CN108179498B - Polymer film and preparation method thereof - Google Patents
Polymer film and preparation method thereof Download PDFInfo
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- CN108179498B CN108179498B CN201711107874.7A CN201711107874A CN108179498B CN 108179498 B CN108179498 B CN 108179498B CN 201711107874 A CN201711107874 A CN 201711107874A CN 108179498 B CN108179498 B CN 108179498B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- Polymers & Plastics (AREA)
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Abstract
The invention relates to a polymer film and a preparation method thereof, and belongs to the technical field of lithium batteries. The polymer film is prepared from a blend of a spinning polymer and epoxy resin through an electrostatic spinning method, wherein the breaking strength of the polymer film is greater than 13Mpa, the breaking elongation is greater than 190%, and the porosity is above 75%.
Description
Technical Field
The invention relates to a polymer film and a preparation method thereof, and belongs to the technical field of lithium batteries.
Background
Because the solid electrolyte is used for replacing the liquid electrolyte, compared with a liquid lithium ion battery, the polymer lithium ion battery has the advantages of thinness, arbitrary area, arbitrary shape and the like, and the battery shell can be manufactured by using the aluminum-plastic composite film, so that the specific capacity of the whole battery can be improved; the polymer lithium ion battery can also adopt polymer as a positive electrode material, and the mass specific energy of the polymer lithium ion battery can be improved by more than 20 percent compared with the current liquid lithium ion battery. The polymer lithium-ion (polymer lithium-ion) battery has the characteristics of miniaturization, thinness and light weight.
Under the condition of high current, the ion battery is easy to cause a large amount of buried dendrites to puncture PP, PE or a composite film thereof, so that potential safety hazards are caused by internal short circuit of the battery. The safety of the battery separator is critical to the safety of the buried ion battery, whether it be a high capacity battery or a high power battery. The buried battery diaphragm which is commercially applied at present is a PP and PE double-layer or three-layer composite diaphragm, and one of the most outstanding problems of the diaphragm which is applied at present is poor physical properties such as breaking strength, breaking elongation and the like, and the polymer diaphragm is easy to damage when working at high temperature.
CN200910006220.4 discloses a separator comprising a base material layer comprising a polyolefin resin material, and a surface layer provided at least on the surface of the positive electrode side of the base material layer and comprising at least one selected from the group consisting of polyvinylidene fluoride, polytetrafluoroethylene and polypropylene, and at least one selected from the group consisting of aromatic polyamide, polyamide-imide and ceramic is present on the outermost surface of the surface layer. The ceramic layer of the separator is extremely likely to fall off in the electrolyte, resulting in problems of poor uniformity and increased resistance.
Disclosure of Invention
The purpose of the invention is that: solves the problems of low porosity and low strength of the polymer film prepared by the blending method.
The technical proposal is as follows:
a polymer film is prepared from the mixture of spinning polymer and epoxy resin through electrostatic spinning method, and has breaking strength greater than 13MPa, breaking elongation greater than 190% and porosity greater than 75%.
The polymer is selected from the group consisting of polyolefins.
The epoxy resin is in a liquid state at 25 ℃, and the epoxy compound has at least two epoxy groups in one molecule.
The epoxy resin is selected from bisphenol A, bisphenol F, bisphenol AD, dihydroxynaphthalene, aminophenol, polyalkylene glycol, poly (alkylene) glycol, modified products of these compounds, etc., and is obtained by epoxidation, and alicyclic epoxy resin.
The epoxy resin refers to modified bisphenol F epoxy resin.
The preparation method of the polymer film comprises the following steps:
step 1, according to parts by weight, 20-40 parts of polymer and 30-45 parts of epoxy resin are dissolved in 15-20 parts of solvent to obtain a first mixture;
step 2, adding 1-3 parts of ammonium bicarbonate into the first mixture, uniformly mixing, adding 10-20 parts of aromatic amine curing agent, and uniformly stirring to obtain a second mixture;
step 3, carrying out electrostatic spinning on the second mixture to obtain a spinning film;
and step 4, heating and solidifying the spinning film to obtain the polymer film.
The aromatic amine curing agent contains an aromatic amine compound which is liquid at 25 ℃, and the aromatic amine compound has at least two amino groups directly bonded to an aromatic ring in one molecule.
The preparation method of the epoxy resin comprises the following steps:
s1, carrying out alcoholysis reaction on 10-15 parts by weight of tung oil, 40-55 parts by weight of fatty alcohol and 0.05-0.08 part by weight of acidic or alkaline catalyst to obtain a first reactant;
s2, adding 40-60 parts of organic anhydride, 5-10 parts of N-methylolmethacrylamide (N-MMAA) and 0.1-0.2 part of polymerization inhibitor for reaction to obtain a second reactant;
s3, adding 5-10 parts of a second reactant, 3-5 parts of 1, 4-butanediol and 3-5 parts of trimethylolpropane into 100-150 parts of bisphenol F epoxy resin for reaction to obtain the modified epoxy resin.
The fatty alcohol is selected from one or more of isomeric tridecanol, isomeric heptanol, polyethylene glycol or polypropylene glycol; the organic anhydride is selected from one or a mixture of several of maleic anhydride, acetic anhydride and phthalic anhydride.
The alkaline catalyst is sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide or calcium oxalate.
The acid catalyst is sulfuric acid, hydrochloric acid, nitric acid or sulfonic acid.
In the S1, the reaction temperature is 180-220 ℃ and the reaction time is 1-10 h.
In the S2, the reaction temperature is 50-200 ℃ and the reaction time is 1-10 h.
In the step S3, the reaction temperature is 110-120 ℃ and the reaction time is 1-3 hours.
Advantageous effects
The polymer film is prepared from a blend of a spinning polymer and an epoxy resin through an electrostatic spinning method, and has the breaking strength of more than 13Mpa, the breaking elongation of more than 190% and the porosity of more than 75%.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments. It will be appreciated by those skilled in the art that the following examples are illustrative of the present invention and should not be construed as limiting the scope of the invention. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The words "comprise," "include," "have" or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Values expressed in a range format are to be understood to include not only the numerical values explicitly recited as the limits of the range, but also all individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a concentration range of "about 0.1% to about 5%" should be interpreted to include not only the explicitly recited concentration of about 0.1% to about 5%, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%) within the indicated range. Percentages in the present invention refer to weight percentages unless otherwise indicated.
The epoxy component in the epoxy resin composition of the present invention is liquid at 25 ℃ and contains an epoxy compound having at least two epoxy groups in one molecule. In order to adjust workability and various characteristics, a reactive diluent having an epoxy group may be used in combination with the epoxy compound. The epoxy compound is a compound having 2 or more epoxy groups contained in the molecule in terms of forming a crosslinked structure capable of exhibiting sufficient heat resistance, and the like. Further, from the viewpoint of obtaining a low-viscosity resin composition, the number of epoxy groups is preferably 4 or less, and more preferably 3 or less. When the number of epoxy groups contained in the molecule is too small, there is a tendency that the heat resistance of the cured product tends to be low and the strength tends to be low, and when the number of epoxy groups is too large, there is a tendency that the viscosity of the resin composition tends to be high and the curing shrinkage tends to be large. The number average molecular weight of the epoxy compound which is liquid at 25℃is preferably 230 to 440, and more preferably 230 to 380, from the viewpoint that a low-viscosity resin composition can be obtained and that the balance of physical properties is good. When the number average molecular weight is too small, the cured product tends to be low in strength and moisture resistance, and when the number average molecular weight is too large, the viscosity of the resin composition tends to be high. The epoxy equivalent of the epoxy compound is preferably 50 to 500, more preferably 90 to 300, from the viewpoint that the mixing amount of the curing agent is in a suitable range.
The epoxy compound may be a known or known liquid epoxy resin. Examples thereof include epoxy resins, alicyclic epoxy resins, and mixtures of these resins, which are liquid at 25 ℃, obtained by epoxidizing modified products of bisphenol a, bisphenol F, bisphenol AD, dihydroxynaphthalene, aminophenol, polyalkylene glycol, poly (alkylene) glycol, and these compounds. Among these, bisphenol a type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, naphthalene type epoxy resins, epoxy resins obtained by epoxidizing aminophenol (glycidyl aminophenol type epoxy resins), and the like are preferable from the viewpoints of low viscosity and excellent heat resistance and moisture resistance. In addition, a mixture of these epoxy compounds may be used.
In one embodiment, the modified epoxy resin may be prepared by:
step 1, according to parts by weight, 10 to 15 parts of tung oil, 40 to 55 parts of fatty alcohol and 0.05 to 0.08 part of acid or alkaline catalyst are subjected to alcoholysis reaction to obtain a first reactant;
step 2, adding 40-60 parts of organic anhydride, 5-10 parts of N-methylolmethacrylamide (N-MMAA) and 0.1-0.2 part of polymerization inhibitor for reaction to obtain a second reactant;
and step 3, adding 5-10 parts of a second reactant and 5-5 parts of 1, 4-butanediol into 100-150 parts of bisphenol F epoxy resin, and reacting to obtain the modified epoxy resin.
The fatty alcohol is selected from one or more of isomeric tridecanol, isomeric heptanol, polyethylene glycol or polypropylene glycol; the organic anhydride is selected from one or a mixture of several of maleic anhydride, acetic anhydride and phthalic anhydride.
The alkaline catalyst is sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide or calcium oxalate.
The acid catalyst is sulfuric acid, hydrochloric acid, nitric acid or sulfonic acid.
In the step 1, the reaction temperature is 180-220 ℃ and the reaction time is 1-10 h.
In the step 2, the reaction temperature is 50-200 ℃ and the reaction time is 1-10 h.
In the step 3, the reaction temperature is 110-120 ℃ and the reaction time is 1-3 hours.
Examples of the polyolefin used in the present invention include polyethylene, polypropylene, and polymers made of resins such as copolymers of ethylene or propylene with other α -olefins.
The polypropylene may be a polymer synthesized using a usual Ziegler-Natta catalyst, or may be a polymer synthesized using a single site catalyst typified by a metallocene. The other alpha-olefin is an olefin having 3 to 10 carbon atoms, and specifically, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and the like are exemplified. These may be used alone or in combination of 1 or more than 2.
In addition, other nucleating agents, antioxidants, lubricants, fillers, plasticizers, etc. may be added to the above-described polyolefin and epoxy resin mixture, as long as the added functional auxiliary does not affect the main properties of the polymer.
Among them, as the antioxidant, for example, triphenyl phosphite, tris (4-methylphenyl) phosphite, tris (4-t-butylphenyl) phosphite, tris (monononylphenyl) phosphite, tris (2-methyl-4-ethylphenyl) phosphite, tris (2-methyl-4-t-butylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tris (2, 6-di-t-butylphenyl) phosphite, tris (2, 4-di-t-butyl-5-methylphenyl) phosphite, tris (mono, dinonylphenyl) phosphite, bis (monononylphenyl) pentaerythritol-di-phosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, bis (2, 4, 6-tri-t-butylphenyl) pentaerythritol-di-phosphite, bis (2, 4-di-t-butyl-5-methylphenyl) pentaerythritol-di-phosphite, 2-dimethylbenzene-bis (4, 6-octylene-2, 6-methyl-octylene phosphite, bis (2, 4-t-butylphenyl) pentaerythritol-di-phosphite can be used, phosphite compounds such as 2, 2-methylenebis (4, 6-di-t-butylphenyl) octyl phosphite, 2-methylenebis (4, 6-dimethylphenyl) hexyl phosphite, and 2, 2-methylenebis (4, 6-di-t-butylphenyl) stearyl phosphite; pentaerythritol-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 1, 6-hexanediol-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 3, 9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1, 1-dimethylethyl }2,4,8, 10-tetraoxaspiro [5,5] undecane, 1, 3-tris [ 2-methyl-4- (3, 5-di-tert-butyl-4-hydroxyphenyl propionyloxy) -5-tert-butylphenyl ] butane and the like hindered phenol compounds; 5, 7-di-tert-butyl-3- (3, 4-dimethylphenyl) -3H-benzofuran-2-one, and the like. These may be used singly or in combination of 2 or more.
The lubricant used in the present invention is not particularly limited as long as it plays a role in improving the fluidity of the thermoplastic polymer, and examples thereof include hydrocarbon lubricants such as liquid paraffin wax, solid paraffin wax, microcrystalline paraffin wax, and polyethylene wax; fatty acid lubricants such as stearic acid, behenyl acid, and 1, 2-hydroxystearic acid; and ester lubricants such as butyl stearate, monoglyceride stearate, pentaerythritol tetrastearate, hardened castor oil, and stearyl stearate.
As the above-mentioned method for producing a polymer film, the following steps can be carried out:
step 1, according to parts by weight, 20-40 parts of polymer and 30-45 parts of epoxy resin are dissolved in 15-20 parts of solvent to obtain a first mixture;
step 2, adding 1-3 parts of ammonium bicarbonate into the first mixture, uniformly mixing, adding 10-20 parts of aromatic amine curing agent, and uniformly stirring to obtain a second mixture;
step 3, carrying out electrostatic spinning on the second mixture to obtain a spinning film;
and step 4, heating and solidifying the spinning film to obtain the polymer film.
It is well known to those skilled in the art that better mixing can be achieved when the polymer is mixed with the epoxy resin, preferably after it has been dissolved with a solvent; after the ammonium bicarbonate is added, heat is generated when the curing agent reacts with the epoxy resin, the heat can synchronously decompose the ammonium bicarbonate into ammonia and carbon dioxide, small pores can be formed in the polymer film after spinning, the strength of the polymer film cannot be affected, and after the curing agent is further cured through heating, the strength of the polymer film can be improved, and the ammonia and the carbon dioxide in the polymer film can be removed.
The solvent used in the present invention is generally more commonly (poly) alkylene glycol monoalkyl ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, etc.; (poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; other ethers such as diglyme, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactate esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; other esters such as methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl 2-oxybutyrate; aromatic hydrocarbons such as toluene and xylene; carboxylic acid amides such as N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide, and the like. These solvents may be used alone or in combination of 2 or more.
The aromatic amine curing agent in the epoxy resin composition of the present invention contains an aromatic amine compound having at least two amino groups directly bonded to an aromatic ring in one molecule and is in a liquid state at 25 ℃. The aromatic amine curing agent is an aromatic amine which is liquid at 25 ℃ and has at least two amino groups directly bonded to an aromatic ring in one molecule; from the viewpoint of obtaining a low-viscosity resin composition, the amino group is preferably 4 or less, more preferably 3 or less. When the number of amino groups contained in the molecule is too small, there is a tendency that the heat resistance of the cured product tends to be low, the strength tends to be low, and when the number of amino groups is too large, there is a tendency that the viscosity of the resin composition tends to be high, the curing shrinkage tends to be large, and the like. Examples of the aromatic amine curing agent include diethyldiaminotoluene, bis (4-amino-3-ethylphenyl) methane, and poly-1, 4-butanediol bis (4-aminobenzoate). Of these, diethyldiaminotoluene and bis (4-amino-3-ethylphenyl) methane are preferable.
In the method, after the polymer and the epoxy resin are prepared into a solution, the film layer can be prepared through electrostatic spinning, and the preparation can be carried out by adopting electrostatic spinning equipment which is known to a person skilled in the art. And after the electrostatic spinning is finished, the surface of the receiver receives the fiber yarn containing the solvent, and after the solvent volatilizes, the spinning fiber is remained on the surface of the receiver, so that the electrostatic spinning film is obtained. Wherein, the inner diameter of the nozzle of the electrostatic spinning equipment is 0.2-1 mm, and the flow rate of the polymer solution in the nozzle is 0.6-2.0 mL/h. The conditions of electrospinning included: the voltage is 5-20 KV, the receiving distance is 6-15 cm, the moving speed of the spray head is 5-6 mm/s, and the rotating speed of the receiver is 300-600 rpm. The total time of the electrospinning can be selected according to the size of the polymer film required, and preferably, the electrospinning time is 3-6 hours, and the thickness of the formed spinning film is 80-150 mu m.
The temperature and time for heating and solidifying the spinning film can be adjusted according to actual conditions, and the temperature can be generally selected to be 40-70 ℃ and the time range is 10-60 min.
The polymer film provided by the invention has the breaking strength of more than 13Mpa, the breaking elongation of more than 190% and the porosity of more than 75%. The polymer matrix which can be used as gel polymer electrolyte is widely used.
Example 1
Step 1, heating 20 parts of polyethylene and 30 parts of modified epoxy resin to 40 ℃ according to parts by weight, and dissolving the mixture in 15 parts of ethyl acetate to obtain a first mixture;
step 2, adding 1 part of ammonium bicarbonate into the first mixture, uniformly mixing, adding 10 parts of diethyl diaminotoluene (DETDA) serving as an aromatic amine curing agent, and uniformly stirring to obtain a second mixture;
step 3, then the second mixture is subjected to electrostatic spinning to obtain a spinning film, and spinning conditions are as follows: the polymer solution is conveyed to a spray head with the inner diameter of 0.7mm on electrostatic spinning equipment at the flow rate of 0.7mL/h under the environment of 20 ℃ and the relative humidity of 40RH percent, and the electrostatic spinning is carried out in a high-voltage electric field of 8KV, wherein the spinning conditions comprise: the receiving distance is 14cm, the moving speed of the spray head is 5.0mm/s, and the rotating speed of the receiver is 550rpm; after the solvent on the surface of the receiver volatilizes, depositing the spinning fiber of the polymer on the receiver to form a spinning film;
and step 4, heating the spinning film to 40 ℃ and curing for 10min to obtain the polymer film.
The preparation method of the modified epoxy resin comprises the following steps:
s1, carrying out alcoholysis reaction on 10 parts by weight of tung oil, 40 parts by weight of isomerised dodecanol and 0.05 part by weight of catalyst sodium hydroxide at 180 ℃ for 1h to obtain a first reactant;
s2, adding 40 parts of acetic anhydride, 5 parts of N-methylolmethacrylamide (N-MMAA) and 0.1 part of polymerization inhibitor sodium sulfate for reaction at 50 ℃ for 1h to obtain a second reactant;
s3, adding a second reactant, 5 parts of 1, 4-butanediol and 3 parts of trimethylolpropane into 100 parts of bisphenol F epoxy resin, and reacting at 110 ℃ for 1 hour to obtain the modified epoxy resin.
Example 2
Step 1, heating 40 parts of polyethylene and 45 parts of modified epoxy resin to 40 ℃ according to parts by weight, and dissolving the mixture in 20 parts of ethyl acetate to obtain a first mixture;
step 2, adding 3 parts of ammonium bicarbonate into the first mixture, uniformly mixing, adding 20 parts of diethyl diaminotoluene (DETDA) serving as an aromatic amine curing agent, and uniformly stirring to obtain a second mixture;
step 3, then the second mixture is subjected to electrostatic spinning to obtain a spinning film, and spinning conditions are as follows: the polymer solution is conveyed to a spray head with the inner diameter of 0.7mm on electrostatic spinning equipment at the flow rate of 0.7mL/h under the environment of 20 ℃ and the relative humidity of 40RH percent, and the electrostatic spinning is carried out in a high-voltage electric field of 8KV, wherein the spinning conditions comprise: the receiving distance is 14cm, the moving speed of the spray head is 5.0mm/s, and the rotating speed of the receiver is 550rpm; after the solvent on the surface of the receiver volatilizes, depositing the spinning fiber of the polymer on the receiver to form a spinning film;
and step 4, heating the spinning film to 70 ℃ and curing for 60 minutes to obtain the polymer film.
The preparation method of the modified epoxy resin comprises the following steps:
s1, carrying out alcoholysis reaction on 15 parts of tung oil, 55 parts of isomerised dodecanol and 0.08 part of catalyst sodium hydroxide according to parts by weight, wherein the reaction temperature is 220 ℃, and the reaction time is 10 hours, so as to obtain a first reactant;
s2, adding 60 parts of acetic anhydride, 10 parts of N-methylolmethacrylamide (N-MMAA) and 0.2 part of polymerization inhibitor sodium sulfate for reaction at 200 ℃ for 10 hours to obtain a second reactant;
s3, adding the second reactant, 10 parts of 1,4 butanediol and 5 parts of trimethylolpropane into 150 parts of bisphenol F epoxy resin, and reacting at 120 ℃ for 3 hours to obtain the modified epoxy resin.
Example 3
Step 1, heating 30 parts of polyethylene and 40 parts of modified epoxy resin to 40 ℃ according to parts by weight, and dissolving the mixture in 16 parts of ethyl acetate to obtain a first mixture;
step 2, adding 2 parts of ammonium bicarbonate into the first mixture, uniformly mixing, adding 15 parts of diethyl diaminotoluene (DETDA) serving as an aromatic amine curing agent, and uniformly stirring to obtain a second mixture;
step 3, then the second mixture is subjected to electrostatic spinning to obtain a spinning film, and spinning conditions are as follows: the polymer solution is conveyed to a spray head with the inner diameter of 0.7mm on electrostatic spinning equipment at the flow rate of 0.7mL/h under the environment of 20 ℃ and the relative humidity of 40RH percent, and the electrostatic spinning is carried out in a high-voltage electric field of 8KV, wherein the spinning conditions comprise: the receiving distance is 14cm, the moving speed of the spray head is 5.0mm/s, and the rotating speed of the receiver is 550rpm; after the solvent on the surface of the receiver volatilizes, depositing the spinning fiber of the polymer on the receiver to form a spinning film;
and step 4, heating the spinning film to 50 ℃ and curing for 30min to obtain the polymer film.
The preparation method of the modified epoxy resin comprises the following steps:
s1, 11 parts of tung oil, 46 parts of isomerised dodecanol and 0.07 part of catalyst sodium hydroxide are subjected to alcoholysis reaction at the temperature of 190 ℃ for 5 hours to obtain a first reactant;
s2, adding 50 parts of acetic anhydride, 7 parts of N-methylolmethacrylamide (N-MMAA) and 0.15 part of polymerization inhibitor sodium sulfate for reaction at a temperature of 100 ℃ for 5 hours to obtain a second reactant;
s3, adding the second reactant, 7 parts of 1,4 butanediol and 4 parts of trimethylolpropane into 120 parts of bisphenol F epoxy resin, and reacting at the temperature of 115 ℃ for 2 hours to obtain the modified epoxy resin.
Comparative example 1
The difference from example 3 is that: the modified epoxy resin was prepared without modification by N-methylolmethacrylamide.
Step 1, heating 30 parts of polyethylene and 40 parts of modified epoxy resin to 40 ℃ according to parts by weight, and dissolving the mixture in 16 parts of ethyl acetate to obtain a first mixture;
step 2, adding 2 parts of ammonium bicarbonate into the first mixture, uniformly mixing, adding 15 parts of diethyl diaminotoluene (DETDA) serving as an aromatic amine curing agent, and uniformly stirring to obtain a second mixture;
step 3, then the second mixture is subjected to electrostatic spinning to obtain a spinning film, and spinning conditions are as follows: the polymer solution is conveyed to a spray head with the inner diameter of 0.7mm on electrostatic spinning equipment at the flow rate of 0.7mL/h under the environment of 20 ℃ and the relative humidity of 40RH percent, and the electrostatic spinning is carried out in a high-voltage electric field of 8KV, wherein the spinning conditions comprise: the receiving distance is 14cm, the moving speed of the spray head is 5.0mm/s, and the rotating speed of the receiver is 550rpm; after the solvent on the surface of the receiver volatilizes, depositing the spinning fiber of the polymer on the receiver to form a spinning film;
and step 4, heating the spinning film to 50 ℃ and curing for 30min to obtain the polymer film.
The preparation method of the modified epoxy resin comprises the following steps:
s1, 11 parts of tung oil, 46 parts of isomerised dodecanol and 0.07 part of catalyst sodium hydroxide are subjected to alcoholysis reaction at the temperature of 190 ℃ for 5 hours to obtain a first reactant;
s2, adding 50 parts of acetic anhydride and 0.15 part of polymerization inhibitor sodium sulfate for reaction at a reaction temperature of 100 ℃ for 5 hours to obtain a second reactant;
s3, adding the second reactant, 7 parts of 1,4 butanediol and 4 parts of trimethylolpropane into 120 parts of bisphenol F epoxy resin, and reacting at the temperature of 115 ℃ for 2 hours to obtain the modified epoxy resin.
Comparative example 2
The difference from example 3 is that: the modified epoxy resin is prepared without modification by tung oil and isomeric dodecanol.
Step 1, heating 30 parts of polyethylene and 40 parts of modified epoxy resin to 40 ℃ according to parts by weight, and dissolving the mixture in 16 parts of ethyl acetate to obtain a first mixture;
step 2, adding 2 parts of ammonium bicarbonate into the first mixture, uniformly mixing, adding 15 parts of diethyl diaminotoluene (DETDA) serving as an aromatic amine curing agent, and uniformly stirring to obtain a second mixture;
step 3, then the second mixture is subjected to electrostatic spinning to obtain a spinning film, and spinning conditions are as follows: the polymer solution is conveyed to a spray head with the inner diameter of 0.7mm on electrostatic spinning equipment at the flow rate of 0.7mL/h under the environment of 20 ℃ and the relative humidity of 40RH percent, and the electrostatic spinning is carried out in a high-voltage electric field of 8KV, wherein the spinning conditions comprise: the receiving distance is 14cm, the moving speed of the spray head is 5.0mm/s, and the rotating speed of the receiver is 550rpm; after the solvent on the surface of the receiver volatilizes, depositing the spinning fiber of the polymer on the receiver to form a spinning film;
and step 4, heating the spinning film to 50 ℃ and curing for 30min to obtain the polymer film.
The preparation method of the modified epoxy resin comprises the following steps:
s1, carrying out a reaction on 50 parts of acetic anhydride, 7 parts of N-methylolmethacrylamide (N-MMAA) and 0.15 part of polymerization inhibitor sodium sulfate in parts by weight, wherein the reaction temperature is 100 ℃, and the reaction time is 5 hours, so as to obtain a first reactant;
s2, adding the first reactant, 7 parts of 1, 4-butanediol and 4 parts of trimethylolpropane into 120 parts of bisphenol F epoxy resin, and reacting at 115 ℃ for 2 hours to obtain the modified epoxy resin.
Performance testing
1. Mechanical property test:
the polymer films of the examples and the comparative examples were subjected to mechanical properties. A conventional tensile testing instrument (Shenzhen Jun Rui) is adopted, the sample is dumbbell-shaped, the size of the sample is 4mm multiplied by 10mm, and the strain rate of the instrument is 20mm/min. The results of the breaking strength and elongation at break tested are shown in the following table.
2. Porosity test:
the example and control polymer films were tested for porosity. The porosity test was performed according to the following formula: p (%) = (M-M0)/(ρ) BuOH ×πr 2 ·d)×100％；
Wherein P is porosity, M0 is mass of the dry film, M is mass after soaking in n-butanol for 2h, r is radius of the film, and d is thickness of the film. The test results are shown in the following table.
3. Liquid absorption test:
the polymer films of the examples and the comparative examples were dried, weighed and immersed in an electrolyte (lithium salt: liPF) 6 The concentration is 1mol/L, the solvent is EC, EMC, DEC, the mass concentration ratio is 2:3:1) for 24 hours, then the liquid on the surface of the membrane is sucked by filter paper, the corresponding gel polymer electrolyte is obtained, the mass at the moment is weighed, and the operation is carried out in a glove box filled with argon.
Calculate the% wicking = (Wi-W)/W x 100% according to the formula;
wherein W is the mass of the dry film; wi is the mass of the dry film after 24 hours of soaking in the electrolyte. The test results are shown in the following table.
4. Conductivity test:
the polymer films of examples and comparative examples were placed between two Stainless Steel (SS) electrodes, absorbing a sufficient amount of electrolyte (lithium salt: liPF 6 Concentration is 1M/L, solvent is EC, EMC, DEC, mass concentration ratio is 2:3:1), the corresponding gel polymer electrolyte is obtained, after the gel polymer electrolyte is sealed in 2016 type button cell, alternating current impedance experiment is carried out, and the intersection point of the linearity and the real axis is the bulk resistance of the gel polymer electrolyte, so that the ion conductivity of the gel polymer electrolyte can be obtained: σ=l/(a·r), where L represents the thickness of the gel polymer electrolyte, a is the contact area of the stainless steel plate and the film, and R is the bulk resistance of the polymer electrolyte. The resulting gel polymer electrolyte conductivity is shown below.
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Fracture strength MPa | 13.6 | 13.9 | 14.6 | 11.3 | 11.8 |
| Elongation at break% | 190 | 190 | 195 | 160 | 150 |
| Porosity% | 82 | 81 | 85 | 75 | 73 |
| Liquid absorption% | 680 | 690 | 720 | 620 | 630 |
| Conductivity mS/cm | 1.5 | 1.4 | 1.7 | 1.1 | 1.2 |
As can be seen from the table, the polymer film provided by the invention has the breaking strength of more than 13Mpa, the breaking elongation of more than 190% and the porosity of more than 75%. In example 3, the porosity of the polymer film can be improved after adding N-methylolmethacrylamide in the preparation of the modified epoxy resin; and the liquid absorption rate of the film layer can be improved through tung oil and isomeric dodecanol modification.
Claims (3)
1. The polymer film is characterized in that the polymer film is prepared by a blend of a spinning polymer and an epoxy resin through an electrostatic spinning method, the breaking strength of the polymer film is more than 13Mpa, the breaking elongation is more than 190%, and the porosity is more than 75%; the polymer is selected from polyolefin;
a method of preparing a polymer film comprising the steps of:
step 1, according to parts by weight, 20-40 parts of polymer and 30-45 parts of modified bisphenol F epoxy resin are dissolved in 15-20 parts of solvent to obtain a first mixture;
the preparation method of the modified bisphenol F epoxy resin comprises the following steps: s1, carrying out alcoholysis reaction on 10-15 parts by weight of tung oil, 40-55 parts by weight of fatty alcohol and 0.05-0.08 part by weight of acidic or alkaline catalyst to obtain a first reactant; s2, adding 40-60 parts of organic anhydride, 5-10 parts of N-methylolmethacrylamide (N-MMAA) and 0.1-0.2 part of polymerization inhibitor for reaction to obtain a second reactant; s3, adding 5-10 parts of a second reactant and 5-5 parts of 1, 4-butanediol into 100-150 parts of bisphenol F epoxy resin, and reacting to obtain modified bisphenol F epoxy resin;
step 2, adding 1-3 parts of ammonium bicarbonate into the first mixture, uniformly mixing, adding 10-20 parts of aromatic amine curing agent, and uniformly stirring to obtain a second mixture;
step 3, carrying out electrostatic spinning on the second mixture to obtain a spinning film;
and step 4, heating and solidifying the spinning film to obtain the polymer film.
2. The polymer film according to claim 1, wherein the aromatic amine curing agent contains an aromatic amine compound having at least two amino groups directly bonded to an aromatic ring in one molecule, which is in a liquid state at 25 ℃.
3. The polymer film of claim 1, wherein the fatty alcohol is selected from one or more of isomeric tridecanols, isomeric heptaols, polyethylene glycols or polypropylene glycols; the organic acid anhydride is selected from one or a mixture of several of maleic anhydride, acetic anhydride and phthalic anhydride; the alkaline catalyst is sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide or calcium oxalate; the acid catalyst is sulfuric acid, hydrochloric acid, nitric acid or sulfonic acid.
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