CN106488946A - The manufacture method of aromatic polymer, stacked film and distance piece - Google Patents
The manufacture method of aromatic polymer, stacked film and distance piece Download PDFInfo
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- CN106488946A CN106488946A CN201580031898.1A CN201580031898A CN106488946A CN 106488946 A CN106488946 A CN 106488946A CN 201580031898 A CN201580031898 A CN 201580031898A CN 106488946 A CN106488946 A CN 106488946A
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/365—Coating
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of manufacture method of aromatic polymer, and described aromatic polymer is suitable for manufacturing the distance piece of the nonaqueous electrolytic solution secondary battery being able to ensure that high security.The manufacture method of the aromatic polymer of the present invention is the manufacture method with the aromatic polymer of structure shown in-C (=O) NH-, this manufacture method is made aromatic diamine and is reacted in organic solvent with the compound with the water-disintegrable reactive group being reacted with amino, wherein, organic solvent contains the water of 200ppm～2500ppm, and the intrinsic viscosity of aromatic polymer is 1.5dL/g～3.0dL/g.
Description
Technical field
The present invention relates to have the manufacture method of the aromatic polymer of structure shown in-C (=O) NH-, stacked film and
Distance piece.
Background technology
The nonaqueous electrolytic solution secondary batteries such as lithium secondary battery are widely used as now for PC, portable phone and just
Take the battery of the equipment such as information terminal.
The energy density of these nonaqueous electrolytic solution secondary batteries with lithium rechargeable battery as representative is high.Therefore, because
The breakage of battery or the breakage of equipment that employs battery and in the case of there is internal short-circuit or external short circuit, big electricity sometimes
Stream flows through and nonaqueous electrolytic solution secondary battery heating.Therefore, for nonaqueous electrolytic solution secondary battery it is desirable to by prevent certain with
On heating guaranteeing high security.
As the method for the safety guaranteeing nonaqueous electrolytic solution secondary battery, typically nonaqueous electrolytic solution secondary battery is assigned
The method giving closing function.Closing function is：When nonaqueous electrolytic solution secondary battery occurs abnormal heating, hindered using distance piece
Ion between disconnected positive pole and negative pole by and prevent the function of generating heat further.That is, as guaranteeing nonaqueous electrolytic solution secondary battery
Safety method, usually for example following method：It is being configured at because of reasons such as the internal short-circuits between positive pole and negative pole
When flowing through abnormal current in the distance piece between the positive pole in this battery and negative pole, block this electric current and stop (closing) in this electricity
Flow through super-high-current in pond, thus give the function that suppression is generated heat further.Here, the use in nonaqueous electrolytic solution secondary battery
In the case that temperature exceedes common use temperature, the distance piece melting because of produced heat, the blocking of its result is formed at interval
The pore of part, thus carries out above-mentioned closing.It is explained, preferably：Distance piece after carrying out above-mentioned closing, even if in battery
Reach a certain degree of high temperature to be also destroyed, the state remaining off because of heat.
As above-mentioned distance piece, be generally used in when there is abnormal heating at e.g., from about 80～180 DEG C melting with poly-
Alkene is the perforated membrane of main constituent.However, the distance piece with above-mentioned perforated membrane as main constituent is due to dimensionally stable at high temperature
Property insufficient, therefore in the period carrying out closing function, distance piece shrinks or distance piece occurs rupture of membranes etc..Even if as a result,
Carry out closing function, there is also positive pole and negative pole directly contact and cause the risk of internal short-circuit.That is, based on above-mentioned perforated membrane
There is the risk that cannot fully suppress the abnormal heating caused by internal short-circuit in the distance piece of composition.It is therefore desirable to be able to guarantee
The distance piece of greater security.
As the perforated membrane of excellent heat resistance, such as in patent documentation 1, propose stacking on polyolefinic micro-porous film
There is the perforated membrane of the heat-resisting porous layer by aromatic polymers such as aromatic series virtue amide.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Laid-Open Patent Publication " Japanese Unexamined Patent Publication 2009-205959 "
Content of the invention
Invention problem to be solved
However, it is difficult in the way of making it have target intrinsic viscosity stably in the perforated membrane that patent documentation 1 is recorded
Manufacture the aromatic polymer for forming heat-resisting porous layer.That is, have be difficult to stably to manufacture can be formed excellent heat-resisting
Porous layer and have specific intrinsic viscosity aromatic polymer problem.
The present invention is the invention considering above-mentioned problem and completing, and its main purpose is to provide a kind of aromatic polymer
Manufacture method, it stably can manufacture aromatic polymer in the way of making it have specific intrinsic viscosity, described fragrance
Adoption compound is suitable for manufacturing the distance piece of nonaqueous electrolytic solution secondary battery, the distance piece of described nonaqueous electrolytic solution secondary battery be
The distance piece of the excellent nonaqueous electrolytic solution secondary battery of the shape stability under high temperature, even if it in the breakage because of battery or makes
In the case of there is internal short-circuit or external short circuit with the breakage of the equipment of battery, also can prevent necessarily above heating,
Such that it is able to guarantee high security.
Means for solving the problems
The present inventor is carried out to the manufacture method of the aromatic polymer with the structure shown in-C (=O) NH- deeply
Research, described aromatic polymer is by making aromatic diamine and having the change of the water-disintegrable reactive group reacting with amino
Compound is reacted in organic solvent and is obtained.Itself it is found that：By adjust organic solvent moisture content such that it is able to so that
It has the mode of specific intrinsic viscosity and stably manufactures aromatic polymer, and described aromatic polymer is suitable for manufacture can
Guarantee the distance piece of the nonaqueous electrolytic solution secondary battery of high security.So that completing the present invention.
In order to solve above-mentioned problem, the manufacture method of the aromatic polymer of the present invention is characterised by, it is that have-C
The manufacture method of the aromatic polymer of structure shown in (=O) NH-, this manufacture method makes aromatic diamine and passes through with having
React with amino and form the compound of the water-disintegrable reactive group of the structure shown in-C (=O) NH- in organic solvent
In reacted, above-mentioned organic solvent contains the water of 200ppm～2500ppm, and the intrinsic viscosity of above-mentioned aromatic polymer is
1.5dL/g～3.0dL/g.
Invention effect
According to the present invention it is possible to stably manufacture the spy with the structure shown in-C (=O) NH- and aromatic polymer
Property viscosity be 1.5dL/g～3.0dL/g aromatic polymer.Therefore, given play to that can provide can be specific to make it have
Intrinsic viscosity mode stably manufacture aromatic polymer manufacture method effect, described aromatic polymer be suitable for system
Make the distance piece of nonaqueous electrolytic solution secondary battery, the distance piece of described nonaqueous electrolytic solution secondary battery dimensionally stable at high temperature
Property is excellent, even if there is internal short-circuit or external short circuit in the breakage because of the breakage of battery or the equipment employing battery
In the case of, also can prevent necessarily above heating, such that it is able to guarantee high security.
Brief description
Fig. 1 is to represent in embodiment and comparative example aromatic diamine and have the water-disintegrable reactive base reacting with amino
The chart of the relation of intrinsic viscosity of the mol ratio of compound of group and aromatic polymer.
Specific embodiment
Hereinafter, an embodiment of the invention is described in detail.It is explained, in this application, " A～B " table
Show more than A and below B.
The manufacture method of the aromatic polymer of the present invention is that have the fragrant adoption of the structure shown in-C (=O) NH-
The manufacture method of compound, this manufacture method is made aromatic diamine and has by being reacted with amino and form-C (=O) NH- institute
The compound of the water-disintegrable reactive group of the structure shown is reacted in organic solvent, and above-mentioned organic solvent contains
The water of 200ppm～2500ppm, the intrinsic viscosity of above-mentioned aromatic polymer is 1.5dL/g～3.0dL/g.
Made in the manufacture field of nonaqueous electrolytic solution secondary battery using the aromatic polymer that above-mentioned manufacture method obtains
Component (heat-resisting porous layer) for constituting distance piece to use.Above-mentioned aromatic polymer is heat-resistant resin, using being applied
Applying (coating) in the base material using as distance piece and makes the simple method such as its drying, can be formed resistance on the surface of this base material
Overabundant heat aperture layer.The thickness of heat-resisting porous layer be preferably more than 1 μm and less than 10 μm, be more preferably more than 1 μm and less than 5 μm, special
You Xuanwei more than 1 μm and less than 4 μm.In addition, the aperture of pore that heat-resisting porous layer has be preferably less than 3 μm, more excellent
Elect less than 1 μm as.By heat-resisting porous layer is formed on above-mentioned base material, such that it is able to the thermostability of distance piece is improved to for example
400 DEG C about.Be explained, heat-resisting porous layer can as needed containing mean diameter be more than 0.01 μm and less than 1 μm,
The filler being formed by organic dust or inorganic powder.
As the above-mentioned base material of the distance piece as nonaqueous electrolytic solution secondary battery, preferred thermoplastic resin.Specifically,
As this thermoplastic resin, can enumerate for example：The polyolefin such as polyethylene, polypropylene, polybutene, ethylene-propylene copolymer；With
And thermoplastic polyurethane.Wherein, in order to stop (closing) to flow through in nonaqueous electrolytic solution secondary battery at lower temperatures
High current, above-mentioned thermoplastic resin is more preferably polyethylene.As this polyethylene, Low Density Polyethylene can be enumerated, high density is gathered
Ethylene, wire polyethylene (ethene-alpha-olefin copolymer) and the ultra-high molecular weight polyethylene that molecular weight is more than 1,000,000
Deng.
Raw material as aromatic polymer is aromatic diamine, can enumerate for example hydroxy diphenylamine, 1,2- phenylenediamine,
1,3- phenylenediamine, 1,4- phenylenediamine, 3,3 '-benzophenone diamidogen, 3,3 '-methylene dianiline (MDA), 3,3 '-diaminourea two
Phenylsulfone, 1,2- naphthylenediamine, 1,3- naphthylenediamine, 1,4- naphthylenediamine, 1,5- naphthylenediamine, 1,6- naphthylenediamine, 1,7- naphthalene two
Amine, 1,8- naphthylenediamine, 2,3- naphthylenediamine, 2,6- naphthylenediamine and 3,3 '-benzidine etc..Wherein, above-mentioned aromatic diamine
More preferably 1,4- phenylenediamine.These aromatic diamines can only be used singly, or in combination of two or more kinds.
Raw material as aromatic polymer is had by being reacted with amino and forms the knot shown in-C (=O) NH-
The compound (hereinafter referred to as compound containing reactive group) of the water-disintegrable reactive group of structure, can enumerate and have acyl group
Compound.Specifically, as this compound containing reactive group, can enumerate for example, dicarboxylic anhydride, acyl dihalide or pass through
React with amino and form the diisocyanate of urea bond (- NH-C (=O) NH-).The compound with acyl group is more preferably virtue
Fragrant compounds of group.
Specifically, as dicarboxylic anhydride, more preferably aromatic diacid acid anhydride.As this aromatic dianhydride, can enumerate for example equal
Acid dianhydride, 3,3 ', 4,4 '-sulfobenzide. tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,2 '-
Double (3,4-dicarboxyphenyi) hexafluoropropane dianhydrides and 3,3 ', 4,4 '-biphenyltetracarboxylic acid dianhydride etc..
As acyl dihalide, more preferably aromatic series acyl dichloride.As this aromatic series acyl dichloride, example can be enumerated
As phthalyl dichloro, tere-phthaloyl dichloride, equal benzene four acyl dichloro, 3,3 ', 4,4 '-sulfobenzide. four formyl dichloro, 3,
3 ', 4,4 '-benzophenone four formyl dichloro, 2,2 '-bis- (3,4- dicarboxyphenyi) HFC-236fa dichloros, 3,3 ', 4,4 '-
Biphenyl tetracarboxylic acyl dichloro, 1,2- benzenedicarboxylic acid dichloride, 1,3- benzenedicarboxylic acid dichloride, 1,4- benzenedicarboxylic acid dichloride, 1,2- naphthalene
Two formyl dichloros, 1,3- naphthalene two formyl dichloro, 1,4- naphthalene two formyl dichloro, 1,5- naphthalene two formyl dichloro, 1,6- naphthalene diformazan
Acyl dichloro, 1,7- naphthalene two formyl dichloro, 1,8- naphthalene two formyl dichloro, 2,3- naphthalene two formyl dichloro, 2,6- naphthalene two formyl two
Chlorine, 3,3 '-connection benzenedicarboxylic acid dichloride, 3,3 '-benzophenone two formyl dichloro and 3,3 '-sulfobenzide. two formyl dichloro etc..
As diisocyanate, more preferably aromatic diisocyanate.As this aromatic diisocyanate, example can be enumerated
As 1,2- phenylene vulcabond, 1,3- phenylene vulcabond, 1,4- phenylene vulcabond, 1,2- Asia naphthalene
Group diisocyanate, 1,3- naphthalene diisocyanate, 1,4- naphthalene diisocyanate, 1,5- naphthylene two Carbimide.
Ester, 1,6- naphthalene diisocyanate, 1,7- naphthalene diisocyanate, 1,8- naphthalene diisocyanate, 2,3- are sub-
Naphthalene diisocyanate, 2,6- naphthalene diisocyanate, 3,3 '-biphenylene diisocyanate, 3,3 '-benzophenone
Diisocyanate and 3,3 '-sulfobenzide. diisocyanate etc..
In foregoing illustrative compound, above-mentioned compound containing reactive group is more preferably aromatic series acyl dihalide,
More preferably tere-phthaloyl dichloride.These compounds containing reactive group can only using a kind or be applied in combination 2 kinds with
On.
Aromatic polymer for example can be by being dissolved with the muriatic organic solvent of alkali metal or alkaline-earth metal
Make above-mentioned aromatic diamine and above-mentioned compound containing reactive group anti-at -20 DEG C～50 DEG C, more preferably -10 DEG C～40 DEG C
React (polymerization) at a temperature of answering and obtain.Above-mentioned aromatic diamine and the above-mentioned mol ratio (fragrance containing reactive group compound
Race's diamidogen/compound containing reactive group) it is usually 1.000～1.050, be preferably 1.000～1.040, more preferably 1.000
～1.030.In addition, the above-mentioned muriatic concentration being dissolved in above-mentioned organic solvent is preferably 2 weight %～10 weight %, more excellent
Elect 3 weight %～8 weight % as.
As above-mentioned chloride, can enumerate for example：The alkali-metal chloride such as sodium chloride and potassium chloride；And magnesium chloride and
The chloride of the alkaline-earth metal such as calcium chloride.Wherein, above-mentioned chloride is more preferably calcium chloride.These chlorides can be only using 1
Plant or be applied in combination two or more.
And, by the mol ratio (aromatic diamine/contain reactivity by aromatic diamine and containing reactive group compound
Group compound) be adjusted in above range, in addition reaction temperature be adjusted in above range, will be dissolved in further organic
The muriatic concentration of solvent is adjusted in above range, such that it is able to obtain sufficiently gathering for forming heat-resisting porous layer
Right aromatic polymer.
As above-mentioned organic solvent, the polar solvent of aprotic can be enumerated.Specifically, as the pole of this aprotic
Property solvent, can enumerate such as METHYLPYRROLIDONE, N,N-dimethylacetamide and DMF etc..
Wherein, the polar solvent of above-mentioned aprotic is more preferably METHYLPYRROLIDONE.These organic solvents can only make
With a kind it is also possible to be applied in combination two or more.
Used in reaction the moisture content of above-mentioned organic solvent be usually 200ppm～2500ppm, be preferably 200ppm～
1500ppm, more preferably 250ppm～1000ppm.In the manufacture method of the present invention, by moisture content for 200ppm～
Above-mentioned aromatic diamine is made to react with above-mentioned compound containing reactive group in the above-mentioned organic solvent of 2500ppm, thus relatively
In the change of the mol ratio of these compounds, the variation of the intrinsic viscosity of the aromatic polymer of gained diminishes.Its result is easy
Control the intrinsic viscosity of this aromatic polymer.The assay method of the moisture content of organic solvent is chatted in an embodiment in detail
State.
That is, if the moisture content of above-mentioned organic solvent is less than 200ppm, with respect to above-mentioned aromatic diamine with above-mentioned containing anti-
The change of the mol ratio of answering property group compound, the variation of the intrinsic viscosity of aromatic polymer becomes big.Therefore, because of this mol ratio
Fine change and the intrinsic viscosity of aromatic polymer change it is difficult to obtain the aromatic series with target intrinsic viscosity
Polymer.On the other hand, if the moisture content of above-mentioned organic solvent is more than 2500ppm, above-mentioned aromatic diamine is with above-mentioned containing anti-
The reaction of answering property group compound cannot fully be carried out it is impossible to obtain reaching the aromatic polymer of target intrinsic viscosity.
Variable quantity with the above-mentioned intrinsic viscosity of 0.01 change of above-mentioned mol ratio is preferably 0.1～0.7dL/g, more
It is preferably 0.2～0.6dL/g, more preferably 0.3～0.5dL/g.
If in addition, the moisture content of above-mentioned organic solvent is more than 200ppm, existing and be not susceptible to side reaction, have above-mentioned
It is difficult in machine solvent to generate the tendency of the insoluble component such as gel.On the other hand, if the moisture content of above-mentioned organic solvent is 2500ppm
Hereinafter, then there is the storage stability height of the solution (polymer composition) of aromatic polymer, be somebody's turn to do in above-mentioned organic solvent
Aromatic polymer is difficult the tendency separating out.If generating the insoluble component such as gel in above-mentioned organic solvent, by aromatic series
Fold, striped is easily produced, the outward appearance that there is heat-resisting porous layer becomes bad tendency in the heat-resisting porous layer that polymer is formed.
With respect to aromatic diamine and containing reactive group compound total amount above-mentioned organic solvent usage amount, go up
State aromatic diamine when the reaction in organic solvent starts and total concentration containing reactive group compound (raw material dense
Degree) be preferably 0.5 weight %～20 weight %, more preferably 1 weight %～15 weight %, more preferably 3 weight %～
12 weight %.
Make above-mentioned aromatic diamine and above-mentioned compound containing reactive group react obtained by aromatic polymer be preferably
Aromatic polyamide, more preferably fully aromatic polyamide.Aromatic polyamide can be the aromatic series polyamides of para-orientation
Amine or the aromatic polyamide of meta orientation.But, from making high mechanical strength and easily forming the aspect of porous, fragrant
Polyamide is more preferably the aromatic polyamide of para-orientation.
And, above-mentioned aromatic polymer has for main chain, the fragrant adoption compound of the structure shown in-C (=O) NH-, special
Property viscosity be 1.5dL/g～3.0dL/g, more preferably 1.7dL/g～2.5dL/g, more preferably 1.8dL/g～2.3dL/
g.It is explained, the assay method of intrinsic viscosity is described in detail in an embodiment.
Above-mentioned intrinsic viscosity can by adjust aromatic diamine with containing reactive group compound above-mentioned mol ratio and/
Or the moisture content of organic solvent is being controlled.In the case that above-mentioned intrinsic viscosity is less than 1.5dL/g, due to above-mentioned aromatic series
The molecular weight of polymer is little, and the elastic modelling quantity of the heat-resisting porous layer therefore being formed declines, contraction when base material melts because of heat
Inhibition step-down.On the other hand, if above-mentioned intrinsic viscosity is more than 3.0dL/g, the molecule quantitative change of above-mentioned aromatic polymer
Too much, therefore the solution (polymer composition) of aromatic polymer is coated on screening characteristics during base material and reduces.
As being aromatic polyamide using the aromatic polymer that the manufacture method of the present invention obtains, specifically, can
Enumerate for example poly- (to phenylene terephthalamide), poly- (metaphenylene isophtalamide), poly- (paraphenylene terephthalamide), poly-
(Benzoylamide), poly- (4,4 '-benzanilide terephthalamide), poly- (to phenylene -4,4 '-biphenylene diformazan
Amide), poly- (metaphenylene -4,4 '-biphenylene diformamide), poly- (to phenylene -2,6- aphthalimide), poly-
(metaphenylene -2,6- aphthalimide), poly- (2- chlorine to phenylene terephthalamide), to phenylene paraphenylene terephthalamide
Amine/2,6- dichloro to phenylene terephthalamide copolymer and metaphenylene terephthalamide/2,6- dichloro are to sub- benzene
Base terephthalamide copolymer etc..Wherein, above-mentioned aromatic polyamide is more preferably poly- (to phenylene terephthalamide).
Aromatic polyamide can be the mixture of foregoing illustrative polymer.
In the manufacture field of nonaqueous electrolytic solution secondary battery, by the solution of aromatic polymer for example apply (coating) in
After above-mentioned base material, remove organic solvent, thus can simply manufacture the layer being formed with heat-resisting porous layer on the surface of this base material
Folded film.Solution coating (coating) of aromatic polymer is organic in the method for base material, the solution removing after coating (coating)
The method of solvent is not particularly limited, and known method may be appropriately used.
The stacked film manufacturing using above-mentioned manufacture method is also comprised in the present invention.And, by suitably adopting known side
Method, such that it is able to simply manufacture the distance piece comprising above-mentioned stacked film.In addition, by suitably adopting known method, thus
The nonaqueous electrolytic solution secondary battery comprising above-mentioned distance piece can simply be manufactured.
Be explained, replace directly using by carry out aromatic polymer obtained by above-mentioned reaction solution it is also possible to
Coating (coating) uses：I () removes the solution obtained by a part of solvent from above-mentioned solution；(ii) add in above-mentioned solution
Solution obtained by solubilizer；(iii) clean above-mentioned solution using water, methanol etc. and remove the solution of chloride gained；(iv) exist
Separate out aromatic polymer while part or all of evaporation making solvent, and be polymerized from this aromatic series using methods such as washings
So as to be dissolved in solution obtained by solvent etc. after thing removing chloride.
The present invention is not limited to the respective embodiments described above, can carry out various changes in the scope shown in claim
More, will in various embodiments respectively disclosed technological means appropriately combined obtained from embodiment be also contained in this
In bright technical scope.And then, by combining technological means disclosed in difference in each embodiment such that it is able to form new skill
Art feature.
Embodiment
Various assay methods in the application are as shown below.In addition, the evaluation of physical property of aromatic polymer is using following
Method carrying out.
(1) moisture content
Using karr-Fischer (KarlFischer) moisture rate meter, according to conventional methods, measure the aqueous of organic solvent
Rate.
(2) intrinsic viscosity
The aromatic polymer preparing the aromatic polymer being dissolved with 0.5g in 96%～98% sulphuric acid of 100ml is molten
Liquid.In addition, preparing 96%～98% sulphuric acid as blank.For above-mentioned aromatic polymer solution and blank, point
Do not determine the flowing time at 30 DEG C according to conventional methods using capillary viscosimeter.According to following formula, by gained flowing when
Between ratio estimated performance viscosity.
Intrinsic viscosity (unit：Dl/g)=ln (T/T0)/C
In formula, T is the flowing time (second) of aromatic polymer solution, T0Flowing time (second) for blank, C table
Show the concentration (g/dl) of the aromatic polymer in aromatic polymer solution.
(3) filter blockage factor
The assay method filtering blockage factor (is issued, issues using changing six editions chemical engineering brief guides on 2 25th, 1999
Institute：Wan Shan Co., Ltd., editor：Civic organization's chemistry engineering meeting) page 813 in " 15 solid-liquid solid and gases separately " " 15 3
Formula described in " table 15 6 block filtering type " of filtration pressure " is calculating.
Specifically, using 2000 mesh (apertures：14 μm) SUS filter (diameter：25mm) side is with 1kgf (about
9.8N) carry out pressurization side and be filtered through the solution (being dissolved with the solution of aromatic polymer in organic solvent) that reaction obtains.
Then, according to following formula, calculate and filter blockage factor.
T/V=KS×t+1/Q0
Filter blockage factor H (unit：m2/m3)=A × KS
In formula, A is filter area (m2), t is filtration time (second), and V is filtration yield (m3), KSRepresent the chart of t/V and t
In slope, 1/Q0Represent the intercept in the chart with t for the t/V.
(4) it is formed at the evaluation of the heat-resisting porous layer (applicator surface) on base material
Using by react the solution (being dissolved with the solution of aromatic polymer in organic solvent) that obtains be coated in as
On the polyethylene of base material, it is consequently formed heat-resisting porous layer.Then, visually observe and have or not striped in the heat-resisting porous layer being formed
And evaluated.With regard to evaluating, when observing the direction orthogonal with coating direction, will there is the area that there are more than 2 stripeds
The situation in domain be set to bad, no existed the region of more than 2 stripeds situation (striped is the situation of less than 1) be set to good
Good.
(embodiment 1)
As aromatic polymer, by the use of following method manufacture as the poly- (to phenylene pair of fully aromatic polyamide
Benzenedicarboxamide) (hereinafter referred to as PPTA).
Using the detachable flask possessing agitator, the 500ml of thermometer, nitrogen inflow pipe and powder body interpolation mouth.Logical
After crossing the inflow nitrogen into this flask and so that it is fully dried, add the N- methyl -2- pyrrole as organic solvent in flask
Pyrrolidone (hereinafter referred to as NMP) 409.2g, adds as muriatic calcium chloride (after being vacuum dried 2 hours at 200 DEG C again
Using) 30.8g, so as to be warmed up to 100 DEG C, calcium chloride is completely dissolved.Afterwards, the temperature making the solution of gained returns to room temperature
(25 DEG C), the moisture content of solution is adjusted to 500ppm.
Then, add as aromatic diamine p-phenylenediamine (hereinafter referred to as PPD) 13.20g so as to be completely dissolved.
While the temperature of this solution being maintained at 20 ± 2 DEG C and stirring, side is added as the paraphenylene terephthalamide containing reactive group compound
Dichloro (hereinafter referred to as TPC) 24.30g (mol ratio：PPD/TPC=1.020).But, the interval that TPC separates about 10 minutes is divided
It is added for three times.After the interpolation of TPC terminates, while the temperature of solution being maintained at 20 ± 2 DEG C and stirring, while making PPD and TPC's
Reaction ripening 1 hour.Thus obtain the solution of PPTA.The PPTA display optical anisotropy of gained.
The result of calculation of the inventory of raw material etc. and the intrinsic viscosity of PPTA is concluded and is recorded in table 1
(embodiment 2)
In addition to the addition of TPC is changed to 24.18g (PPD/TPC=1.025), carry out similarly to Example 1
Operation and reaction, obtain the solution of PPTA.The result of calculation of the inventory of raw material etc. and the intrinsic viscosity of PPTA is concluded and records
In table 1
(embodiment 3)
In addition to the addition of TPC is changed to 24.06g (PPD/TPC=1.030), carry out similarly to Example 1
Operation and reaction, obtain the solution of PPTA.The result of calculation of the inventory of raw material etc. and the intrinsic viscosity of PPTA is concluded and records
In table 1
(embodiment 4)
Mode except reaching 300ppm according to the moisture content making the solution being dissolved with calcium chloride in NMP be adjusted with
Outward, carry out operation similarly to Example 1 and reaction, obtain the solution of PPTA.Characteristic by the inventory of raw material etc. and PPTA
Estimating of viscosity result is concluded and is recorded in table 1 then, and the result of the evaluation of physical property of above-mentioned PPTA is recorded in table 2.
(embodiment 5)
The mode that moisture content according to making the solution being dissolved with calcium chloride in NMP reaches 300ppm is adjusted, and
The addition of TPC is changed to 24.18g (PPD/TPC=1.025), in addition, carry out operation similarly to Example 1 and
Reaction, obtains the solution of PPTA.The result of calculation of the inventory of raw material etc. and the intrinsic viscosity of PPTA is concluded and is recorded in table 1
(embodiment 6)
The mode that moisture content according to making the solution being dissolved with calcium chloride in NMP reaches 300ppm is adjusted, and
The addition of TPC is changed to 24.06g (PPD/TPC=1.030), in addition, carry out operation similarly to Example 1 and
Reaction, obtains the solution of PPTA.The result of calculation of the inventory of raw material etc. and the intrinsic viscosity of PPTA is concluded and is recorded in table 1
(embodiment 7)
The mode that moisture content according to making the solution being dissolved with calcium chloride in NMP reaches 2000ppm is adjusted, and
The addition of TPC is changed to 24.78g (PPD/TPC=1.000), in addition, carry out operation similarly to Example 1 and
Reaction, obtains the solution of PPTA.The result of calculation of the inventory of raw material etc. and the intrinsic viscosity of PPTA is concluded and is recorded in table 1
(embodiment 8)
In addition to the addition of TPC is changed to 24.22g (PPD/TPC=1.023), carry out similarly to Example 1
Operation and reaction, obtain the solution of PPTA.The result of calculation of the inventory of raw material etc. and the intrinsic viscosity of PPTA is concluded and records
In table 1 then, the result of the evaluation of physical property of above-mentioned PPTA is recorded in table 2.
(embodiment 9)
In addition to the addition of TPC is changed to 24.18g (PPD/TPC=1.025), carry out similarly to Example 1
Operation and reaction, obtain the solution of PPTA.The result of calculation of the inventory of raw material etc. and the intrinsic viscosity of PPTA is concluded and records
In table 1 then, the result of the evaluation of physical property of above-mentioned PPTA is recorded in table 2.
(comparative example 1)
Mode except reaching 120ppm according to the moisture content making the solution being dissolved with calcium chloride in NMP be adjusted with
Outward, carry out operation similarly to Example 1 and reaction, obtain the solution of PPTA.Characteristic by the inventory of raw material etc. and PPTA
Estimating of viscosity result is concluded and is recorded in table 1.In this PPTA, the amount of insoluble component is many.Although attempting carrying out the thing of above-mentioned PPTA
Property evaluate, but the solution of the PPTA of gained no mobility, therefore cannot calculate filtration blockage factor (can not measure).In addition,
The solution of PPTA cannot be coated on base material, therefore cannot form heat-resisting porous layer (can not evaluate).Result note by comparative example 1
It is loaded in table 2.
(comparative example 2)
The mode that moisture content according to making the solution being dissolved with calcium chloride in NMP reaches 120ppm is adjusted, and
The addition of TPC is changed to 24.18g (PPD/TPC=1.025), in addition, carry out operation similarly to Example 1 and
Reaction, obtains the solution of PPTA.The result of calculation of the inventory of raw material etc. and the intrinsic viscosity of PPTA is concluded and is recorded in table 1
(comparative example 3)
The mode that moisture content according to making the solution being dissolved with calcium chloride in NMP reaches 120ppm is adjusted, and
The addition of TPC is changed to 24.06g (PPD/TPC=1.030), in addition, carry out operation similarly to Example 1 and
Reaction, obtains the solution of PPTA.The result of calculation of the inventory of raw material etc. and the intrinsic viscosity of PPTA is concluded and is recorded in table 1
(comparative example 4)
The mode that moisture content according to making the solution being dissolved with calcium chloride in NMP reaches 3000ppm is adjusted, and
The addition of TPC is changed to 24.78g (PPD/TPC=1.000), in addition, carry out operation similarly to Example 1 and
Reaction, obtains the solution of PPTA.The result of calculation of the inventory of raw material etc. and the intrinsic viscosity of PPTA is concluded and is recorded in table 1
[table 1]
[table 2]
Mol ratio by the aromatic diamine (PPD) in embodiment and comparative example and compound containing reactive group (TPC)
Draw a diagram and shown in Figure 1 with the relation of the intrinsic viscosity of the aromatic polymer (PPTA) of gained.By mol ratio (PPD/
TPC) the linear approximate of each moisture content is tried to achieve in the intrinsic viscosity (longitudinal axis) of the aromatic polymer of (transverse axis) and gained, and calculates companion
With each moisture content mol ratio 0.01 change intrinsic viscosity variable quantity.Its result is：When moisture content is for 120ppm
For 0.89dL/g, it is 0.53dL/g when moisture content is for 300ppm, be 0.40dL/g when moisture content is for 500ppm.Thus sentence
Fixed：If moisture content reduces to 120ppm from 300ppm, the variable quantity of intrinsic viscosity drastically becomes big, if moisture content is not enough
200ppm, then be difficult to for the intrinsic viscosity of aromatic polymer to be controlled to desired value.In addition judge：It is 3000ppm in moisture content
When, even if mol ratio is 1.000, target intrinsic viscosity also cannot be obtained.
And then, the filtration blockage factor of the aromatic polymer being obtained using the NMP polymerization for 500ppm for the moisture content is abundant
Low, and corrugationless, striped in the heat-resisting porous layer being formed using this aromatic polymer, therefore can form outward appearance good
Heat-resisting porous layer.
Therefore, clearly judged by the result that table 2 is recorded：Can using the aromatic polymer that the manufacture method of the present invention obtains
To be suitable as the heat-resisting porous layer of the distance piece comprising stacked film.
Industrial applicability
The manufacture method of the aromatic polymer of the present invention can be widely used in for example being able to ensure that the non-of high security
In the manufacture field of water electrolysis liquid secondary battery.
Claims (12)
1. a kind of manufacture method of aromatic polymer, it is the aromatic polymer with the structure shown in-C (=O) NH-
Manufacture method,
This manufacture method is made aromatic diamine and has by being reacted with amino and form the structure shown in-C (=O) NH-
The compound of water-disintegrable reactive group is reacted in organic solvent,
Described organic solvent contains the water of 200ppm～2500ppm,
The intrinsic viscosity of described aromatic polymer is 1.5dL/g～3.0dL/g.
2. manufacture method according to claim 1, wherein, described organic solvent contains the water of 200ppm～1500ppm.
3. manufacture method according to claim 1 and 2, wherein, has the described compound of water-disintegrable reactive group
For having the compound of acyl group.
4. the manufacture method according to any one of claims 1 to 3, wherein, described aromatic polymer is all aromatic
Polyamide.
5. the manufacture method according to any one of Claims 1 to 4, wherein, described aromatic diamine with have water-disintegrable
The described compound of reactive group mol ratio be aromatic diamine/compound be 1.000～1.050.
6. the manufacture method according to any one of Claims 1 to 5, its make described aromatic diamine with have water-disintegrable
The described compound of reactive group is reacted under -20 DEG C～50 DEG C of reaction temperature.
7. the manufacture method according to any one of claim 1～6, wherein, described organic solvent is dissolved with chloride, and
The muriatic concentration dissolving in organic solvent is 2 weight %～10 weight %.
8. the manufacture method according to any one of claim 1～7, wherein, when the reaction in described organic solvent starts
Described aromatic diamine and have water-disintegrable reactive group described compound total concentration be 0.5 weight %～20
Weight %.
9. a kind of manufacture method of stacked film, its virtue that will be manufactured using the manufacture method any one of claim 1～8
The solution of fragrant adoption compound is coated on base material and removes organic solvent.
10. a kind of stacked film, it is to be manufactured using the manufacture method described in claim 9.
A kind of 11. distance pieces, it comprises the stacked film described in claim 10.
12. a kind of nonaqueous electrolytic solution secondary battery, it comprises the distance piece described in claim 11.
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| JP2014136953 | 2014-07-02 | ||
| JP2014-136953 | 2014-07-02 | ||
| PCT/JP2015/068840 WO2016002785A1 (en) | 2014-07-02 | 2015-06-30 | Aromatic polymer manufacturing method, layered film, and separator |
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| JP (1) | JPWO2016002785A1 (en) |
| KR (1) | KR20170028318A (en) |
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| CN107903391A (en) * | 2017-10-31 | 2018-04-13 | 上海恩捷新材料科技股份有限公司 | Solution-type aromatic polymer and application thereof |
| WO2019085899A1 (en) * | 2017-10-31 | 2019-05-09 | Shanghai Energy New Materials Technology Co., Ltd. | Methods for preparing polymer solutions, separators, electrochemical devices and products thereof |
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| US20210408636A1 (en) | 2020-06-30 | 2021-12-30 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery laminated separator |
| KR20220002144A (en) | 2020-06-30 | 2022-01-06 | 스미또모 가가꾸 가부시키가이샤 | Composition |
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| CN1087315C (en) * | 1994-02-11 | 2002-07-10 | 阿克佐诺贝尔公司 | Process for the batchwise preparation of poly-p-phenylene terephthalamide |
| TWM381105U (en) * | 2010-01-11 | 2010-05-21 | Top Victory Invest Ltd | Power-saving control circuit |
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| JPS61103926A (en) * | 1984-10-29 | 1986-05-22 | Teijin Ltd | Control of polymerization degree for aromatic polyamide |
| JPS6254725A (en) * | 1985-05-29 | 1987-03-10 | Teijin Ltd | Aromatic polyamide and its production |
| DE4010941A1 (en) * | 1990-04-05 | 1991-10-10 | Hoechst Ag | METHOD FOR PRODUCING AROMATIC POPYAMIDES WITH HIGH HYDROLYSIS RESISTANCE |
| CA2181421C (en) * | 1995-07-18 | 2007-02-13 | Tsutomu Takahashi | Para-oriented aromatic polyamide porous film |
| JP3279189B2 (en) * | 1995-07-18 | 2002-04-30 | 住友化学工業株式会社 | Para-oriented aromatic polyamide porous film, production method thereof and use thereof |
| JP2964961B2 (en) * | 1995-10-06 | 1999-10-18 | 東レ株式会社 | Aromatic polyamide film and magnetic recording medium |
| JPH09263634A (en) * | 1996-03-29 | 1997-10-07 | Toray Ind Inc | Aromatic polyamide composition |
| JP2003040999A (en) * | 2001-07-27 | 2003-02-13 | Sumitomo Chem Co Ltd | Fully aromatic polyamide, fully aromatic polyamide porous film and separator for nonaqueous electrolytic solution secondary battery |
| JP2009205959A (en) | 2008-02-28 | 2009-09-10 | Teijin Ltd | Manufacturing method of nonaqueous electrolyte battery separator |
| JP2010113804A (en) * | 2008-10-08 | 2010-05-20 | Sumitomo Chemical Co Ltd | Nonaqueous electrolyte secondary battery |
| JP5714441B2 (en) * | 2010-08-06 | 2015-05-07 | 住友化学株式会社 | Separator |
-
2015
- 2015-06-30 KR KR1020167035878A patent/KR20170028318A/en not_active Application Discontinuation
- 2015-06-30 JP JP2016531395A patent/JPWO2016002785A1/en active Pending
- 2015-06-30 CN CN201580031898.1A patent/CN106488946B/en active Active
- 2015-06-30 WO PCT/JP2015/068840 patent/WO2016002785A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087315C (en) * | 1994-02-11 | 2002-07-10 | 阿克佐诺贝尔公司 | Process for the batchwise preparation of poly-p-phenylene terephthalamide |
| TWM381105U (en) * | 2010-01-11 | 2010-05-21 | Top Victory Invest Ltd | Power-saving control circuit |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903391A (en) * | 2017-10-31 | 2018-04-13 | 上海恩捷新材料科技股份有限公司 | Solution-type aromatic polymer and application thereof |
| WO2019085899A1 (en) * | 2017-10-31 | 2019-05-09 | Shanghai Energy New Materials Technology Co., Ltd. | Methods for preparing polymer solutions, separators, electrochemical devices and products thereof |
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| JPWO2016002785A1 (en) | 2017-04-27 |
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