CN114409885B - Low-extraction motor film and preparation method thereof - Google Patents
Low-extraction motor film and preparation method thereof Download PDFInfo
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- CN114409885B CN114409885B CN202210146422.4A CN202210146422A CN114409885B CN 114409885 B CN114409885 B CN 114409885B CN 202210146422 A CN202210146422 A CN 202210146422A CN 114409885 B CN114409885 B CN 114409885B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6826—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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Abstract
The invention discloses a low extraction motor film and a preparation method thereof, comprising the following steps: and (3) carrying out esterification reaction on raw materials terephthalic acid and ethylene glycol, and then carrying out polycondensation reaction in the presence of a composite catalyst to obtain polyester resin, wherein the polyester resin is subjected to extrusion slicing, melt extrusion, casting and biaxial stretching film formation to obtain the low-extraction motor film, the composite catalyst is a rare earth MOFs grafted tributyl tin pyridine sulfonate composite, and the mass ratio of terephthalic acid to the catalyst is 100:0.01-0.10. The preparation method of the low extraction motor film effectively reduces the content of the oligomer in the motor polyester film, reduces the precipitation of the oligomer in the motor operation process, and prolongs the service life of the motor.
Description
Technical Field
The invention relates to the technical field of membrane materials, in particular to a low extraction motor membrane and a preparation method thereof.
Background
With the increasing living standard, home appliances such as air conditioners, refrigerators and freezers are widely used. As an important component of home appliances, a motor is required to maintain stable operation for a long period of time under high temperature and insulation conditions. Therefore, biaxially oriented polyester films having high properties such as high long-term heat resistance index and excellent insulation properties are generally used for heat-resistant insulated motors.
However, in the polyester synthesis process, the oligomer is a main byproduct generated in the polyester polymerization process and the degradation process, and the main component is a cyclic trimer. The existence of the oligomers can bring a certain adverse effect to the biaxially oriented film forming, and in the film forming process, the oligomers can adhere to the film to cause inner film pollution, so that fog spots are formed on the surface of the film to influence the quality of the film. In addition, when the polyester film is applied to motor operation, the oligomers can be slowly separated out in the motor operation process, so that the motor is blocked and insulation failure is caused. Meanwhile, the operation temperature of the motor is high, and the precipitation of the oligomer caused by the heating treatment is more serious. Therefore, the high temperature resistance of the motor polyester film is required, and the oligomer content in the polyester film is also required to be controlled within a certain range, namely the low extraction polyester film. Therefore, research to reduce the oligomer content of polyester films has also become an important point of research in the industry.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a low-extraction motor film and a preparation method thereof, so that the content of oligomers in a motor polyester film can be effectively reduced, the precipitation of the oligomers in the motor operation process is reduced, and the service life of the motor is prolonged.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method of preparing a low extraction motor film, the method comprising the steps of: and (3) carrying out esterification reaction on raw materials terephthalic acid and ethylene glycol, and then carrying out polycondensation reaction in the presence of a composite catalyst to obtain polyester resin, wherein the polyester resin is subjected to extrusion slicing, melt extrusion, casting and biaxial stretching film formation to obtain the low-extraction motor film, the composite catalyst is a rare earth MOFs grafted tributyl tin pyridine sulfonate composite, and the mass ratio of terephthalic acid to the catalyst is 100:0.01-0.10. The rare earth MOFs grafted tributyltin pyridine sulfonate serving as a composite catalyst is used as a catalyst and a thermal oxygen stabilizer in polymerization production, so that thermal degradation of polyester in the film forming process can be reduced, the content of low extract in a motor film can be effectively reduced, and the influence of biaxial stretching film forming is reduced.
Preferably, the preparation method of the composite catalyst comprises the following steps: dissolving tributyl tin pyridine sulfonate in tetrahydrofuran, adding modified rare earth MOFs, reacting for 24-48 h at 60-90 ℃, filtering after the reaction is finished, washing a product with tetrahydrofuran, and vacuum drying for 12-24 h at 90-100 ℃ to obtain a rare earth MOFs grafted tributyl tin pyridine sulfonate compound, wherein the mass volume ratio of tributyl tin pyridine sulfonate to tetrahydrofuran is 0.05-0.15 g/mL, and the mass ratio of the modified rare earth MOFs to tributyl tin pyridine sulfonate is 1.5-3: 1.
preferably, the preparation method of the modified rare earth MOFs comprises the following steps: adding rare earth MOFs and a silane coupling agent 3-bromopropyl trimethoxy silane into ethyl acetate, reacting for 6-48 h at 70-90 ℃, filtering after the reaction is finished, washing a product with ethyl acetate, and vacuum drying for 12-24 h at 90-100 ℃ to obtain modified rare earth MOFs, wherein the mass ratio of the rare earth MOFs to the 3-bromopropyl trimethoxy silane is 1.5-3: 1.
preferably, the preparation method of the rare earth MOFs comprises the following steps: dissolving lanthanum nitrate and 2,2' -dihydroxyl-1, 1' -binaphthyl-3, 3' -dicarboxylic acid in a mixed solution, stirring for 25-35 min, then filling the mixed solution into an autoclave, carrying out hydrothermal reaction at 90-110 ℃ for 18-24 h, cooling to room temperature, washing with methanol, boiling in boiling methanol for 10-20 h, and vacuum drying to obtain rare earth MOFs, wherein the mixed solution comprises the following components in percentage by mass of 15-30: 1:1 dimethyl sulfoxide, 1-propanol and deionized water, wherein the mass volume ratio of lanthanum nitrate to the mixed solution is 0.03-0.05 g/mL, and the molar ratio of lanthanum nitrate to 2,2' -dihydroxy-1, 1' -binaphthyl-3, 3' -dicarboxylic acid is 2:1. 2,2' -dihydroxy-1, 1' -binaphthyl-3, 3' -dicarboxylic acid is used as an organic ligand of a Metal Organic Frameworks (MOFs), and the carboxyl functional groups carried by the organic ligand and rare earth lanthanum ions are utilized to carry out self-assembly to form a network structure.
Preferably, the preparation method of the tributyltin pyridine sulfonate comprises the following steps: adding 4- (2-bromoethyl) pyridine and tributyltin sulfamate into toluene, stirring and refluxing at 50-80 ℃ until a yellowish solid precipitate is obtained, vacuum filtering and washing the yellowish solid precipitate, and vacuum drying at 60-80 ℃ for 6-24 hours to obtain tributyltin pyridine sulfonate, wherein the molar ratio of 4- (2-bromoethyl) pyridine, tributyltin sulfamate and toluene is 1:1:3 to 10.
The rare earth MOFs grafted tributyltin pyridine sulfonate of the composite catalyst plays a key role in preparing a high-performance motor film. Rare earth MOFs are metal organic framework materials containing polyhydroxy structures that readily react with silane coupling agents to yield modified MOFs. The bromo group on the modified MOFs is tightly connected with tributyltin pyridine sulfonate through a chemical bond. Therefore, the rare earth MOFs grafted tributyltin pyridine sulfonate of the composite catalyst has the advantages of good porosity, low density, difficult inactivation, easy separation, environmental friendliness and the like, simultaneously brings about a huge specific surface area, increases active sites, and fully exerts the catalytic performance of the catalyst.
Preferably, the specific steps of the esterification reaction are as follows: 100 parts of terephthalic acid, 60-65 parts of ethylene glycol and 0.1-0.2 part of cobalt acetate are uniformly mixed, the reaction temperature of the esterification reaction is set to be 200-250 ℃, the reaction pressure is set to be 0.1-0.2 MPa, the water yield of the esterification reaction is higher than 95% of the water yield of the theoretical complete reaction of terephthalic acid and ethylene glycol, and the reaction is stopped. The addition of cobalt acetate is not only beneficial to the esterification reaction, but also can reduce the etherification of glycol in the polycondensation stage as an ether inhibitor.
Preferably, the specific steps of the polycondensation reaction are: and adding 10-15 parts of a third monomer into the materials after the esterification reaction, wherein the adding amount of the composite catalyst is 0.01-0.1 part, the polycondensation reaction temperature is 240-270 ℃, the pressure is 100-1000 Pa, the reaction time is 30-60 min, and the polyester resin is obtained after the reaction is finished and cooled.
Preferably, the third monomer is 1-fluoro-2, 3-propanediol and/or 2, 2-difluoro-1, 3-propanediol. The addition of the third monomer fluorine-containing propylene glycol increases the stability of the polyester resin structure and helps to inhibit the hydrolysis process of the high molecular structure of the polyester resin, thereby reducing the content of oligomers in the polyester resin.
Preferably, methyl cage type silsesquioxane, dibenzo-24-crown ether-8, nano calcium carbonate and polyester resin are added in the melt extrusion process for co-melt extrusion, and the melt temperature is 275-285 ℃ and the melt time is 3-7 min. The added methyl cage type silsesquioxane and dibenzo-24-crown ether-8 further improve the thermal stability of the polyester resin in the high-temperature melt extrusion process and inhibit the hydrolysis and degradation processes of the polyester resin; the nano calcium carbonate has other reinforcing and lubricating effects.
Another aspect of the present invention is to provide a low extraction motor film, which is prepared by using the preparation method of the low extraction motor film.
The invention has the beneficial effects that:
according to the preparation method of the low extraction motor film, the rare earth MOFs grafted tributyltin pyridine sulfonate is used as a composite catalyst, so that the content of oligomers in the motor polyester film is effectively reduced, the precipitation of the oligomers in the motor operation process is reduced, and the service life of the motor is prolonged.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art.
Example 1
The preparation method of the low extraction motor film of the embodiment comprises the following steps: and (3) carrying out esterification reaction on raw materials terephthalic acid and ethylene glycol, and then carrying out polycondensation reaction in the presence of a composite catalyst to obtain polyester resin, wherein the polyester resin is subjected to extrusion slicing, melt extrusion, casting and biaxially oriented film forming to obtain the low extraction motor film, the composite catalyst is a rare earth MOFs grafted tributyltin pyridine sulfonate composite, and the mass ratio of the terephthalic acid to the catalyst is 100:0.01.
The preparation method of the composite catalyst comprises the following steps: dissolving tributyl tin pyridine sulfonate in tetrahydrofuran, adding modified rare earth MOFs, reacting at 60 ℃ for 48 hours, filtering after the reaction is finished, washing a product with tetrahydrofuran, and vacuum drying at 90 ℃ for 12 hours to obtain a rare earth MOFs grafted tributyl tin pyridine sulfonate compound, wherein the mass-volume ratio of tributyl tin pyridine sulfonate to tetrahydrofuran is 0.05g/mL, and the mass ratio of the modified rare earth MOFs to tributyl tin pyridine sulfonate is 1.5:1.
the preparation method of the modified rare earth MOFs comprises the following steps: adding rare earth MOFs and a silane coupling agent 3-bromopropyl trimethoxy silane into ethyl acetate, reacting for 12 hours at 70 ℃, filtering after the reaction is finished, washing a product with ethyl acetate, and vacuum drying for 24 hours at 100 ℃ to obtain modified rare earth MOFs, wherein the mass ratio of the rare earth MOFs to the 3-bromopropyl trimethoxy silane is 2:1.
the preparation method of the rare earth MOFs comprises the following steps: dissolving lanthanum nitrate and 2,2' -dihydroxyl-1, 1' -binaphthyl-3, 3' -dicarboxylic acid in a mixed solution, stirring for 25min, filling into an autoclave, carrying out hydrothermal reaction at 90 ℃ for 18h, cooling to room temperature, washing with methanol, boiling in boiling methanol for 10h, and carrying out vacuum drying to obtain the rare earth MOFs, wherein the mixed solution comprises the following components in percentage by mass: 1:1, 1-propanol and deionized water, wherein the mass volume ratio of lanthanum nitrate to the mixed solution is 0.03g/mL, and the molar ratio of lanthanum nitrate to 2,2' -dihydroxy-1, 1' -binaphthyl-3, 3' -dicarboxylic acid is 2:1.
the preparation method of the tributyltin pyridine sulfonate comprises the following steps: adding 4- (2-bromoethyl) pyridine and tributyltin sulfamate into toluene, stirring and refluxing at 50 ℃ until a yellowish solid precipitate is obtained, vacuum filtering and washing the yellowish solid precipitate, and vacuum drying at 60 ℃ for 24 hours to obtain tributyltin pyridine sulfonate, wherein the molar ratio of 4- (2-bromoethyl) pyridine, tributyltin sulfamate and toluene is 1:1:3.
the specific steps of the esterification reaction are as follows: 100 parts of terephthalic acid, 60 parts of ethylene glycol and 0.1 part of cobalt acetate are uniformly mixed, the reaction temperature of the esterification reaction is set to be 200 ℃, the reaction pressure is set to be 0.1MPa, the water yield of the esterification reaction is higher than 95% of the theoretical complete reaction water yield of the terephthalic acid and the ethylene glycol, and the reaction is stopped.
The specific steps of the polycondensation reaction are as follows: and adding 10-15 parts of third monomer 1-fluoro-2, 3-propanediol into the material after the esterification reaction, wherein the adding amount of the composite catalyst is 0.01 part, the polycondensation reaction temperature is 240 ℃, the pressure is 500Pa, the reaction time is 30min, and the polyester resin is obtained after cooling when the intrinsic viscosity reaches 0.686dl/g reaction.
In the process of melt extrusion, methyl cage type silsesquioxane, dibenzo-24-crown ether-8 and nano calcium carbonate are added for co-melt extrusion with polyester resin, wherein the mass ratio of the methyl cage type silsesquioxane to the dibenzo-24-crown ether-8 to the nano calcium carbonate to the polyester resin is 7:5:1:100, the melting temperature was set at 285℃and the melting time was 3min. The working conditions of the cast sheet are as follows: cooling the polyester melt by a cold drum with the surface temperature of 15 ℃, and forming a cast sheet with the crystallinity of less than 5% by a high-voltage electrostatic film-attaching system; the working conditions of the biaxial stretching film forming are as follows: the cast sheet is longitudinally stretched along the length direction, the temperature of a preheating roller is controlled at 85 ℃, the stretching temperature is controlled at 125 ℃, the cooling temperature is controlled at 20 ℃, and the stretching ratio is controlled at 3.5 times; then the film after longitudinal stretching is led into a heated transverse stretching roller set, the temperature of a preheating roller is controlled at 110 ℃, the stretching temperature is controlled at 135 ℃, the stretching ratio is controlled at 3.5 times, after transverse stretching is finished, the film is shaped at the shaping temperature of 230 ℃ and then gradually cooled to normal temperature, and the crystallinity of the polyester film is controlled to be more than 30%; finally, the low extraction motor film is obtained, and the film thickness is 35 mu m.
Example 2
The preparation method of the low extraction motor film of the embodiment comprises the following steps: and (3) carrying out esterification reaction on raw materials terephthalic acid and ethylene glycol, and then carrying out polycondensation reaction in the presence of a composite catalyst to obtain polyester resin, wherein the polyester resin is subjected to extrusion slicing, melt extrusion, casting and biaxial stretching film formation to obtain the low-extraction motor film, the composite catalyst is a rare earth MOFs grafted tributyl tin pyridine sulfonate composite, and the mass ratio of the terephthalic acid to the catalyst is 100:0.05.
The preparation method of the composite catalyst comprises the following steps: dissolving tributyl tin pyridine sulfonate in tetrahydrofuran, adding modified rare earth MOFs, reacting for 36 hours at 70 ℃, filtering after the reaction is finished, washing a product with tetrahydrofuran, and vacuum drying for 24 hours at 100 ℃ to obtain a rare earth MOFs grafted tributyl tin pyridine sulfonate compound, wherein the mass-volume ratio of tributyl tin pyridine sulfonate to tetrahydrofuran is 0.1g/mL, and the mass ratio of the modified rare earth MOFs to tributyl tin pyridine sulfonate is 2:1.
the preparation method of the modified rare earth MOFs comprises the following steps: adding rare earth MOFs and a silane coupling agent 3-bromopropyl trimethoxy silane into ethyl acetate, reacting for 12 hours at 80 ℃, filtering after the reaction is finished, washing a product with ethyl acetate, and vacuum drying for 12 hours at 90 ℃ to obtain modified rare earth MOFs, wherein the mass ratio of the rare earth MOFs to the 3-bromopropyl trimethoxy silane is 3:1.
the preparation method of the rare earth MOFs comprises the following steps: dissolving lanthanum nitrate and 2,2' -dihydroxyl-1, 1' -binaphthyl-3, 3' -dicarboxylic acid in a mixed solution, stirring for 35min, filling into an autoclave, carrying out hydrothermal reaction at 110 ℃ for 24h, cooling to room temperature, washing with methanol, boiling in boiling methanol for 20h, and carrying out vacuum drying to obtain the rare earth MOFs, wherein the mixed solution comprises the following components in percentage by mass: 1:1, 1-propanol and deionized water, wherein the mass volume ratio of lanthanum nitrate to the mixed solution is 0.04g/mL, and the molar ratio of lanthanum nitrate to 2,2' -dihydroxy-1, 1' -binaphthyl-3, 3' -dicarboxylic acid is 2:1.
the preparation method of the tributyltin pyridine sulfonate comprises the following steps: adding 4- (2-bromoethyl) pyridine and tributyltin sulfamate into toluene, stirring and refluxing at 80 ℃ until a yellowish solid precipitate is obtained, vacuum filtering and washing the yellowish solid precipitate, and vacuum drying at 60 ℃ for 24 hours to obtain tributyltin pyridine sulfonate, wherein the molar ratio of 4- (2-bromoethyl) pyridine, tributyltin sulfamate and toluene is 1:1:6.
the specific steps of the esterification reaction are as follows: 100 parts of terephthalic acid, 62 parts of ethylene glycol and 0.15 part of cobalt acetate are uniformly mixed, the reaction temperature of the esterification reaction is set to be 220 ℃, the reaction pressure is set to be 0.15MPa, the water yield of the esterification reaction is higher than 95% of the theoretical complete reaction water yield of the terephthalic acid and the ethylene glycol, and the reaction is stopped.
The specific steps of the polycondensation reaction are as follows: and adding 12 parts of a third monomer 2, 2-difluoro-1, 3-propylene glycol into the material after the esterification reaction, wherein the adding amount of the composite catalyst is 0.05 part, the polycondensation reaction temperature is 250 ℃, the pressure is 700Pa, the reaction time is 40min, and the polyester resin is obtained after cooling when the intrinsic viscosity reaches 0.661dl/g and the reaction is finished.
The process and working conditions of the polyester resin extrusion sheet, melt extrusion, casting sheet and biaxially oriented film were the same as those of example 1, and the film thickness of the obtained low extraction motor film was 40. Mu.m.
Example 3
The preparation method of the low extraction motor film of the embodiment comprises the following steps: and (3) carrying out esterification reaction on raw materials terephthalic acid and ethylene glycol, and then carrying out polycondensation reaction in the presence of a composite catalyst to obtain polyester resin, wherein the polyester resin is subjected to extrusion slicing, melt extrusion, casting and biaxially oriented film forming to obtain the low extraction motor film, the composite catalyst is a rare earth MOFs grafted tributyltin pyridine sulfonate composite, and the mass ratio of the terephthalic acid to the catalyst is 100:0.10.
The preparation method of the composite catalyst comprises the following steps: dissolving tributyl tin pyridine sulfonate in tetrahydrofuran, adding modified rare earth MOFs, reacting for 48 hours at 90 ℃, filtering after the reaction is finished, washing a product with tetrahydrofuran, and vacuum drying for 24 hours at 100 ℃ to obtain a rare earth MOFs grafted tributyl tin pyridine sulfonate compound, wherein the mass-volume ratio of tributyl tin pyridine sulfonate to tetrahydrofuran is 0.15g/mL, and the mass ratio of the modified rare earth MOFs to tributyl tin pyridine sulfonate is 3:1.
the preparation method of the modified rare earth MOFs comprises the following steps: adding rare earth MOFs and a silane coupling agent 3-bromopropyl trimethoxy silane into ethyl acetate, reacting for 48 hours at 90 ℃, filtering after the reaction is finished, washing a product with ethyl acetate, and vacuum drying for 24 hours at 100 ℃ to obtain modified rare earth MOFs, wherein the mass ratio of the rare earth MOFs to the 3-bromopropyl trimethoxy silane is 3:1.
the preparation method of the rare earth MOFs comprises the following steps: dissolving lanthanum nitrate and 2,2' -dihydroxyl-1, 1' -binaphthyl-3, 3' -dicarboxylic acid in a mixed solution, stirring for 35min, filling into an autoclave, carrying out hydrothermal reaction at 110 ℃ for 24h, cooling to room temperature, washing with methanol, boiling in boiling methanol for 20h, and carrying out vacuum drying to obtain the rare earth MOFs, wherein the mixed solution comprises the following components in percentage by mass: 1:1, 1-propanol and deionized water, wherein the mass volume ratio of lanthanum nitrate to the mixed solution is 0.05g/mL, and the molar ratio of lanthanum nitrate to 2,2' -dihydroxy-1, 1' -binaphthyl-3, 3' -dicarboxylic acid is 2:1.
the preparation method of the tributyltin pyridine sulfonate comprises the following steps: adding 4- (2-bromoethyl) pyridine and tributyltin sulfamate into toluene, stirring and refluxing at 80 ℃ until a yellowish solid precipitate is obtained, vacuum filtering and washing the yellowish solid precipitate, and vacuum drying at 70 ℃ for 24 hours to obtain tributyltin pyridine sulfonate, wherein the molar ratio of 4- (2-bromoethyl) pyridine, tributyltin sulfamate and toluene is 1:1:10.
the specific steps of the esterification reaction are as follows: 100 parts of terephthalic acid, 65 parts of ethylene glycol and 0.2 part of cobalt acetate are uniformly mixed, the reaction temperature of the esterification reaction is set to be 250 ℃, the reaction pressure is set to be 0.2MPa, the water yield of the esterification reaction is higher than 95% of the theoretical complete reaction water yield of the terephthalic acid and the ethylene glycol, and the reaction is stopped.
The specific steps of the polycondensation reaction are as follows: and adding 15 parts of third monomer 1-fluoro-2, 3-propanediol into the material after the esterification reaction, wherein the adding amount of the composite catalyst is 0.1 part, the polycondensation reaction temperature is 260 ℃, the pressure is 900Pa, the reaction time is 60min, and the polyester resin is obtained after the cooling after the intrinsic viscosity reaches 0.658dl/g reaction.
The process and working conditions of the polyester resin extrusion sheet, melt extrusion, casting sheet and biaxially oriented film were the same as those of example 1, and the film thickness of the obtained low extraction motor film was 30. Mu.m.
Comparative example 1
The composition of the raw materials and the preparation steps of the preparation method of the low extraction motor film of the comparative example are basically the same as those of the example 1, except that the third monomer 1-fluoro-2, 3-propanediol is not added in the polycondensation reaction process in the preparation method of the comparative example.
Comparative example 2
The composition of the raw materials and the preparation steps of the preparation method of the low extraction motor membrane of the comparative example are basically the same as those of the embodiment 1, except that in the preparation method of the comparative example, the composite catalyst is rare earth MOFs and tributyltin pyridine sulfonate is not grafted.
Comparative example 3
The composition of the raw materials and the preparation steps of the preparation method of the low extraction motor film of the comparative example are basically the same as those of the embodiment 1, except that in the preparation method of the comparative example, methyl cage type silsesquioxane is not added to the raw materials in the process of melt extrusion.
The low extraction motor films prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to performance test, and the performance results thereof are shown in table 1:
TABLE 1
The tensile strength and breakdown voltage were tested according to standard GB/T13542.2-2009, and the heat resistance was tested according to standard GB/T11026-2016.
Oligomer deposition test, using an injection molding machine (DAKUMAR Dekuma 268 TON-650 TON PET special-purpose injection molding machine), obtaining a polyester film (film thickness 20-50 μm) at a polyester resin temperature of 260℃and standing in a dryer at 60℃for one week, and then testing whether or not an oligomer was deposited on the film surface.
The foregoing has shown and described the basic principles, principal 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, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims.
Claims (9)
1. A method for preparing a low extraction motor film, comprising the steps of: the method comprises the steps of carrying out esterification reaction on raw materials of terephthalic acid and ethylene glycol, and then carrying out polycondensation reaction in the presence of a composite catalyst to obtain polyester resin, wherein the polyester resin is subjected to extrusion slicing, melt extrusion, casting and biaxially oriented film forming to obtain the low extraction motor film, the composite catalyst is a rare earth MOFs grafted tributyl tin pyridine sulfonate composite, and the mass ratio of terephthalic acid to the catalyst is 100:0.01-0.10;
the preparation method of the composite catalyst comprises the following steps: dissolving tributyl tin pyridine sulfonate in tetrahydrofuran, adding modified rare earth MOFs, reacting at 60-90 ℃ for 24-48 h, filtering after the reaction, washing the product with tetrahydrofuran, and vacuum drying at 90-100 ℃ for 12-24 h to obtain a rare earth MOFs grafted tributyl tin pyridine sulfonate compound;
the preparation method of the modified rare earth MOFs comprises the following steps: adding rare earth MOFs and a silane coupling agent 3-bromopropyl trimethoxy silane into ethyl acetate, reacting for 6-48 h at 70-90 ℃, filtering after the reaction, washing the product with ethyl acetate, and vacuum drying for 12-24 h at 90-100 ℃ to obtain modified rare earth MOFs;
the preparation method of the rare earth MOFs comprises the following steps: dissolving lanthanum nitrate and 2,2' -dihydroxyl-1, 1' -binaphthyl-3, 3' -dicarboxylic acid in a mixed solution, stirring for 25-35 min, filling into an autoclave, carrying out hydrothermal reaction at 90-110 ℃ for 18-24 h, cooling to room temperature, washing with methanol, boiling in boiling methanol for 10-20 h, and vacuum drying to obtain rare earth MOFs, wherein the mixed solution comprises the following components in percentage by mass of 15-30: 1:1 dimethyl sulfoxide, 1-propanol and deionized water;
the specific steps of the polycondensation reaction are as follows: adding 10-15 parts of a third monomer into the material after the esterification reaction, wherein the third monomer is 1-fluoro-2, 3-propanediol and/or 2, 2-difluoro-1, 3-propanediol;
in the process of melt extrusion, methyl cage type silsesquioxane, dibenzo-24-crown ether-8, nano calcium carbonate and polyester resin are added for co-melt extrusion.
2. The method for preparing a low extraction motor film according to claim 1, wherein the mass-to-volume ratio of tributyltin pyridine sulfonate to tetrahydrofuran is 0.05-0.15 g/mL, and the mass ratio of the modified rare earth MOFs to tributyltin pyridine sulfonate is 1.5-3: 1.
3. the method for preparing a low extraction motor film according to claim 1, wherein the mass ratio of the rare earth MOFs to the 3-bromopropyl trimethoxysilane is 1.5-3: 1.
4. the method for preparing a low extraction motor film according to claim 1, wherein the mass-volume ratio of lanthanum nitrate to the mixed solution is 0.03-0.05 g/mL, and the molar ratio of lanthanum nitrate to 2,2' -dihydroxy-1, 1' -binaphthyl-3, 3' -dicarboxylic acid is 2:1.
5. the method for preparing a low extraction motor film according to claim 1, wherein the method for preparing tributyltin pyridine sulfonate comprises the following steps: adding 4- (2-bromoethyl) pyridine and tributyltin sulfamate into toluene, stirring and refluxing at 50-80 ℃ until a yellowish solid precipitate is obtained, vacuum filtering and washing the yellowish solid precipitate, and vacuum drying at 60-80 ℃ for 6-24 hours to obtain tributyltin pyridine sulfonate, wherein the molar ratio of 4- (2-bromoethyl) pyridine, tributyltin sulfamate and toluene is 1:1:3 to 10.
6. The method for preparing a low extraction motor film according to claim 1, wherein the esterification reaction comprises the following specific steps: 100 parts of terephthalic acid, 60-65 parts of ethylene glycol and 0.1-0.2 part of cobalt acetate are uniformly mixed, the reaction temperature of the esterification reaction is set to be 200-250 ℃, the reaction pressure is set to be 0.1-0.2 MPa, the water yield of the esterification reaction is higher than 95% of the water yield of the theoretical complete reaction of terephthalic acid and ethylene glycol, and the reaction is stopped.
7. The method for preparing a low extraction motor film according to claim 1, wherein the amount of the composite catalyst is 0.01 to 0.1 part, the polycondensation reaction temperature is 240 to 270 ℃, the pressure is 100 to 1000Pa, the reaction time is 30 to 60 minutes, and the polyester resin is obtained after the reaction is completed and cooled.
8. The method for producing a low extraction motor film according to claim 1, wherein the melting temperature is 275 to 285 ℃ and the melting time is 3 to 7min.
9. A low extraction motor film, wherein the motor film is prepared by the method of any one of claims 1 to 8.
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