CN114891146B - High-heat-resistance vinylidene fluoride copolymer and preparation method and application thereof - Google Patents
High-heat-resistance vinylidene fluoride copolymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a high heat-resistant vinylidene fluoride copolymer, and a preparation method and application thereof. The invention takes maleimide derivative and acryl derivative as comonomer, and carries out copolymerization reaction with vinylidene fluoride monomer to prepare a vinylidene fluoride copolymer. According to the invention, the stabilizer composition containing the acrylamide polymer is added in the preparation process of the vinylidene fluoride copolymer, so that the stability of a polymerization system is enhanced, gel or large particles are prevented from occurring in the polymerization process, and the vinylidene fluoride copolymer product with concentrated particle size distribution is obtained. The vinylidene fluoride copolymer prepared by the invention not only has excellent thermal stability, but also has relatively concentrated particle size distribution.
Description
Technical Field
The invention belongs to the technical field of fluoride engineering, relates to a fluorine-containing polymer, and in particular relates to a high-heat-resistance vinylidene fluoride copolymer, and a preparation method and application thereof.
Background
Polyvinylidene fluoride (PVDF) is a generic term for vinylidene fluoride homopolymers and copolymers, and is the second largest class of fluororesin next to polytetrafluoroethylene. Polyvinylidene fluoride is widely applied to industries such as lithium batteries, paint, wind power photovoltaic, electronics and electricity and the like due to excellent chemical stability, weather resistance, adhesion, dielectric property, piezoelectricity and the like.
Due to vinylidene fluoride structural unit-CH 2 -CF 2 The asymmetry is present, so that head-to-head, head-to-tail and tail-to-tail structures are easily formed on the polyvinylidene fluoride molecular chain during the polymerization, which affects the regularity of the polymer molecular chain, resulting in a decrease in crystallinity and thermal stability of the product. In addition, fluorine atoms and hydrogen atoms on adjacent carbon atoms in the polyvinylidene fluoride molecular chain are easy to undergo elimination reaction, and hydrogen fluoride is removed, so that the thermal stability of the polymer is adversely affected. In the practical downstream application links, especially in lithium electricity, wind power photovoltaic and electronic and electric industries, there are extreme cases of local overheating of products, so polyvinylidene fluoride must have excellent thermal stability to prevent the application temperature from exceeding the thermal stability range of polyvinylidene fluoride, resulting in reduced product performance and even potential safety hazard.
The prior art has mainly increased the thermal stability of polyvinylidene fluoride by introducing comonomers or changing the method of the initiating system. Among them, the method of introducing the comonomer most commonly adopts the copolymerization of the acrylic monomer and vinylidene fluoride. The patent CN 101679563B facilitates control of the randomly distributed acrylic unit fraction above 40% by continuously feeding an aqueous hydrophilic acrylic monomer solution into the polymerizer, thereby improving the thermal stability of the vinylidene fluoride copolymer. The patent CN 103270058B uses vinylidene fluoride, acrylic monomer and optionally one or more other fluorinated monomers as comonomers and performs a polymerization reaction in an aqueous medium comprising at least one fluorinated surfactant and at least one non-functional perfluoropolyether oil, the resulting vinylidene fluoride copolymer retaining good thermal stability and exhibiting enhanced dissolution characteristics in organic solvents. Patent CN 103270060B invents a vinylidene fluoride copolymer whose comonomers include trifluoroethylene and acrylic monomers, which exhibits improved breakdown voltage and enhanced adhesion strength, and maintains excellent thermal stability. Although the method for copolymerizing the acrylic acid monomer can improve the thermal stability of polyvinylidene fluoride to a certain extent, the effect is very limited; and the most critical is that the introduced acrylic monomer contains ester groups and is not resistant to hydrolysis, especially in some alkaline environments, such as ternary positive electrode materials, the acrylic monomer is easy to accelerate hydrolysis, so that polyvinylidene fluoride loses the effect of a positive electrode binder, and the service life of the battery is influenced.
In addition, the method for changing the initiation system mainly comprises the step of preparing polyvinylidene fluoride by compounding an initiator. Patent CN 101434670a uses a redox initiator to prepare a polyvinylidene fluoride with high chain regularity, exhibiting excellent thermal stability and improved weatherability. The patent CN 102134292A adopts an organic initiator of combination of organic hydrogen peroxide and organic peroxide, and adds ester or mercaptan as a regulator to obtain a mixed organic initiator solution, and adds the mixed organic initiator solution in a continuous mode to prepare the polyvinylidene fluoride with high melt fluidity, and the polymerized product has moderate molecular weight, narrow distribution coefficient, good thermal stability and strong weather resistance. The method adjusts the polymer chain segment structure by changing the initiation system, and can improve the thermal stability of polyvinylidene fluoride to a certain extent, but has low initiation efficiency, long polymerization reaction time, low production efficiency and lack of industrial economic value.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a highly heat-resistant vinylidene fluoride copolymer which is excellent in heat stability and has a relatively concentrated particle size distribution. The invention takes the maleimide derivative and the acryloyl derivative as comonomers to carry out copolymerization reaction with the vinylidene fluoride monomer to prepare the vinylidene fluoride copolymer with excellent thermal stability.
Another object of the present invention is to add a stabilizer composition containing an acrylamide polymer during the preparation of the above-mentioned vinylidene fluoride copolymer, to enhance the stability of the polymerization system, to prevent the occurrence of gels or large particles during the polymerization, and to facilitate the obtaining of a vinylidene fluoride copolymer product having a concentrated particle size distribution.
In order to achieve the above object, the present invention has the following technical scheme:
the invention provides a high heat-resistant vinylidene fluoride copolymer, the comonomer of which comprises:
(a) Vinylidene fluoride (VDF),
(b) A maleimide derivative having a structure represented by the following formula 1:
in formula 1, R 1 Selected from hydrogen atom, halogen atom, hydroxy, amino, C1-C12 hydrocarbon group, at least one halogen atom or hydroxy-or amino-substituted C1-C12 hydrocarbon group, R 2 、R 3 Each independently selected from hydrogen atom, halogen atom, C1-C12 hydrocarbon group, R 2 And R is 3 The same as or different from each other;
(c) An acryl derivative having a structure represented by the following formula 2:
in formula 2, X 1 Selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a C1-C8 alkyl group, a C1-C8 alkoxy group, and an nitroxide group, R 4 、R 5 、R 6 Each independently selected from hydrogen atom, halogen atom, C1-C8 hydrocarbon group, R 4 、R 5 、R 6 The same as or different from each other;
and optionally (d) other fluorovinyl monomers.
In the substituent groups of the formula 1 and the formula 2, the hydrocarbon group specifically refers to a part of hydrocarbon substances composed of hydrocarbon two elements, wherein one hydrogen atom of the hydrocarbon substances is removed. Further, the hydrocarbon groups can be correspondingly classified into alkyl groups, alkenyl groups, alkynyl groups and aromatic hydrocarbon groups according to whether the hydrocarbon substance contains an unsaturated bond and the kind of the unsaturated bond; the hydrocarbon group can be classified into an aliphatic hydrocarbon group, a cyclic hydrocarbon group and an aromatic hydrocarbon group according to whether or not the hydrocarbon substance contains a cyclic structure and the type of the cyclic structure.
In the invention, in the structural formula 1 of the maleimide derivative, R 2 And R is 3 Preferably hydrogen atom, when R 1 When the maleimide derivative is hydrogen atom, the maleimide derivative is maleimide; when R is 1 When the hydroxyl is hydroxyl, the maleimide derivative is N-hydroxyl maleimide; when R is 1 When the amino group is the maleimide derivative is N-amino maleimide; when R is 1 When the derivative is methyl, the maleimide derivative is N-methyl maleimide; when R is 1 When the derivative is ethyl, the maleimide derivative is N-ethylmaleimide; when R is 1 When the maleimide derivative is cyclohexyl, the maleimide derivative is N-cyclohexylmaleimide; when R is 1 When phenyl is adopted, the maleimide derivative is N-phenyl maleimide; when R is 1 When benzyl, the maleimide derivative is N-benzyl maleimide; when R is 1 When the maleimide derivative is 2-hydroxyethyl, the maleimide derivative is N- (2-hydroxyethyl) maleimide; when R is 1 When the maleimide derivative is 2-aminoethyl, the maleimide derivative is N- (2-aminoethyl) maleimide. In an embodiment of the present invention, the maleimide derivative is selected from any one or a combination of at least two of the above specific substances maleimide, N-hydroxy maleimide, N-amino maleimide, N-methyl maleimide, N-ethyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, N-benzyl maleimide, N- (2-hydroxyethyl) maleimide, N- (2-amino ethyl) maleimide, preferably N-Hydroxy Maleimide (HML).
In the invention, the maleimide derivative is used in an amount of 0.4 to 8% by mass, preferably 0.8 to 4.5% by mass, based on the mass of vinylidene fluoride.
In the present invention, the maleimide derivative as a comonomer plays a critical role in improving the heat resistance of the vinylidene fluoride copolymer. The maleimide derivative has a stable five-membered ring structure and contains imide groups, and can effectively absorb, conduct and digest heat without structural damage, so that when the unit structure of the maleimide derivative is introduced into the molecular chain of the vinylidene fluoride polymer, the heat resistance of the obtained vinylidene fluoride copolymer is obviously enhanced.
In the invention, in the structural formula 2 of the acryloyl derivative, R 4 、R 5 And R is 6 Preferably hydrogen atom, when X 1 When the hydrogen atom is adopted, the acryloyl derivative is acrolein; when X is 1 When the chlorine atom is the chlorine atom, the acrylic acid derivative is acrylic acid chloride; when X is 1 When the hydroxyl is hydroxyl, the acrylic acid derivative is acrylic acid; when X is 1 When the amino group is the acrylic acid derivative is acrylamide; when X is 1 When methyl, the acryloyl derivative is methyl vinyl ketone; when X is 1 When methoxy, the acryl derivative is methyl acrylate; when X is 1 When the acrylic acid is ethoxy, the acrylic acid derivative is ethyl acrylate; when X is 1 When the acrylic acid is butoxy, the acrylic acid derivative is butyl acrylate; when X is 1 When the derivative is nitrogen oxygen hexacyclic ring, the acryloyl derivative is N-acryloyl morpholine. In an embodiment of the present invention, the acryl derivative is selected from any one or a combination of at least two of the above specific substances of acrolein, acryl chloride, acrylic acid, acrylamide, methyl vinyl ketone, methyl acrylate, ethyl acrylate, butyl acrylate, N-acryl morpholine, preferably Acrylamide (AM) and/or N-Acryl Morpholine (AMP).
In the present invention, the amount of the acryl derivative is 0.2 to 5% by mass, preferably 0.5 to 4.2% by mass, based on the mass of vinylidene fluoride.
In the present invention, the vinylidene fluoride copolymer may optionally contain one or more other fluorovinyl monomers in addition to the three monomers of vinylidene fluoride, maleimide derivative and acryl derivative, where the other fluorovinyl monomers refer to fluorovinyl monomers other than vinylidene fluoride monomers;
preferably, the other fluorine-containing vinyl monomer is selected from any one or a combination of at least two of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether.
In the invention, the dosage of the other fluorine-containing vinyl monomers is 0 to 3.8 percent of the mass of the vinylidene fluoride.
Particularly, the vinylidene fluoride copolymer is prepared by polymerization reaction of a comonomer with water as a dispersion medium, and in the preparation process, a stabilizer composition is added into the water, and experiments show that the comonomer composed of the vinylidene fluoride copolymer can enhance the stability of a polymerization system, prevent gel or large particles from occurring in the polymerization process and be beneficial to obtaining a vinylidene fluoride copolymer product with concentrated particle size distribution.
The stabilizer composition of the present invention comprises an acrylamide polymer and optionally one or more water-soluble polymers.
Preferably, the stabilizer composition wherein the acrylamide polymer is used in an amount of 0.15 to 1.2% by mass of the comonomer (a) vinylidene fluoride; the water-soluble polymer dosage is 0.1-0.35% of the mass of vinylidene fluoride.
Preferably, the acrylamide polymer contained in the stabilizer composition may be an acrylamide homopolymer or an acrylamide copolymer, and has a weight average molecular weight of 60 to 800 g/mol, preferably 100 to 500 g/mol;
more preferably, the acrylamide copolymer is an acrylamide-acrylic acid copolymer wherein the molar ratio of acrylamide units to acrylic acid units is from 99:1 to 70:30.
Preferably, the water-soluble polymer contained in the stabilizer composition is selected from any one or a combination of at least two of methylcellulose, hydroxymethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methylcellulose, hydroxyethyl ethylcellulose, hydroxypropyl methylcellulose, polyvinyl alcohol, polyethylene glycol, preferably hydroxyethyl cellulose.
The stabilizer composition used in the invention is a polymer with better water solubility, contains a large number of polar groups such as amide groups, carboxyl groups and hydroxyl groups, and contains a large number of fluorine atoms and imide groups with strong polarity on the molecular chain of the vinylidene fluoride copolymer, so that the stabilizer composition is adsorbed on the surface of the molecular chain of the polyvinylidene fluoride, and generates stronger intermolecular force through Van der Waals force, hydrogen bond and other forms, thereby playing a role in stabilizing and dispersing a polymerization system, effectively preventing coalescence of liquid drops and avoiding occurrence of gel and large particles. In addition, the acrylamide polymer contained in the stabilizer composition has very high molecular weight, and is generally over a million and even reaches the grade of tens of millions in the market at present, so that the acrylamide polymer contains quite long polymer chains, can be wound around polyvinylidene fluoride molecular chains, and can isolate and protect polymer liquid drops in a physical way, thereby achieving the purposes of stabilizing a polymerization system and controlling particle size.
In a preferred embodiment of the present invention, the vinylidene fluoride copolymer is a vinylidene fluoride-N-hydroxymaleimide-acrylamide copolymer (VDF-HML-AM copolymer) or a vinylidene fluoride-N-hydroxymaleimide-N-acryloylmorpholine copolymer (VDF-HML-AMP copolymer).
The vinylidene fluoride copolymer of the invention not only has excellent thermal stability, but also has relatively concentrated particle size distribution. Specifically, the vinylidene fluoride copolymer undergoes a weight loss of 0.5% by weight at a temperature greater than 380 ℃ and a weight loss of 1% by weight at a temperature greater than 430 ℃ as tested by TGA under nitrogen atmosphere according to ISO 11358 standard; the average particle diameter D50 of the vinylidene fluoride copolymer is less than 230 mu m, and the width of the particle diameter distribution is less than 0.62 after analysis by a laser particle size analyzer.
The invention also provides a preparation method of the high heat-resistant vinylidene fluoride copolymer, which is prepared by polymerization reaction of a comonomer with water as a dispersion medium, specifically adopts a suspension polymerization method, and is characterized in that a stabilizer composition is added into the water, and the preparation method comprises the following steps: mixing vinylidene fluoride, maleimide derivative, acryl derivative and optional other fluorine-containing vinyl monomers with water, and simultaneously adding a stabilizer composition to perform suspension polymerization reaction to obtain a high heat-resistant vinylidene fluoride copolymer;
in the present invention, the water is added in an amount of 110 to 450% by mass, preferably 120 to 300% by mass, of the comonomer (a) vinylidene fluoride.
In the present invention, the suspension polymerization is carried out at a reaction temperature of 45 to 120℃and preferably 45 to 90℃for a reaction time of 4 to 16 hours and preferably 5 to 10 hours.
In the invention, the suspension polymerization reaction is carried out under the reaction pressure of 5-15MPaA; in the invention, the reaction pressure is controlled by the passing amount of the vinylidene fluoride, the vinylidene fluoride monomer adopts a continuous feeding mode, a certain amount (for example, 20-80% of the total mass of the vinylidene fluoride) of vinylidene fluoride is firstly passed on to the bottom before the reaction starts, the vinylidene fluoride monomer is continuously passed into the system in the reaction process, and the reaction pressure is maintained at 5-15MPaA.
In the invention, the suspension polymerization reaction comprises the operation of introducing nitrogen and deoxidizing before the reaction, so that the oxygen content is less than or equal to 10ppm.
In addition, as with other suspension polymerization methods, the preparation raw material of the invention also contains a chain transfer agent, and the specific requirement is not met, and common types can be selected from any one or at least two of dimethyl carbonate, diethyl carbonate, methylethyl carbonate, ethyl acetate, methyl acetate, ethyl propionate, ethanol, n-propanol, isopropanol, acetone, diethyl ether and methyl tertiary butyl ether, preferably diethyl carbonate;
preferably, the chain transfer agent is added in an amount of 0.15 to 0.62% by mass of the vinylidene fluoride comonomer (a).
In the present invention, the suspension polymerization reaction, the preparation raw material further comprises an initiator, and the specific is not particularly required, and common types are, for example, any one or a combination of at least two selected from methyl ethyl ketone peroxide, dibenzoyl peroxide, t-butyl benzoyl peroxide, t-butyl peroxymaleate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, t-amyl peroxypivalate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, diethyl peroxydicarbonate, dicyclohexyl peroxydicarbonate and di-2-ethylhexyl peroxydicarbonate, preferably diisopropyl peroxydicarbonate;
preferably, the initiator is added in an amount of 0.08 to 0.55% by mass of the vinylidene fluoride comonomer (a).
In the present invention, after the suspension polymerization reaction is completed, the post-treatment processes of recovering unreacted monomers, washing, filtering, drying, etc. are also included, and are not particularly required for the conventional operation in the field, for example, the post-treatment methods adopted in some examples are specifically: stopping polymerization after the pressure is reduced to the atmospheric pressure, recovering unreacted monomers, washing with deionized water until the conductivity of the washing liquid is reduced to below 1 mu S/cm, and finally obtaining a copolymer product through filtration and drying.
The vinylidene fluoride copolymer disclosed by the invention is suitable for being applied to lithium battery binders and diaphragms, fluorocarbon coatings, solar back plate films, hollow fiber films, petrochemical products and any other fields.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the invention takes the maleimide derivative and the acryloyl derivative as comonomers to carry out copolymerization reaction with the vinylidene fluoride monomer, and adds a stabilizer composition containing an acrylamide polymer in the polymerization process to prepare the vinylidene fluoride copolymer, which has excellent thermal stability and relatively concentrated particle size distribution.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate the present invention further, but are not to be construed as limiting the present invention.
The main raw material source information adopted in the embodiment of the invention is as follows, and other raw materials are obtained through common commercial purchase unless specified otherwise:
vinylidene fluoride: purchased from Shandong China Shenzhou New Material Co., ltd;
hexafluoropropylene: purchased from eastern mountain polymeric materials limited;
perfluoromethyl vinyl ether: purchased from Shenzhen New Mebang technology Co., ltd;
maleimide, N-hydroxymaleimide, N-methylmaleimide, N-cyclohexylmaleimide: purchased from Shanghai Ala Biochemical technologies Co., ltd;
acrylic acid, acrylamide, methyl vinyl ketone, ethyl acrylate, N-acryloylmorpholine: purchased from national pharmaceutical group chemical reagent company, inc;
acrylamide homopolymer (trade mark FLOPAM FA 920 SH, weight average molecular weight 350 vang/mol), acrylamide-acrylic acid copolymer (trade mark FLOPAM AN 934 BPM, weight average molecular weight 160 vang/mol): purchased from aisen (china) flocculant limited.
The specific test conditions and analysis methods adopted by the main performance indexes of the embodiment of the invention are as follows:
(1) Polymerization System stability
After the polymerization reaction was completed, the presence or absence of distinct agglomerates and gels in the polymerization vessel was observed.
(2) Particle size analysis
The particle size and particle size distribution of the vinylidene fluoride copolymer were measured by a laser particle sizer, the vinylidene fluoride copolymer was dispersed in an isophorone solvent, and the average particle size D50 and the particle size distribution width of the sample were analyzed by a wet method.
(3) Analysis of thermal stability
TGA analysis of vinylidene fluoride copolymers in dynamic mode under nitrogen atmosphere according to ISO 11358 standard, the temperatures corresponding to the samples losing 0.5% wt, 0.75% wt and 1% wt respectively are recorded, the higher these temperatures the better the thermal stability of the vinylidene fluoride copolymer.
Example 1
The preparation method of the high heat-resistant vinylidene fluoride copolymer comprises the following steps:
adding 7.6Kg deionized water, 7.5g acrylamide homopolymer and 17.5g hydroxymethyl cellulose into a 15L high-pressure reaction kettle, starting stirring at the rotating speed of 600r/min, introducing nitrogen to remove oxygen to ensure that the oxygen content is less than or equal to 10ppm, adding 3.5Kg vinylidene fluoride (70 percent), 190g hexafluoropropylene, 20g maleimide and 250g acrylic acid, heating the system to 60 ℃, continuously introducing vinylidene fluoride monomers to ensure that the reaction pressure is maintained at 10MPaA, adding 31g ethyl acetate and 4g dibenzoyl peroxide, starting polymerization, after the reaction is carried out for 4 hours, reducing the pressure in the kettle to the atmospheric pressure through degassing, stopping polymerization, wherein the total mass of the vinylidene fluoride raw materials added into the reaction system is 5Kg, recovering unreacted monomers, repeatedly washing polymer slurry in the kettle with deionized water until the conductivity of a washing solution is reduced to below 1 mu S/cm, and finally filtering and drying to obtain a finished product.
Example 2
The preparation method of the high heat-resistant vinylidene fluoride copolymer comprises the following steps:
14.5Kg of deionized water, 60g of acrylamide homopolymer and 5g of polyethylene glycol are added into a 15L high-pressure reaction kettle, stirring is started, the rotating speed is 600r/min, nitrogen is introduced to remove oxygen, the oxygen content is less than or equal to 10ppm, then 1.5Kg of vinylidene fluoride (30 percent) is added, 400g of N-cyclohexylmaleimide and 10g of methyl vinyl ketone are added, the temperature of the system is raised to 110 ℃, the reaction pressure is kept at 12MPaA by continuously introducing the vinylidene fluoride monomer, 7.5g of isopropanol and 27.5g of tert-butyl peroxymaleate are added, polymerization reaction is started, after the reaction is carried out for 12 hours, the pressure in the kettle is reduced to atmospheric pressure through degassing, polymerization is stopped, the total mass of the vinylidene fluoride raw material added into the reaction system is 5Kg, the unreacted monomer is recovered, the polymer slurry in the kettle is repeatedly washed by deionized water until the conductivity of the washing liquid is reduced to below 1 mu S/cm, and finally the finished product is obtained through filtration and drying.
Example 3
The preparation method of the high heat-resistant vinylidene fluoride copolymer comprises the following steps:
9.5Kg of deionized water, 12.5g of acrylamide-acrylic acid copolymer and 7.5g of hydroxypropyl methyl cellulose are added into a 15L high-pressure reaction kettle, stirring is started, the rotating speed is 600r/min, nitrogen is introduced for deoxidization, the oxygen content is less than or equal to 10ppm, then 2Kg of vinylidene fluoride (40 percent, 100g of perfluoromethyl vinyl ether, 250g of N-methyl maleimide and 75g of ethyl acrylate are added, the temperature of the system is increased to 50 ℃, vinylidene fluoride monomers are continuously introduced to maintain the reaction pressure at 7MPaA, 22.5g of methyl tertiary butyl ether and 12.5g of tert-butyl peroxypivalate are added, polymerization reaction is started, after 8 hours of reaction, the pressure in the kettle is reduced to the atmospheric pressure through degassing, the polymerization is stopped, the mass of the vinylidene fluoride raw materials added into the reaction system is 5 ppm in total, the unreacted monomers are recovered, the polymer slurry in the kettle is repeatedly washed by the deionized water until the conductivity of the washing liquid is reduced to below 1 mu S/cm, and finally, the finished product is obtained through filtration and drying.
Example 4
The preparation method of the high heat-resistant vinylidene fluoride copolymer comprises the following steps:
8.5Kg of deionized water, 30g of acrylamide homopolymer and 10g of hydroxyethyl cellulose are added into a 15L high-pressure reaction kettle, stirring is started, the rotating speed is 600r/min, nitrogen is introduced to remove oxygen, the oxygen content is less than or equal to 10ppm, then 2.5Kg of vinylidene fluoride (50 percent of the vinylidene fluoride is added), 200g of N-hydroxyl maleimide and 125g of acrylamide are added, the temperature of the system is raised to 70 ℃, the reaction pressure is kept at 9MPaA by continuously introducing vinylidene fluoride monomers, 17.5g of diethyl carbonate and 20g of diisopropyl peroxydicarbonate are added, polymerization reaction is started, after 7 hours of reaction, the pressure in the kettle is reduced to atmospheric pressure through degassing, polymerization is stopped, the total mass of the vinylidene fluoride raw materials added into the reaction system is 5Kg, unreacted monomers are recovered, polymer slurry in the kettle is repeatedly washed by deionized water until the conductivity of a washing liquid is reduced to below 1 mu S/cm, and finally, the finished product is obtained through filtration and drying.
Example 5
The preparation method of the high heat-resistant vinylidene fluoride copolymer comprises the following steps:
adding 12.5Kg deionized water, 15g acrylamide-acrylic acid copolymer and 15g hydroxyethyl cellulose into a 15L high-pressure reaction kettle, starting stirring at 600r/min, introducing nitrogen to remove oxygen to ensure that the oxygen content is less than or equal to 10ppm, adding 3Kg vinylidene fluoride (60 percent), 150g N-hydroxy maleimide and 175g N-acryloylmorpholine, heating the system to 90 ℃, continuously introducing vinylidene fluoride monomer to ensure that the reaction pressure is maintained at 11MPaA, adding 12.5g diethyl carbonate and 15g diisopropyl peroxydicarbonate, starting polymerization, reducing the pressure in the kettle to the atmospheric pressure through degassing after the reaction for 6h, stopping polymerization, wherein the mass of the vinylidene fluoride raw material added into the reaction system is 5 mu S/cm in total, recovering unreacted monomer, repeatedly washing polymer slurry in the kettle by deionized water until the conductivity of a washing solution is reduced to below 1 mu S/cm, and finally filtering and drying to obtain a finished product.
Example 6
A highly heat resistant vinylidene fluoride copolymer was prepared as in example 4, except that: the amount of N-hydroxy maleimide is changed from 200g to 100g, and other conditions are unchanged.
Example 7
A highly heat resistant vinylidene fluoride copolymer was prepared as in example 4, except that: the amount of acrylamide homopolymer was changed from 30g to 20g, with the other conditions unchanged.
Example 8
A highly heat resistant vinylidene fluoride copolymer was prepared as in example 4, except that: the amount of N-hydroxy maleimide is changed from 200g to 100g, and the amount of acrylamide homopolymer is changed from 30g to 20g, with the other conditions unchanged.
Comparative example 1
A vinylidene fluoride copolymer was prepared as in example 4, except that: the N-hydroxy maleimide was replaced with an equal amount of deionized water, with the other conditions unchanged.
Comparative example 2
A vinylidene fluoride copolymer was prepared as in example 4, except that: the acrylamide was replaced with an equal amount of deionized water, with the other conditions unchanged.
Comparative example 3
A vinylidene fluoride copolymer was prepared as in example 4, except that: the acrylamide homopolymer was replaced with an equal amount of hydroxyethylcellulose, with the other conditions unchanged.
The vinylidene fluoride copolymer products obtained in each of the examples and comparative examples were analyzed according to the performance test method of the present invention, and the results are shown in Table 1.
Table 1 results of product performance tests in examples and comparative examples
As can be seen from the analysis data in Table 1, compared with comparative examples 1-3, examples 1-8 of the present invention have the advantages of good polymerization system stability, no caking and no gelation problem, and smaller average particle size and particle size distribution width; and the vinylidene fluoride copolymer exhibits excellent thermal stability, particularly being subjected to a weight loss of 0.5% by weight at a temperature of greater than 380 ℃ and 1% by weight at a temperature of greater than 430 ℃.
Further analysis, by comparing examples 4 and 6 with examples 7 and 8, shows that the amount of maleimide derivative is reduced and the thermal stability of the vinylidene fluoride copolymer is lowered; by comparing examples 4 and 7 with examples 6 and 8, it is demonstrated that the amount of acrylamide polymer in the stabilizer composition is reduced and the average particle size and the width of the particle size distribution of the vinylidene fluoride copolymer are increased; by comparing examples 4 and 8, it is demonstrated that the amount of acrylamide polymer in the maleimide derivative and the stabilizer composition is simultaneously reduced, the thermal stability of the vinylidene fluoride copolymer is lowered, and the average particle diameter and the width of the particle diameter distribution are increased.
Therefore, the vinylidene fluoride copolymer of the present invention has not only excellent thermal stability but also relatively concentrated particle size distribution, and is suitable for application in lithium battery binders and separators, fluorocarbon coatings, solar back sheet films, hollow fiber films, petrochemical products and any other fields.
Claims (19)
1. A highly heat resistant vinylidene fluoride copolymer characterized in that the comonomer comprises:
(a) Vinylidene fluoride is used as a catalyst for the production of ethylene,
(b) A maleimide derivative having a structure represented by the following formula 1:
in formula 1, R 1 Selected from hydrogen atom, halogen atom, hydroxy, amino, C1-C12 hydrocarbon group, at least one halogen atom or hydroxy-or amino-substituted C1-C12 hydrocarbon group, R 2 、R 3 Each independently selected from hydrogen atom, halogen atom, C1-C12 hydrocarbon group, R 2 And R is 3 The same as or different from each other;
(c) An acryl derivative having a structure represented by the following formula 2:
in formula 2, X 1 Selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a C1-C8 alkyl group, a C1-C8 alkoxy group, and an nitroxide group, R 4 、R 5 、R 6 Each independently selected from hydrogen atom, halogen atom, C1-C8 hydrocarbon group, R 4 、R 5 、R 6 The same as or different from each other;
and optionally (d) other fluorovinyl monomers;
the vinylidene fluoride copolymer is prepared by polymerization reaction of a comonomer with water as a dispersion medium, and a stabilizer composition is added into the water, wherein the stabilizer composition comprises an acrylamide polymer and optionally one or more water-soluble macromolecules.
2. Vinylidene fluoride copolymer according to claim 1, characterized in that the maleimide derivative is selected from any one or a combination of at least two of maleimide, N-hydroxy maleimide, N-amino maleimide, N-methyl maleimide, N-ethyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, N-benzyl maleimide, N- (2-hydroxyethyl) maleimide, N- (2-aminoethyl) maleimide;
the acrylic acid derivative is selected from any one or a combination of at least two of acrolein, acrylic acid chloride, acrylic acid, acrylamide, methyl vinyl ketone, methyl acrylate, ethyl acrylate, butyl acrylate and N-acryloyl morpholine;
the other fluorine-containing vinyl monomer is selected from any one or a combination of at least two of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether and perfluoropropyl vinyl ether.
3. The vinylidene fluoride copolymer of claim 1, wherein the maleimide derivative is used in an amount of 0.4 to 8% by mass of vinylidene fluoride;
the dosage of the acryloyl derivative is 0.2-5% of the mass of vinylidene fluoride;
the dosage of the other fluorine-containing vinyl monomers is 0 to 3.8 percent of the mass of the vinylidene fluoride.
4. A vinylidene fluoride copolymer according to claim 3, wherein the maleimide derivative is used in an amount of 0.8 to 4.5% by mass of vinylidene fluoride.
5. A vinylidene fluoride copolymer according to claim 3, wherein the amount of the acryl derivative is 0.5 to 4.2% by mass of vinylidene fluoride.
6. The vinylidene fluoride copolymer of claim 1, wherein the stabilizer composition, wherein the acrylamide polymer is present in an amount of 0.15 to 1.2% by mass of vinylidene fluoride; the water-soluble polymer dosage is 0.1-0.35% of the mass of vinylidene fluoride.
7. Vinylidene fluoride copolymer according to claim 1, characterized in that the acrylamide polymer is chosen from acrylamide homopolymers, or acrylamide copolymers, having a weight average molecular weight of 60-800 g/mol;
the water-soluble polymer is selected from any one or a combination of at least two of methyl cellulose, hydroxymethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxypropyl methyl cellulose, polyvinyl alcohol and polyethylene glycol.
8. The vinylidene fluoride copolymer of claim 7, wherein the acrylamide polymer has a weight average molecular weight of 100 to 500 vang/mol.
9. The vinylidene fluoride copolymer of claim 7, wherein the acrylamide copolymer is an acrylamide-acrylic acid copolymer having a molar ratio of acrylamide units to acrylic acid units of from 99:1 to 70:30.
10. The vinylidene fluoride copolymer of claim 1, wherein the vinylidene fluoride copolymer is a vinylidene fluoride-N-hydroxymaleimide-acrylamide copolymer or a vinylidene fluoride-N-hydroxymaleimide-N-acrylomorpholine copolymer.
11. Vinylidene fluoride copolymer according to claim 1, characterized in that it is subjected to a TGA test under nitrogen atmosphere according to ISO 11358 standard, to a weight loss of 0.5% wt at a temperature of more than 380 ℃ and to a weight loss of 1% wt at a temperature of more than 430 ℃;
the average particle diameter D50 of the vinylidene fluoride copolymer is less than 230 mu m, and the width of the particle diameter distribution is less than 0.62 after analysis by a laser particle size analyzer.
12. A process for the preparation of a vinylidene fluoride copolymer according to any of claims 1 to 11, characterized in that the steps comprise: the vinylidene fluoride, maleimide derivative, acryl derivative, optional other fluorine-containing vinyl monomer and water are mixed, and a stabilizer composition is added at the same time to carry out suspension polymerization reaction, thus obtaining the vinylidene fluoride copolymer with high heat resistance.
13. The preparation method according to claim 12, wherein the water is added in an amount of 110 to 450% by mass of vinylidene fluoride.
14. The preparation method according to claim 13, wherein the water is added in an amount of 120-300% by mass of vinylidene fluoride.
15. The method of claim 12, wherein the suspension polymerization reaction comprises a preparation raw material comprising a chain transfer agent and an initiator.
16. The production method according to claim 15, wherein the chain transfer agent is added in an amount of 0.15 to 0.62% by mass of vinylidene fluoride; the addition amount of the initiator is 0.08-0.55% of the mass of the vinylidene fluoride.
17. The method according to claim 12, wherein the suspension polymerization is carried out at a temperature of 45 to 120 ℃ for a time of 4 to 16 hours; the reaction pressure is 5-15MPaA;
the suspension polymerization reaction comprises the operation of introducing nitrogen to remove oxygen before the reaction, so that the oxygen content is less than or equal to 10ppm.
18. The process of claim 17, wherein the suspension polymerization is carried out at a temperature of 45-90 ℃ for a time of 5-10 hours.
19. Use of the vinylidene fluoride copolymer of any one of claims 1 to 11 or prepared by the process of any one of claims 12 to 18 in the fields of lithium battery binders and separators, fluorocarbon coatings, solar back sheet films, hollow fiber films, petrochemical products.
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| WO2018092675A1 (en) * | 2016-11-15 | 2018-05-24 | 株式会社クレハ | Vinylidene fluoride copolymer, binder composition, electrode mix, electrode, and nonaqueous-electrolyte secondary battery |
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