CN111004479B - PBT/PVDF composite membrane and production process thereof - Google Patents
PBT/PVDF composite membrane and production process thereof Download PDFInfo
- Publication number
- CN111004479B CN111004479B CN201911110148.XA CN201911110148A CN111004479B CN 111004479 B CN111004479 B CN 111004479B CN 201911110148 A CN201911110148 A CN 201911110148A CN 111004479 B CN111004479 B CN 111004479B
- Authority
- CN
- China
- Prior art keywords
- pbt
- parts
- pvdf
- resin
- composite membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a PBT/PVDF composite membrane, which is characterized by being prepared from the following raw materials in parts by weight: 25-35 parts of vinyl sulfonated modified PBT resin, 30-40 parts of PBT resin, 10-15 parts of PVDF resin, 5-10 parts of 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber and 0.5-1.5 parts of initiator. The invention also provides a production process of the PBT/PVDF composite membrane. The PBT/PVDF composite film disclosed by the invention combines the advantages of PBT and PVDF, and has the advantages of good comprehensive performance, excellent impact resistance, heat resistance, chemical corrosion resistance and toughness, high mechanical strength, small molding shrinkage, good weather resistance and water resistance and low preparation cost.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a PBT/PVDF composite membrane and a production process thereof.
Background
In recent years, with the rapid development of science and technology and the industry of plastic products, plastics represented by polybutylene terephthalate (PBT) have attracted much attention. The PBT resin main chain is composed of saturated linear molecules, each repeating unit of which is a rigid benzene ring and flexible fatty alcohol which are connected, and the high geometric regularity and the rigid part of the molecules enable the polymer to have high mechanical strength, outstanding chemical reagent resistance, heat resistance and excellent electrical property; the PBT resin has the advantages of good chemical corrosion resistance, good flexibility, glossy transparent surface, weather resistance, low water absorption and the like, becomes a good after-taste engineering plastic, and is widely applied to the fields of automobiles, electronic and electric products, industrial machinery, polymer alloys, blending industry and the like.
With the expansion of the application range and the increase of the requirements of people on the performance of new materials, the PBT in the prior art can not meet the requirements, because the existing PBT resin generally has the defects of low notch impact strength and large molding shrinkage, in order to improve the performances, the commonly adopted measure is to add various additives into the PBT, however, the addition of a large amount of additives can influence the processing fluidity of the material on one hand, and on the other hand, the compatibility problem between the additives and the PBT base material is easy to cause the outward seepage phenomenon, so that the stability of the material performance is not good, besides, the addition of a large amount of additives can cause the inconsistent transverse and longitudinal shrinkage of the product, so that the product is easy to warp.
Polyvinylidene fluoride (PVDF) is a homopolymer of vinylidene fluoride, a high strength, corrosion resistant material. The material has excellent weather resistance, low permeability to most of gas and liquid, ultraviolet ray and nuclear radiation resistance, heat resistance, corrosion resistance, ageing resistance, high mechanical strength, high impact strength, good processability and long service life, but has poor heat conductivity, high melt viscosity and high price. In addition, due to the low friction coefficient of PVDF, PVDF is not easy to bond during processing, but the compatibility of adhesives adopted in the prior art is poor, namely PVDF films cannot be bonded effectively, or steel plate base layers cannot be bonded effectively, so that products containing PVDF films are poor in structural stability, short in service life, low in toughness, poor in bending resistance, and prone to damage due to slight acting force between layers.
If the advantages of PBT and PVDF are effectively combined, a membrane product with more excellent comprehensive performance can be expected to be developed, and scientific researchers at home and abroad make many attempts and achieve some achievements, but the comprehensive performance of the product in the prior art needs to be further improved due to the compatibility problem of PBT and PVDF.
Therefore, the development of the PBT/PVDF composite membrane with better comprehensive performance is very important, and the PBT/PVDF composite membrane has very important significance for promoting the development of the composite material industry.
Disclosure of Invention
The invention mainly aims to provide the PBT/PVDF composite membrane and the production process thereof, and the process is simple, short in flow, convenient to operate, low in energy consumption, suitable for continuous large-scale production and high in economic value and social value; the prepared PBT/PVDF composite film combines the advantages of PBT and PVDF, and has the advantages of good comprehensive performance, excellent impact resistance, heat resistance, chemical corrosion resistance and toughness, high mechanical strength, small molding shrinkage, good weather resistance and water resistance, and low preparation cost.
In order to achieve the purpose, the invention provides a PBT/PVDF composite membrane, which is characterized by being prepared from the following raw materials in parts by weight: 25-35 parts of vinyl sulfonated modified PBT resin, 30-40 parts of PBT resin, 10-15 parts of PVDF resin, 5-10 parts of 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber and 0.5-1.5 parts of initiator.
Further, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
Further, the preparation method of the 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber comprises the following steps: dispersing the mullite nanofibers in an organic solvent to obtain a dispersion, adding 3-triethoxysilylpropyltrimethylammonium chloride into the dispersion, stirring and reacting at 60-80 ℃ for 6-8 hours, and then removing the organic solvent by rotary evaporation to obtain the 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofibers.
Preferably, the mass ratio of the mullite nano fiber to the organic solvent to the 3-triethoxysilylpropyltrimethylammonium chloride is (3-5): (10-20): 0.4.
Preferably, the organic solvent is one of ethanol, dichloromethane, acetone and tetrahydrofuran.
Preferably, the average diameter of the mullite nanofibers is 300nm, and the preparation method refers to the chinese patent application No. 201910394011.5, example 1, for the pre-preparation.
Further, the preparation method of the vinyl sulfonated modified PBT resin comprises the following steps:
step S1, adding the PBT resin into hexafluoroisopropanol, stirring for 15-30 minutes, then adding chlorosulfonic acid into the hexafluoroisopropanol in an ice bath, stirring for reaction for 1-3 hours, then heating to 40-50 ℃, continuing to stir for reaction for 2-4 hours, then performing rotary evaporation to remove the solvent, washing the product with water for 2-5 times, then washing with ethanol for 3-6 times, and then placing the product in a vacuum drying oven at 80-90 ℃ for drying to constant weight to obtain sulfonated PBT resin;
and step S2, soaking the sulfonated PBT resin prepared in the step S1 in dichloromethane containing 2-vinyl-3H-4-quinazolinone, 4-dimethylaminopyridine and N, N' -dicyclohexylcarbodiimide for 8-12 hours, taking out, washing with water for 3-5 times, washing with ethanol for 3-6 times, and performing rotary evaporation to remove the ethanol to obtain the vinyl sulfonated modified PBT resin.
Preferably, the mass ratio of the PBT resin, the hexafluoroisopropanol and the chlorosulfonic acid in the step S1 is 1 (3-5) to (0.1-0.3).
Preferably, the mass ratio of the sulfonated PBT resin, the 2-vinyl-3H-4-quinazolinone, the 4-dimethylaminopyridine, the N, N' -dicyclohexylcarbodiimide and the dichloromethane in the step S2 is 1:0.2:0.12:0.06 (10-15).
Preferably, the PBT resin is a U.S. tacona 1700A high molecular weight PBT Celanex; the PVDF resin has a weight average molecular weight of 40 ten thousand and is available from Riquzhou Ruihai chemical Co.
The invention also aims to provide a production process of the PBT/PVDF composite membrane, which is characterized by comprising the following steps: uniformly mixing vinyl sulfonated modified PBT resin, PVDF resin, 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nano-fiber and an initiator to form a mixture, adding the mixture into a mixed solvent with the mass 20-30 times that of the mixture, stirring for 10-20 minutes, carrying out ultrasonic treatment for 15-25 minutes, pouring the mixture into a casting film tray, scraping the mixture by using a scraper to form a film, and drying the film at 80-90 ℃ for 4-8 hours to obtain the PBT/PVDF composite film.
Preferably, the mixed solvent is prepared by mixing hexafluoroisopropanol and N, N-dimethylacetamide according to a mass ratio of 5 (2-3).
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) the PBT/PVDF composite membrane disclosed by the invention is simple in production process, short in flow, convenient to operate, low in energy consumption, suitable for continuous large-scale production and high in economic value and social value.
(2) The PBT/PVDF composite film disclosed by the invention overcomes the defects of low notch impact strength and large molding shrinkage of the traditional PBT resin, overcomes the defects of weak structural stability, short service life, low toughness, poor bending resistance, easy damage caused by slight acting force between layers and high cost of the traditional PVDF material, combines the advantages of PBT and PVDF, and has the advantages of good comprehensive performance, excellent impact resistance, heat resistance, chemical corrosion resistance and toughness, high mechanical strength, small molding shrinkage, good weather resistance and water resistance and low preparation cost.
(3) The PBT/PVDF composite membrane disclosed by the invention takes the blending of PBT resin and PVDF resin as a base material, the vinyl sulfonated modified PBT resin is added as a bridging component, the 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber is taken as a reinforcing component, vinyl introduced into the vinyl sulfonated modified PBT resin is generated by a grafting reaction with the PVDF resin in a membrane forming stage, sulfonic groups on the vinyl sulfonated modified PBT resin and quaternary ammonium salt on the 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber are connected together by an ion exchange reaction, the vinyl sulfonated modified PBT resin and the PBT resin have the same main chain structure and good compatibility, and all raw material components form an organic whole with excellent comprehensive performance.
(4) According to the PBT/PVDF composite membrane disclosed by the invention, the 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nano fiber can improve the dispersibility and compatibility of the mullite nano fiber, and the quaternary ammonium salt structure is introduced, so that the antistatic property and antibacterial property of the material can be improved, and the surface activity is improved, so that the PBT/PVDF composite membrane can be better bonded with other base materials, and the service life is prolonged; on one hand, the PBT resin is sulfonated to provide reaction sites for subsequent reaction with quaternary ammonium salt, on the other hand, the addition of sulfonic acid groups can enhance the flame retardance and serve as branched chains, so that the molecular chains have larger spaces, and the toughness and elasticity of the material are improved.
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 PBT resin is American Tycona 1700A high molecular weight PBT Celanex; the PVDF resin has a weight average molecular weight of 40 ten thousand and is purchased from thoroughfare Ruiguani chemical Co., Ltd; the average diameter of the mullite nano fiber is 300nm, and the preparation method refers to the Chinese patent invention example 1 with the application number of 201910394011.5 for the preparation in advance.
Example 1
The PBT/PVDF composite membrane is characterized by being prepared from the following raw materials in parts by weight: 25 parts of vinyl sulfonated modified PBT resin, 30 parts of PBT resin, 10 parts of PVDF resin, 5 parts of 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber and 0.5 part of azobisisobutyronitrile.
The preparation method of the 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber comprises the following steps: dispersing 30g of mullite nano fiber in 100g of ethanol to obtain a dispersion, adding 4g of 3-triethoxysilylpropyltrimethylammonium chloride into the dispersion, stirring and reacting at 60 ℃ for 6 hours, and then removing the ethanol by rotary evaporation to obtain the 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nano fiber.
The preparation method of the vinyl sulfonated modified PBT resin comprises the following steps:
step S1, adding 100g of PBT resin into 300g of hexafluoroisopropanol, stirring for 15 minutes, then adding 10g of chlorosulfonic acid into the mixture under ice bath, stirring for reaction for 1 hour, then heating to 40 ℃, continuing stirring for reaction for 2 hours, then performing rotary evaporation to remove the solvent, washing the product with water for 2 times, then washing the product with ethanol for 3 times, and then drying the product in a vacuum drying oven at 80 ℃ to constant weight to obtain the sulfonated PBT resin;
step S2, soaking 100g of the sulfonated PBT resin prepared in the step S1 in 1000g of dichloromethane containing 20g of 2-vinyl-3H-4-quinazolinone, 12g of 4-dimethylaminopyridine and 6g of N, N' -dicyclohexylcarbodiimide for 8 hours, taking out, washing with water for 3 times, washing with ethanol for 3 times, and then removing the ethanol through rotary evaporation to obtain the vinyl sulfonated modified PBT resin.
The production process of the PBT/PVDF composite membrane is characterized by comprising the following steps: uniformly mixing vinyl sulfonated modified PBT resin, PVDF resin, 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nano-fiber and azobisisobutyronitrile to form a mixture, adding the mixture into a mixed solvent with the mass 20 times that of the mixture, stirring for 10 minutes, performing ultrasonic treatment for 15 minutes, pouring the mixture into a casting film tray, scraping the mixture by using a scraper to form a film, and drying the film at 80 ℃ for 4 hours to obtain a PBT/PVDF composite film; the mixed solvent is formed by mixing hexafluoroisopropanol and N, N-dimethylacetamide according to a mass ratio of 5:2.
Example 2
The PBT/PVDF composite membrane is characterized by being prepared from the following raw materials in parts by weight: 27 parts of vinyl sulfonated modified PBT resin, 32 parts of PBT resin, 11 parts of PVDF resin, 6 parts of 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber and 0.7 part of azodiisoheptonitrile.
The preparation method of the 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber comprises the following steps: dispersing 35g of mullite nanofiber in 120g of dichloromethane to obtain a dispersion, adding 4g of 3-triethoxysilylpropyltrimethylammonium chloride into the dispersion, stirring and reacting at 65 ℃ for 6.5 hours, and then removing the dichloromethane by rotary evaporation to obtain the 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber.
The preparation method of the vinyl sulfonated modified PBT resin comprises the following steps:
step S1, adding 100g of PBT resin into 350g of hexafluoroisopropanol, stirring for 20 minutes, then adding 15g of chlorosulfonic acid into the mixture under an ice bath, stirring for reaction for 1.5 hours, then heating to 42 ℃, continuing to stir for reaction for 2.5 hours, then performing rotary evaporation to remove the solvent, washing the product with water for 3 times, then washing with ethanol for 4 times, and then placing the product in a vacuum drying oven at 82 ℃ for drying to constant weight to obtain sulfonated PBT resin;
step S2, 100g of the sulfonated PBT resin prepared in the step S1 is soaked in 1150g of dichloromethane containing 20g of 2-vinyl-3H-4-quinazolinone, 12g of 4-dimethylaminopyridine and 6g of N, N' -dicyclohexylcarbodiimide for 9 hours, then the sulfonated PBT resin is taken out and washed with water for 4 times, then washed with ethanol for 4 times, and finally the ethanol is removed by rotary evaporation to obtain the vinyl sulfonated modified PBT resin.
The production process of the PBT/PVDF composite membrane is characterized by comprising the following steps: uniformly mixing vinyl sulfonated modified PBT resin, PVDF resin, 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nano-fiber and azodiisoheptonitrile to form a mixture, adding the mixture into a mixed solvent with the mass being 22 times that of the mixture, stirring for 12 minutes, carrying out ultrasonic treatment for 17 minutes, pouring the mixture into a casting film tray, scraping the mixture by using a scraper to form a film, and drying the film at 82 ℃ for 5 hours to obtain a PBT/PVDF composite film; the mixed solvent is prepared by mixing hexafluoroisopropanol and N, N-dimethylacetamide according to a mass ratio of 5: 2.3.
Example 3
The PBT/PVDF composite membrane is characterized by being prepared from the following raw materials in parts by weight: 30 parts of vinyl sulfonated modified PBT resin, 35 parts of PBT resin, 13 parts of PVDF resin, 7.5 parts of 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber and 1 part of azobisisobutyronitrile.
The preparation method of the 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber comprises the following steps: dispersing 40g of mullite nanofiber in 150g of acetone to obtain a dispersion, adding 4g of 3-triethoxysilylpropyltrimethylammonium chloride into the dispersion, stirring and reacting at 70 ℃ for 7 hours, and then removing the acetone by rotary evaporation to obtain the 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber.
The preparation method of the vinyl sulfonated modified PBT resin comprises the following steps:
step S1, adding 100g of PBT resin into 400g of hexafluoroisopropanol, stirring for 23 minutes, then adding 20g of chlorosulfonic acid into the mixture under an ice bath, stirring for reacting for 2 hours, then heating to 45 ℃, continuing to stir for reacting for 3 hours, then performing rotary evaporation to remove the solvent, washing the product with water for 4 times, then washing the product with ethanol for 5 times, and then drying the product in a vacuum drying oven at 85 ℃ to constant weight to obtain the sulfonated PBT resin;
step S2, soaking 100g of the sulfonated PBT resin prepared in the step S1 in 1300g of dichloromethane containing 20g of 2-vinyl-3H-4-quinazolinone, 12g of 4-dimethylaminopyridine and 6g of N, N' -dicyclohexylcarbodiimide for 10 hours, taking out, washing with water for 4 times, washing with ethanol for 5 times, and then removing the ethanol through rotary evaporation to obtain the vinyl sulfonated modified PBT resin.
The production process of the PBT/PVDF composite membrane is characterized by comprising the following steps: uniformly mixing vinyl sulfonated modified PBT resin, PVDF resin, 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nano-fiber and azobisisobutyronitrile to form a mixture, adding the mixture into a mixed solvent with the mass 25 times that of the mixture, stirring for 15 minutes, carrying out ultrasonic treatment for 20 minutes, pouring the mixture into a casting film tray, scraping the mixture by using a scraper to form a film, and drying the film at 85 ℃ for 6 hours to obtain a PBT/PVDF composite film; the mixed solvent is formed by mixing hexafluoroisopropanol and N, N-dimethylacetamide according to a mass ratio of 5: 2.5.
Example 4
The PBT/PVDF composite membrane is characterized by being prepared from the following raw materials in parts by weight: 33 parts of vinyl sulfonated modified PBT resin, 38 parts of PBT resin, 14 parts of PVDF resin, 9 parts of 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber and 1.4 parts of initiator; the initiator is formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 3: 5.
The preparation method of the 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber comprises the following steps: dispersing 45g of mullite nanofiber in 185g of tetrahydrofuran to obtain a dispersion, adding 4g of 3-triethoxysilylpropyltrimethylammonium chloride into the dispersion, stirring and reacting at 78 ℃ for 7.8 hours, and then removing the tetrahydrofuran by rotary evaporation to obtain the 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber.
The preparation method of the vinyl sulfonated modified PBT resin comprises the following steps:
step S1, adding 100g of PBT resin into 460g of hexafluoroisopropanol, stirring for 28 minutes, then adding 25g of chlorosulfonic acid into the mixture under an ice bath, stirring for reacting for 2.8 hours, then heating to 48 ℃, continuing to stir for reacting for 4 hours, then performing rotary evaporation to remove the solvent, washing the product with water for 4 times, then washing with ethanol for 5 times, and then placing the product in a vacuum drying oven at 88 ℃ for drying to constant weight to obtain the sulfonated PBT resin;
step S2, soaking 100g of the sulfonated PBT resin prepared in the step S1 in 1400g of dichloromethane containing 20g of 2-vinyl-3H-4-quinazolinone, 12g of 4-dimethylaminopyridine and 6g of N, N' -dicyclohexylcarbodiimide for 11 hours, taking out, washing with water for 5 times, washing with ethanol for 5 times, and then removing the ethanol through rotary evaporation to obtain the vinyl sulfonated modified PBT resin.
The production process of the PBT/PVDF composite membrane is characterized by comprising the following steps: uniformly mixing vinyl sulfonated modified PBT resin, PVDF resin, 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nano-fiber and an initiator to form a mixture, adding the mixture into a mixed solvent with the mass 28 times that of the mixture, stirring for 18 minutes, carrying out ultrasonic treatment for 24 minutes, pouring the mixture into a casting film tray, scraping the mixture by using a scraper to form a film, and drying the film at 88 ℃ for 7 hours to obtain the PBT/PVDF composite film; the mixed solvent is formed by mixing hexafluoroisopropanol and N, N-dimethylacetamide according to a mass ratio of 5: 2.8.
Example 5
The PBT/PVDF composite membrane is characterized by being prepared from the following raw materials in parts by weight: 35 parts of vinyl sulfonated modified PBT resin, 40 parts of PBT resin, 15 parts of PVDF resin, 10 parts of 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber and 1.5 parts of azodiisoheptonitrile.
The preparation method of the 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber comprises the following steps: dispersing 50g of mullite nano fiber into 200g of ethanol to obtain a dispersion, adding 4g of 3-triethoxysilylpropyltrimethylammonium chloride into the dispersion, stirring and reacting at 80 ℃ for 8 hours, and then removing the ethanol by rotary evaporation to obtain the 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nano fiber.
The preparation method of the vinyl sulfonated modified PBT resin comprises the following steps:
step S1, adding 100g of PBT resin into 500g of hexafluoroisopropanol, stirring for 30 minutes, then adding 30g of chlorosulfonic acid into the mixture under ice bath, stirring for reaction for 3 hours, then heating to 50 ℃, continuing stirring for reaction for 4 hours, then performing rotary evaporation to remove the solvent, washing the product with water for 5 times, then washing with ethanol for 6 times, and then drying in a vacuum drying oven at 90 ℃ to constant weight to obtain the sulfonated PBT resin;
step S2, soaking 100g of the sulfonated PBT resin prepared in the step S1 in 1500g of dichloromethane containing 20g of 2-vinyl-3H-4-quinazolinone, 12g of 4-dimethylaminopyridine and 6g of N, N' -dicyclohexylcarbodiimide for 12 hours, taking out, washing with water for 5 times, washing with ethanol for 6 times, and then removing the ethanol through rotary evaporation to obtain the vinyl sulfonated modified PBT resin.
The production process of the PBT/PVDF composite membrane is characterized by comprising the following steps: uniformly mixing vinyl sulfonated modified PBT resin, PVDF resin, 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nano-fiber and azodiisoheptonitrile to form a mixture, adding the mixture into a mixed solvent with the mass 30 times that of the mixture, stirring for 20 minutes, carrying out ultrasonic treatment for 25 minutes, pouring the mixture into a casting film tray, scraping the mixture by using a scraper to form a film, and drying the film at 90 ℃ for 8 hours to obtain a PBT/PVDF composite film; the mixed solvent is formed by mixing hexafluoroisopropanol and N, N-dimethylacetamide according to a mass ratio of 5: 2.8.
Comparative example 1
The invention provides a PBT/PVDF composite membrane, the formula and the production process of which are similar to those of example 1, except that no vinyl sulfonated modified PBT resin is added.
Comparative example 2
The invention provides a PBT/PVDF composite membrane, the formula and the production process of which are similar to those of example 1, except that 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber is not added.
Comparative example 3
The invention provides a commercially available PBT film which is purchased from Zhejiang.
The film samples prepared in examples 1 to 5 and comparative examples 1 to 3 above were subjected to the relevant performance tests, and the test results and test methods are shown in table 1.
TABLE 1
| Item | Heat resistance temperature | Tensile strength | Bending strength | Notched impact strength 23 deg.C |
| Unit of | ℃ | MPa | MPa | KJ/m2 |
| Test standard | GB1035-70 | GB/T1040.1-2006 | GB/T9341-2008 | GB/T20186.1-2006 |
| Example 1 | 185 | 70.2 | 140 | 8.0 |
| Example 2 | 188 | 71.6 | 143 | 8.3 |
| Example 3 | 191 | 72.3 | 145 | 8.5 |
| Example 4 | 193 | 73.6 | 147 | 8.8 |
| Example 5 | 196 | 75.0 | 150 | 9.0 |
| Comparative example 1 | 177 | 60.3 | 130 | 7.2 |
| Comparative example 2 | 174 | 59.5 | 127 | 7.0 |
| Comparative example 3 | 160 | 55.0 | 125 | 5.8 |
As can be seen from Table 1, the PBT/PVDF composite membrane disclosed by the embodiment of the invention has excellent mechanical properties and heat resistance, which are the result of synergistic effect of the components and the structure of each raw material.
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 (7)
1. The PBT/PVDF composite membrane is characterized by being prepared from the following raw materials in parts by weight: 25-35 parts of vinyl sulfonated modified PBT resin, 30-40 parts of PBT resin, 10-15 parts of PVDF resin, 5-10 parts of 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofiber and 0.5-1.5 parts of initiator;
the preparation method of the vinyl sulfonated modified PBT resin comprises the following steps:
step S1, adding the PBT resin into hexafluoroisopropanol, stirring for 15-30 minutes, then adding chlorosulfonic acid into the hexafluoroisopropanol in an ice bath, stirring for reaction for 1-3 hours, then heating to 40-50 ℃, continuing to stir for reaction for 2-4 hours, then performing rotary evaporation to remove the solvent, washing the product with water for 2-5 times, then washing with ethanol for 3-6 times, and then placing the product in a vacuum drying oven at 80-90 ℃ for drying to constant weight to obtain sulfonated PBT resin; the mass ratio of the PBT resin to the hexafluoroisopropanol to the chlorosulfonic acid is 1 (3-5) to 0.1-0.3;
step S2, soaking the sulfonated PBT resin prepared in the step S1 in dichloromethane containing 2-vinyl-3H-4-quinazolinone, 4-dimethylaminopyridine and N, N' -dicyclohexylcarbodiimide for 8-12 hours, taking out, washing with water for 3-5 times, washing with ethanol for 3-6 times, and performing rotary evaporation to remove ethanol to obtain the vinyl sulfonated modified PBT resin; the mass ratio of the sulfonated PBT resin to the 2-vinyl-3H-4-quinazolinone to the 4-dimethylaminopyridine to the N, N' -dicyclohexylcarbodiimide to the dichloromethane is 1:0.2:0.12:0.06 (10-15).
2. The PBT/PVDF composite membrane according to claim 1, wherein the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
3. The PBT/PVDF composite membrane of claim 1, wherein the preparation method of the 3-triethoxysilylpropyltrimethylammonium chloride-modified mullite nanofiber comprises the following steps: dispersing the mullite nanofibers in an organic solvent to obtain a dispersion, adding 3-triethoxysilylpropyltrimethylammonium chloride into the dispersion, stirring and reacting at 60-80 ℃ for 6-8 hours, and then removing the organic solvent by rotary evaporation to obtain the 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nanofibers.
4. The PBT/PVDF composite membrane according to claim 3, wherein the mass ratio of the mullite nanofibers to the organic solvent to the 3-triethoxysilylpropyltrimethylammonium chloride is (3-5): 10-20): 0.4.
5. The PBT/PVDF composite membrane according to claim 3, wherein the organic solvent is one of ethanol, dichloromethane, acetone, and tetrahydrofuran.
6. The PBT/PVDF composite membrane according to any one of claims 1 to 5, wherein the production process of the PBT/PVDF composite membrane comprises the following steps: uniformly mixing vinyl sulfonated modified PBT resin, PVDF resin, 3-triethoxysilylpropyltrimethylammonium chloride modified mullite nano-fiber and an initiator to form a mixture, adding the mixture into a mixed solvent with the mass 20-30 times that of the mixture, stirring for 10-20 minutes, carrying out ultrasonic treatment for 15-25 minutes, pouring the mixture into a casting film tray, scraping the mixture by using a scraper to form a film, and drying the film at 80-90 ℃ for 4-8 hours to obtain the PBT/PVDF composite film.
7. The PBT/PVDF composite membrane according to claim 6, wherein the mixed solvent is a mixture of hexafluoroisopropanol and N, N-dimethylacetamide in a mass ratio of 5 (2-3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911110148.XA CN111004479B (en) | 2019-11-14 | 2019-11-14 | PBT/PVDF composite membrane and production process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911110148.XA CN111004479B (en) | 2019-11-14 | 2019-11-14 | PBT/PVDF composite membrane and production process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111004479A CN111004479A (en) | 2020-04-14 |
| CN111004479B true CN111004479B (en) | 2022-03-18 |
Family
ID=70113426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911110148.XA Active CN111004479B (en) | 2019-11-14 | 2019-11-14 | PBT/PVDF composite membrane and production process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111004479B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6537475B1 (en) * | 1995-08-31 | 2003-03-25 | Prisma Fibers, Inc. | Melt extrusion spinning polyamide fibers with sulfonated reagent |
| CN101343356A (en) * | 2008-07-18 | 2009-01-14 | 东南大学 | Method for sulfonated modified waste polyester plastics |
| CN104497539B (en) * | 2015-01-13 | 2016-04-20 | 上海中镭新材料科技有限公司 | The wear-resisting PC/ABS Alloy And Preparation Method of high light HI high impact |
| CN106566209A (en) * | 2016-10-21 | 2017-04-19 | 上海航天设备制造总厂 | Preparing method of sulfonation octaphenyl multi-face low polysilsesquioxane/polysuccinic acid butanediol ester |
-
2019
- 2019-11-14 CN CN201911110148.XA patent/CN111004479B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111004479A (en) | 2020-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104294594B (en) | The preparation method of the super thin fabric face of a kind of water and oil repellant | |
| JP6868876B2 (en) | Aramid epoxy resin and its manufacturing method | |
| CN108948686B (en) | Glass fiber reinforced ASA/PBT alloy automobile lamp base material and preparation method thereof | |
| CN108164751B (en) | Reactive halogen-free flame retardant suitable for TPV (thermoplastic vulcanizate), and preparation method and application thereof | |
| CN107877893A (en) | Preparation method of electromagnetic shielding PP film | |
| CN105803672A (en) | Preparation method of conductive nanofiber membrane | |
| CN110819048A (en) | Graphene modified composite emulsion for rubber material and preparation method thereof | |
| CN107266849A (en) | A kind of low temperature resistant plating PC/ABS alloy materials drawn cruelly and preparation method | |
| CN109608841A (en) | A kind of preparation method and product of MXene enhancing polylactic acid 3D printing material | |
| CN116217848A (en) | Preparation method of phenolic resin containing unsaturated double bond structure | |
| CN106084705A (en) | A kind of high intensity antistatic composite material sheet material and preparation method thereof | |
| CN111004479B (en) | PBT/PVDF composite membrane and production process thereof | |
| CN103709741A (en) | CNT (Carbon Nano Tube)/nylon6 composite material and preparation method thereof | |
| CN115232274B (en) | Benzoxazine oligomer toughening agent based on long aliphatic chain phenol and its preparation method and application | |
| CN110437570A (en) | A kind of multi-layer core-shell particle toughening composite material of polymethyl methacrylate and preparation method | |
| CN117646289B (en) | Antifouling and antibacterial textile fabric and preparation method thereof | |
| CN101619143B (en) | Method for preparing fiber-loaded beta nucleating agent and application thereof in modified polypropylene | |
| CN104448278B (en) | A kind of antifouling fire-retardant anti-molten droplet polyester and preparation method thereof | |
| CN116769295A (en) | Conductive PC (polycarbonate) for conductive carrier tape sheet and preparation method thereof | |
| CN104532390B (en) | A kind of conductive fabric and preparation method thereof | |
| CN118684860B (en) | Preparation method of multifunctional epoxy resin and its application in conductive adhesive | |
| CN106317776A (en) | Method for preparing polyester fiber reinforced epoxy composite material based on chemical modification | |
| CN107141633A (en) | A kind of composite fibre toughening polyvinyl chloride plastic tube and preparation method thereof | |
| CN115286901A (en) | High-strength high-impact PBT (polybutylene terephthalate) material and preparation method thereof | |
| CN113429606B (en) | A kind of polymer waterproof roll material and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 215156 Building 1, 289 Caofeng Road, Xukou Town, Wuzhong District, Suzhou City, Jiangsu Province Patentee after: Suzhou New Guangyi Electronics Co.,Ltd. Address before: 215156 Building 1, 289 Caofeng Road, Xukou Town, Wuzhong District, Suzhou City, Jiangsu Province Patentee before: SUZHOU XINGUANGYI ELECTRONICS Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |