-fluorophenylboronic acid methyl imino diacetate.
6. The high strength, high thermal stability poly (4-methyl-1-pentene) microporous membrane of claim 5, wherein the molar ratio of 4-chloromethylstyrene, 4-fluorophenylboronic acid methyl imino diacetate, basic catalyst, acetonitrile is 1:1 (0.8-1.2) to (8-14).
7. The high strength, high thermal stability poly 4-methyl-1-pentene microporous membrane of claim 5, wherein said basic catalyst is at least one of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate.
8. The high strength, high thermal stability poly-4-methyl-1-pentene microporous membrane of claim 1, wherein said poly-4-methyl-1-pentene is poly-4-methyl-1-pentene
Figure FDA0002877891110000021
MX004 poly-4-methyl-1-pentene; the high density polyethylene is a high density polyethylene having a grade of 3300F.
9. A method of making a high strength, high thermal stability poly 4-methyl-1-pentene microporous membrane according to any of claims 1 to 8, comprising the steps of: the preparation method comprises the steps of uniformly mixing the raw materials in parts by weight to obtain a mixture, adding the mixture into a double-screw extruder for melt extrusion, performing casting film forming, sequentially performing biaxial tension, heat setting, radiation grafting crosslinking, washing with ethanol, and drying to obtain the high-strength and high-thermal-stability poly 4-methyl-1-pentene microporous film.
10. The method for preparing a high-strength and high-thermal-stability poly (4-methyl-1-pentene) microporous membrane according to claim 9, wherein the melt extrusion temperature is 300-350 ℃; the magnification of the biaxial stretching is (5-8) × (10-15); the temperature of the heat setting is 120-150 ℃, and the setting time is 5-10 min; the radiation grafting crosslinking is carried out in nitrogen atmosphere, the radiation energy of the radiation grafting crosslinking is 5MeV-15MeV, and the radiation dose is 80KGy-200 KGy.
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