JP4339729B2 - Aromatic polyketone and intermediate thereof, method for producing aromatic polyketone, gasket for electrochemical element, separator for electrochemical element, and electrochemical element - Google Patents

Description

  The present invention relates to an aromatic polyketone and an intermediate thereof, a method for producing an aromatic polyketone, a gasket for an electrochemical element, a separator for an electrochemical element, and an electrochemical element including these.

An aromatic polyketone is a chemically stable compound and a material having excellent mechanical properties and heat resistance. Conventionally, most of such aromatic polyketones are so-called aromatic polyether ketones having an ether ring in addition to an aromatic ring and a carbonyl group in the main chain. In contrast, a wholly aromatic polyketone whose main chain is composed only of an aromatic ring and a carbonyl group is expected to exhibit more excellent properties such as heat resistance than conventional aromatic polyether ketones. Is. In recent years, those wholly described in Non-Patent Documents 1 to 4 have been reported as such wholly aromatic polyketones.
Macromolecules, 1993, 26, 19, p. 5262-5263 Polymer processing, 1997, 46, 5, p. 199-207 Macromolecules, 2000, 33, 22, p. 8125-8129 Polymer Journal, 2003, 35, 12, p. 998-1002

  By the way, electrochemical elements such as electric double layer capacitors and lithium ion secondary batteries are often used in small electronic devices such as mobile phones, digital cameras, portable notebook personal computers, and personal digital assistants (PDAs). ing. Such an electrochemical element is used in various forms such as a coin type, a button type (hereinafter collectively referred to as a “coin type”), a cylindrical type, a square type, and a laminated type. These electrochemical elements are generally composed of an electrode, an electrolytic solution, an electrochemical element including a separator disposed between the electrodes, and a container or gasket for sealing them.

  For example, when mounting a coin-type electrochemical element on a substrate or the like in an electronic device, conventionally, a holder for mounting the element is previously set on the substrate by soldering or the like, and then the holder is mounted on the holder. Wearing an electrochemical element has been performed.

  In recent years, in order to further reduce the size of electronic equipment and simplify the manufacturing process, a mounting method in which a coin-type electrochemical element is soldered directly on a substrate instead of using a holder has become mainstream. ing. As such a mounting method, for example, cream solder is applied to a predetermined portion of a substrate, an element is placed thereon, and then the entire substrate is heated to a high temperature exceeding 200 ° C. to soften the cream solder. A so-called solder reflow mounting method for fixing elements is widely used.

  Under such circumstances, the electrochemical element is required to have heat resistance that can withstand the high temperature during reflow described above. In particular, separators and gaskets used in electrochemical elements have conventionally been made of resin materials having low heat resistance (for example, polypropylene (melting point: 160 to 170 ° C.)), and this improves the heat resistance of the electrochemical elements. Since it contributed to the reduction, a highly heat-resistant material that can replace them is eagerly desired.

  Polyphenylene sulfide (PPS, melting point: 280 ° C.) is known as a material having high heat resistance instead of the conventional resin material. Recently, even such PPS has heat resistance in application to electrochemical devices. It tends to be insufficient in terms of sex. That is, recently, from the viewpoint of environmental protection, lead-free solder containing no lead is often used for soldering. When reflow is performed using such lead-free solder, a temperature of about 260 ° C. is required. However, it is difficult to say that the PPS has sufficient heat resistance against such high temperatures.

  Accordingly, the present inventors have focused on the excellent characteristics such as heat resistance of the aromatic polyketone of the above prior art and tried to apply it to separators and gasket materials for electrochemical devices. However, these aromatic polyketones have been difficult to process into films and the like. Moreover, since the processed film etc. were insufficient in strength, it was proved unpreferable as a material used for a separator, a gasket, and the like.

  The present invention has been made in view of such circumstances, and has an excellent heat resistance, is easily processed, has excellent flexibility, and is an aromatic polyketone suitable as a material for an electrochemical device. The purpose is to provide. The present invention also provides a method for producing the aromatic polyketone and an intermediate in the process, a separator and gasket for an electrochemical element obtained from the aromatic polyketone, and an electrochemical element provided with these separator or gasket. Objective.

［式中、Ｒ^１１及びＲ^１２はそれぞれ独立に炭素数２以上のアルキル基、Ｒ^１３及びＲ^１４はそれぞれ独立に水素原子又はアルキル基、Ｒ^１５は下記一般式（２ａ）又は（２ｂ）；

で表される２価の基を示す。］ In order to achieve the above object, the aromatic polyketone of the present invention has a repeating unit represented by the following general formula (1).

Wherein R ¹¹ and R ¹² are each independently an alkyl group having 2 or more carbon atoms, R ¹³ and R ¹⁴ are each independently a hydrogen atom or an alkyl group, and R ¹⁵ is the following general formula (2a) or (2b);

The bivalent group represented by these is shown. ]

  The aromatic polyketone is a novel aromatic polyketone and has a biphenyl structure in which an alkoxy group having 2 or more carbon atoms is bonded to the 2,2′-position in the main chain. Since this aromatic polyketone is a so-called wholly aromatic polyketone having only an aromatic ring and a carbonyl group in the main chain, it has excellent heat resistance. In addition, since the main chain has a biphenyl structure having an alkoxy group having 2 or more carbon atoms in the 2,2 'position, it has excellent flexibility. Therefore, it is possible to form a film having excellent heat resistance and flexibility, and it is suitable as a material for separators, gaskets and the like of electrochemical devices. Furthermore, the aromatic polyketone having the biphenyl structure is superior in solubility in a solvent as compared with the above-described conventional aromatic polyketone, and is easy to process when used for applications such as separators and gaskets. .

［式中、Ｒ^３１及びＲ^３２はそれぞれ独立に炭素数２以上のアルキル基、Ｒ^３３及びＲ^３４はそれぞれ独立に水素原子又はアルキル基を示す。］ The present invention also provides an aromatic polyketone comprising a repeating unit represented by the following general formula (3).

[Wherein, R ³¹ and R ³² each independently represent an alkyl group having 2 or more carbon atoms, and R ³³ and R ³⁴ each independently represent a hydrogen atom or an alkyl group. ]

  Such an aromatic polyketone is a novel aromatic polyketone, and is a wholly aromatic polyketone having, in the main chain, a biphenyl structure to which an alkoxy group having 2 or more carbon atoms is bonded, as described above. An aromatic polyketone having such a structure can also be formed into a film having excellent heat resistance and flexibility, and is also easy to process because of its excellent solubility in a solvent.

［式中、Ｒ^３１及びＲ^３２はそれぞれ独立に炭素数２以上のアルキル基、Ｒ^３３及びＲ^３４はそれぞれ独立に水素原子又はアルキル基を示す。］ The present invention further provides an aromatic polyketone intermediate suitable for the production of the aromatic polyketone represented by the general formula (3). That is, an aromatic polyketone intermediate represented by the following general formula (4) is provided.

[Wherein, R ³¹ and R ³² each independently represent an alkyl group having 2 or more carbon atoms, and R ³³ and R ³⁴ each independently represent a hydrogen atom or an alkyl group. ]

  The aromatic polyketone intermediate having such a structure can easily form the aromatic polyketone represented by the general formula (3) by a coupling reaction or the like.

［式中、Ｒ^１１及びＲ^１２はそれぞれ独立に炭素数２以上のアルキル基、Ｒ^１３及びＲ^１４はそれぞれ独立に水素原子又はアルキル基を示す。］ Moreover, this invention provides the method of manufacturing suitably the aromatic polyketone represented by the said General formula (1). That is, the method for producing an aromatic polyketone of the present invention comprises reacting a 2,2′-dialkoxybiphenylene compound represented by the following general formula (5) with an aromatic dicarboxylic acid or an aromatic dicarboxylic acid chloride. It is characterized by.

[Wherein, R ¹¹ and R ¹² each independently represent an alkyl group having 2 or more carbon atoms, and R ¹³ and R ¹⁴ each independently represent a hydrogen atom or an alkyl group. ]

  Since the biphenyl compound having the structure represented by the chemical formula (5) has excellent properties as an acyl accepting monomer, it reacts with an aromatic dicarboxylic acid or an acid chloride thereof to generate a high molecular weight aromatic polyketone. Can be generated. Therefore, the aromatic polyketone represented by the general formula (1) can be easily obtained by such a production method.

［式中、Ｒ^３１及びＲ^３２はそれぞれ独立に炭素数２以上のアルキル基、Ｒ^３３及びＲ^３４はそれぞれ独立に水素原子又はアルキル基を示す。］ The present invention further provides a method for suitably producing the aromatic polyketone represented by the general formula (3). That is, the method for producing an aromatic polyketone of the present invention includes a step of obtaining an intermediate by reacting a 2,2′-dialkoxybiphenylene compound represented by the following general formula (6) with halobenzoic acid. It is characterized by.

[Wherein, R ³¹ and R ³² each independently represent an alkyl group having 2 or more carbon atoms, and R ³³ and R ³⁴ each independently represent a hydrogen atom or an alkyl group. ]

  Normally, when an aromatic compound undergoes a first-stage acylation reaction, it becomes extremely difficult to undergo the second-stage acylation due to its electron-withdrawing property. In contrast, the compound represented by the general formula (6) easily undergoes a two-step acylation reaction to generate an intermediate of the aromatic polyketone represented by the general formula (4). have. Therefore, according to the production method including such an intermediate production step, the aromatic polyketone represented by the general formula (3) can be easily obtained.

  Moreover, in the said manufacturing method, it is preferable when it further has the process of coupling the intermediate body obtained at the said process with a coupling agent. A high molecular weight aromatic polyketone can be easily obtained by coupling using such a coupling agent.

  The present invention also provides a separator for an electrochemical element containing an aromatic polyketone represented by the general formula (1) or the general formula (3). Furthermore, this invention provides the gasket for electrochemical elements containing the aromatic polyketone represented by the said General formula (1) or the said General formula (3). Since these separators and gaskets are made of the above aromatic polyketone, which is excellent in heat resistance and flexibility, the electrochemical element including these can be used even when mounted on a substrate or the like by solder reflow. Deterioration of characteristics is extremely small.

  Furthermore, this invention provides an electrochemical element provided with the separator or gasket of the said invention. That is, the electrochemical element of the present invention includes a pair of electrodes, a separator disposed between the pair of electrodes, an electrolyte solution contained in the electrode and the separator, and a container that accommodates the electrode, the separator, and the electrolyte solution, The separator contains the aromatic polyketone of the present invention.

  Alternatively, the electrochemical device of the present invention includes a pair of electrodes, a separator disposed between the pair of electrodes, an electrolyte solution contained in the electrode and the separator, and a pair of electrodes that are sandwiched between the electrode, the separator, and the electrolyte solution. A metal container member and a gasket for electrically insulating the pair of container members may be provided, and the gasket may contain the aromatic polyketone of the present invention. In this case, it is more preferable that the separator also contains the aromatic polyketone of the present invention.

  According to the present invention, it is possible to provide an aromatic polyketone that has excellent heat resistance, is easy to process, has excellent flexibility, and is suitable as a material for an electrochemical element. Moreover, it becomes possible to provide the manufacturing method of the said aromatic polyketone, the intermediate body in that case, the separator and gasket for electrochemical elements obtained from the said aromatic polyketone, and an electrochemical element provided with these separators or gaskets. .

  BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the aromatic polyketone of the present invention, a method for producing the same, a separator for an electrochemical element, a gasket for an electrochemical element, and an electrochemical element including these will be described in detail below.

(Aromatic polyketone represented by general formula (1) and method for producing the same)
In the aromatic polyketone represented by the general formula (1), R ¹¹ and R ¹² are each independently preferably an alkyl group having 2 to 10 carbon atoms, and more preferably an alkyl group having 4 to 6 carbon atoms. Moreover, as R <^13> and R < ¹⁴ >, a hydrogen atom is preferable.

Specifically, such an aromatic polyketone may be a poly [(2,2, wherein R ¹¹ and R ¹² are each an ethyl group, R ¹³ and R ¹⁴ are each a hydrogen atom, and R ¹⁵ is a paraphenylene group. 2′-diethoxy-5,5′-biphenylene) terephthaloyl], R ¹¹ and R ¹² are each an ethyl group, R ¹³ and R ¹⁴ are each a hydrogen atom, and R ¹⁵ is a metaphenylene group. [(2,2′-diethoxy-5,5′-biphenylene) isophthaloyl], R ¹¹ and R ¹² are each an ethyl group, R ¹³ and R ¹⁴ are each a hydrogen atom, and R ¹⁵ is the above chemical formula ( 2b), which is a group represented by poly [(2,2′-diethoxy-5,5′-biphenylene) carbonyl (1,4-phenylene) oxy (1,4-phen Ren) carbonyl], and the like.

  The aromatic polyketone having such a structure is produced by reacting the 2,2′-diethoxybiphenyl compound represented by the general formula (5) with an aromatic dicarboxylic acid or an aromatic dicarboxylic acid dichloride. be able to. In such a reaction, the aromatic ring in the 2,2′-dialkoxyphenyl compound is acylated with an aromatic dicarboxylic acid derivative, whereby polymerization of both occurs.

Formula (5) as ^R 11 ^{to R 14} are in represented by 2,2'-dialkoxy biphenyl compounds, similar to ^R 11 ^{to R 14} in each aromatic polyketone represented by the general formula (1) Functional groups are preferred. From the viewpoint of easily obtaining the biphenyl compound, it is more preferable that R ¹¹ and R ¹² are the same functional group.

で表されるものが好ましい。なお、式中、Ｒ^１５は上記と同義であり、Ｘ^７１及びＸ^７２はそれぞれ独立にヒドロキシル基又は塩素原子である。これらのなかでは、Ｘ^７１及びＸ^７２の両方が塩素原子である芳香族ジカルボン酸クロリドが好ましい。具体的には、テレフタロイルクロリド、イソフタロイルクロリド、オキシビス安息香酸クロリド等が挙げられる。 Examples of the aromatic dicarboxylic acid or aromatic dicarboxylic acid chloride include dicarboxylic acids having one or two aromatic rings or acid chlorides thereof, and are represented by the above general formula (2a) or (2b). A dicarboxylic acid having a valent group or an acid chloride thereof is preferred. Examples of such aromatic dicarboxylic acids or acid chlorides thereof include the following general formula (7);

The thing represented by these is preferable. In the formula, R ¹⁵ is as defined above, and X ⁷¹ and X ⁷² are each independently a hydroxyl group or a chlorine atom. Of these, aromatic dicarboxylic acid chlorides in which both X ⁷¹ and X ⁷² are chlorine atoms are preferred. Specific examples include terephthaloyl chloride, isophthaloyl chloride, oxybisbenzoic acid chloride, and the like.

  In the reaction of the 2,2′-dialkoxybiphenyl compound with the aromatic dicarboxylic acid or acid chloride thereof, after dissolving them in a solvent, an activator (for example, a catalyst) is added to the mixture. It is preferable to generate by. The solvent is not particularly limited as long as it is a solvent that can dissolve both, and examples thereof include an alkyl halide solvent, specifically, dichloroethane. Examples of the activator include those commonly used in Friedel-Craft type acylation reactions, such as Lewis acid activators such as aluminum chloride, acid catalysts such as trifluoromethanesulfonic acid, pentoxide, etc. Examples thereof include a direct condensing agent such as a diphosphorus-methanesulfonic acid mixture.

  For example, when a Lewis acid activator is used, the reaction temperature in this reaction is maintained at about 5 ° C. at the time of addition of the activator, and is increased to about 50 ° C. after sufficiently mixing the activator. It is preferable. By doing so, the 2,2′-dialkoxybiphenyl compound is suppressed from being excessively acylated, whereby an aromatic polyketone having a sufficient molecular weight can be obtained. In this case, the reaction time is preferably about 4 to 24 hours. Further, when this reaction is carried out in the presence of a direct condensing agent such as a diphosphorus pentoxide-methanesulfonic acid mixture, the reaction temperature is preferably about 60-100 ° C. and the reaction time is 8-24 hours.

  And after predetermined time passes, it is preferable to drop a liquid mixture on acidic alcohol (for example, hydrochloric acid / methanol mixture etc.), and to complete reaction. By carrying out like this, the target product (aromatic polyketone) can be precipitated as a solid component, and thereby the product can be easily separated. By such a production method, the aromatic polyketone represented by the general formula (1) is suitably produced.

Such an aromatic polyketone production method can be represented by a reaction scheme of the following formula (8) as an example. Note that all symbols in the formula have the same meaning as described above.

(Aromatic polyketone represented by the general formula (3))
In the aromatic polyketone represented by the general formula (3), R ³¹ and R ³² are each independently preferably an alkyl group having 2 to 10 carbon atoms, and more preferably an alkyl group having 4 to 6 carbon atoms. Moreover, as ^R33 and ^R34 , a hydrogen atom is preferable.

As an aromatic polyketone having such a structure, poly [(2,2′-diethoxy-5,5′-biphenylene) in which R ³¹ and R ³² are ethyl groups and R ³³ and R ³⁴ are hydrogen atoms. Carbonyl (4,4′-biphenylene) carbonyl] or poly [(2,2′-dihexyloxy-5,5′-biphenylene) in which R ³¹ and R ³² are hexyl groups and R ³³ and R ³⁴ are hydrogen atoms ) Carbonyl (4,4'-biphenylene) carbonyl] and the like.

で表される。なお、式中、Ｘ^９０は塩素原子又は臭素原子を示す。また、当該ハロ安息香酸のベンゼン環は、上記ビフェニル化合物との反応を妨げない限り、他の置換基を更に有していてもよい。 These aromatic polyketones can be produced by the method shown below. That is, first, the 2,2′-dialkoxybiphenyl compound represented by the general formula (6) is reacted with halobenzoic acid to obtain an intermediate. In such a reaction, the above-mentioned intermediate is generated by acylating two aromatic rings in the 2,2′-dialkoxybiphenyl compound with halobenzoic acid. The 2,2′-dialkoxybiphenyl compound is preferably the same as the compound represented by the general formula (5). In addition, the halobenzoic acid is preferably a para-substituted product or a meta-substituted product in which a halogen is substituted at the para-position to the carboxyl group-substituted position in the benzene ring of benzoic acid, and more preferably a chloro-substituted product. . Such halobenzoic acid has the following general formula (9);

It is represented by In the formula, X ⁹⁰ represents a chlorine atom or a bromine atom. In addition, the benzene ring of the halobenzoic acid may further have other substituents as long as the reaction with the biphenyl compound is not hindered.

The reaction between the 2,2′-dialkoxybiphenyl compound and halobenzoic acid is preferably carried out in the presence of a diphosphorus pentoxide-methanesulfonic acid mixture. Such a mixture functions as a condensing agent and a solvent in the above reaction. The mixing ratio of the two is preferably such that diphosphorus pentoxide / methanesulfonic acid is about 1/10 in terms of mass ratio. Moreover, it is preferable that the reaction temperature in this reaction shall be about 60-100 degreeC, and an intermediate can be efficiently obtained by making it react for about 4 to 24 hours at such reaction temperature. As a result of such a reaction, the aromatic polyketone intermediate represented by the general formula (4) is obtained in a suitable case. The synthesis of such an intermediate can be represented by a reaction scheme of the following formula (10) as an example. In addition, all the codes | symbols in a formula are synonymous with the above.

  The aromatic polyketone represented by the general formula (3) can be produced by obtaining an intermediate in this way and then coupling and polymerizing the intermediate. The coupling of the intermediate is preferably caused by treating the intermediate with a coupling agent. As the coupling agent, a combination of a catalyst and a reducing agent is preferable. More specifically, the catalyst includes nickel bromide, and the reducing agent includes zinc. In addition to these coupling agents, it is preferable to use triphenylphosphine or 2,2′-bipyridine in combination because the coupling of the intermediate tends to be further promoted.

  The coupling is preferably performed at 100 to 120 ° C. and more preferably at 100 ° C. in a polar solvent such as N, N-dimethylformamide under an inert gas atmosphere such as nitrogen. After coupling under such conditions, the reaction can be stopped by charging the mixed solution into acidic alcohol (hydrochloric acid / methanol mixed solution) or the like. This also makes it possible to separate the target product (aromatic polyketone) as a solid component. By such a production method, the aromatic polyketone represented by the general formula (3) is obtained.

Such intermediate coupling can be represented by a reaction scheme of the following formula (11) as an example. In the formula, PPh ₃ represents triphenylphosphine, bpy represents 2,2′-bipyridine, and other symbols are as defined above.

(Electrochemical element)
FIG. 1 is a diagram schematically showing a cross-sectional structure of an electric double layer capacitor which is an example of an electrochemical element.

  The electric double layer capacitor 1 shown in FIG. 1 includes a capacitor body 13, and a positive electrode can 2 and a negative electrode can 14 that accommodate the capacitor body 13 sandwiched from above and below. The positive electrode can 2 and the negative electrode can 14 are in contact with each other with the gasket 16 interposed therebetween, whereby both are electrically insulated.

  The capacitor body 13 includes the electrodes 6 and 10, the separator 8 sandwiched between the electrodes 6 and 10, and current collectors provided on the opposite surfaces of the electrodes 6 and 10 with respect to the separator. 4 and the current collector 12. Although not shown, the electrodes 6 and 10 and the separator 8 are each impregnated with an electrolyte solution. The electric double layer capacitor 1 having such a structure is a so-called coin-type electric double layer capacitor.

  The positive electrode can 2 and the negative electrode can 14 are containers for accommodating the capacitor element body 13 therein, and are intended to be electrically connected to the outside of the capacitor element body 13. These positive electrode can 2 and negative electrode can 14 can be made of conductive metal or the like, and specifically, stainless steel or nickel-plated stainless steel (the surface to be plated is And the like composed of the outside of the can). Further, since a high potential is applied to the positive electrode can, sus316 or aluminum having excellent corrosion resistance is used.

  The electrodes 6 and 10 function as a positive electrode or a negative electrode in the electric double layer capacitor 1, and are formed by impregnating a porous material having electrical conductivity with an electrolyte solution. Examples of such a porous substance include activated carbon. Further, the current collectors 4 and 12 are for taking out current from the electrodes 6 and 10, and those made of a conductive metal material can be suitably used.

  As the electrolyte solution impregnated in the electrodes 6, 10 and the separator 8, an electrolytic solution generally used for an electric double layer capacitor can be applied without limitation. For example, as a typical example, a quaternary ammonium salt such as tetraethylammonium tetrafluoroborate dissolved in an organic solvent such as propylene carbonate, diethylene carbonate, or acetonitrile can be used.

  The separator 8 (electrochemical element separator) in the capacitor body 13 is a film-like porous body containing the aromatic polyketone of the present invention, and is made of the aromatic polyketone of the present invention.

  Here, a method for forming the separator 8 from the aromatic polyketone of the present invention will be described. First, the aromatic polyketone represented by the general formula (1) or the aromatic polyketone represented by the general formula (3) is dissolved in a solvent such as chloroform to obtain a solution. This solution is dropped on a substrate such as a glass plate to form a film containing an aromatic polyketone. Then, before all the solvent evaporates from the obtained film, this film is immersed in water together with the substrate. And after predetermined time progress, this film | membrane is taken out from water and dried. Thereby, the porous film which consists of the above-mentioned aromatic polyketone is obtained.

  Such a method for forming a porous film is a so-called casting method. As reported in Non-Patent Documents 1 to 4 described above, a conventional aromatic polyketone having a 2,2′-dimethoxy-5,5′-biphenylene skeleton is soluble in an organic solvent. Was not seen at all. For this reason, when a conventional aromatic polyketone is used, it is difficult to carry out such a casting method. Therefore, it has been extremely difficult to apply a conventional wholly aromatic polyketone to a separator of an electric double layer capacitor. On the other hand, since the aromatic polyketone of the present invention can be dissolved in a solvent, it can be easily applied to a casting method. Therefore, according to the aromatic polyketone of the present invention, a porous film that can be used as the separator 8 in the electric double layer capacitor 1 can be easily formed.

  Furthermore, in the electric double layer capacitor 1, the gasket 16 (electrochemical element gasket) also contains the aromatic polyketone of the present invention, and preferably comprises the aromatic polyketone of the present invention. . Such a gasket 16 can be obtained by a known molding method such as injection molding of the above-described polyketone. By caulking this gasket with the positive electrode can 2 and the negative electrode can 14, insulation between the positive electrode and the negative electrode can be achieved. Thereby, the electrochemical element 13 can be sealed.

  Since the separator 8 and the gasket 16 in the electric double layer capacitor 1 having such a configuration are made of the aromatic polyketone of the present invention, the separator 8 and the gasket 16 have extremely excellent heat resistance. For this reason, even if this electrochemical element 1 is mounted on a substrate or the like by reflow, for example, the deterioration of the characteristics of the electrochemical element due to the deterioration of the separator 8 and the gasket 16 is extremely small. These separators 8 and gaskets 16 also have excellent flexibility. For this reason, even when a physical impact or the like is applied to the electrochemical element 1 including the separator 8 and the gasket 16, damage such as breakage is significantly reduced. As described above, the electrochemical element 1 including the separator 8 and the gasket 16 is extremely excellent in durability, and as a result, has high reliability when mounted on an electronic device.

  In addition, the electrochemical element of this invention is not restricted to embodiment mentioned above, A various change is possible in the range which does not deviate from the summary. For example, the separator and the gasket in the electrochemical element may not necessarily be made of the aromatic polyketone of the present invention. If any one of these is formed from the aromatic polyketone of the present invention, the effect of improving characteristics such as heat resistance can be sufficiently obtained.

  Further, the electrochemical element of the present invention is not limited to the above-described electric double layer capacitor, and any electrochemical element to which the electrochemical element separator or gasket of the present invention can be applied will be included in the present invention. May be included.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.
[Synthesis of aromatic polyketone represented by the above general formula (1)]

(Example 1)
In 1 mL of 1,2-dichloroethane solution containing 2,2′-diethoxybiphenyl (0.2 mmol) and terephthaloyl chloride (0.2 mmol), while keeping the temperature of the solution at 5 ° C., the total amount is 1 0.08 mmol of aluminum chloride was added in small portions. Next, the mixed solution to which the total amount of aluminum chloride was added was stirred for 1 hour while maintaining the temperature at 5 ° C., then the temperature was raised to 50 ° C., and the mixture was further stirred for 20 hours to be reacted. After completion of the stirring, the reaction was stopped by dropping this mixed solution into a mixed solution of hydrochloric acid and methanol (volume ratio 1/9).

A solid component was separated and collected from the obtained mixed solution, and the obtained solid component was washed with acetone to obtain a product aromatic polyketone. When this product was analyzed by ¹ H-NMR, the δ values were as follows, and it was found that the product was poly [(2,2′-diethoxy-5,5′-biphenylene) terephthaloyl]. did. The yield was 56%.
¹ H-NMR (300 MHz, CDCl ₃ ): 1.36 (6H, t, J = 7.2 Hz), 4.14 (4H, q, J = 7.2 Hz), 6.97-7.01 (2H , M), 7.80-7.85 (8H, m)

(Example 2)
A product was obtained in the same manner as in Example 1 except that isophthalic chloride was used instead of terephthalic chloride. When the obtained product was analyzed by ¹ H-NMR, the δ value was as shown below, and the product was poly [(2,2′-diethoxy-5,5′-biphenylene) isophthaloyl]. There was found. The yield was 84%.
¹ H-NMR (300 MHz, CDCl ₃ ): 1.38 (6H, t, J = 7.2 Hz), 4.17 (4H, q, J = 7.2 Hz), 6.99-7.03 (2H M), 7.50-7.52 (1H, m), 7.80-8.01 (6H, m), 8.25-8.27 (1H, m)

(Example 3)
2,2′-diethoxybiphenyl (0.2 mmol) and oxybisbenzoic acid (0.2 mmol) were placed in a one-necked flask, and a total of 1.6 g of diphosphorus pentoxide-methanesulfonic acid mixture was added to the flask. (Diphosphorus pentoxide / methanesulfonic acid = 1/10; mass ratio) was added in small portions. The mixed solution to which this mixture was added was stirred at 60 ° C. for 24 hours to be reacted. After the stirring was completed, the reaction was stopped by adding this mixed solution dropwise to distilled water. The precipitated solid component was collected by suction filtration, and then the solid component was washed with water three times to obtain a product. When the obtained product was analyzed by ¹ H-NMR, the δ value was as follows, and the product was poly [(2,2′-diethoxy-5,5′-biphenylene) carbonyl (1,4 -Phenylene) oxy (1,4-phenylene) carbonyl]. The yield was 96%.
¹ H-NMR (300 MHz, CDCl ₃ ): 1.33 (6H, t, J = 7.2 Hz), 4.12 (4H, q, J = 7.2 Hz), 7.00 (2H, d, J = 7.2 Hz), 7.10-7.12 (4H, m), 7.75-7.92 (8H, m)
[Synthesis of aromatic polyketone represented by the above general formula (3)]
<Synthesis of Intermediate>

(Example 4)
An aromatic polyketone intermediate was produced according to the scheme represented by the above formula (10). That is, 2,2′-diethoxybiphenyl (0.1 mol) and 4-chlorobenzoic acid (0.3 mol) were placed in a one-necked flask, and then 40 g of diphosphorus pentoxide-methanesulfone in a total amount in the flask. The acid mixture (diphosphorus pentoxide / methanesulfonic acid = 1/10; mass ratio) was added in small portions. The liquid mixture to which this mixture was added was stirred at 100 ° C. for 8 hours to be reacted. After the stirring was completed, the reaction was stopped by pouring this mixed solution into water.

The reaction mixture was neutralized by adding 6M aqueous sodium hydroxide solution little by little, and the reaction product was extracted with chloroform. To the resulting extract, anhydrous magnesium sulfate was added and dried. Thereafter, anhydrous magnesium sulfate was removed from the extract, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel chromatography (eluent: mixed solution of hexane / ethyl acetate = 5/1) to obtain an intermediate product. When the obtained product was analyzed by ¹ H-NMR, the δ value (ppm) was as shown below, and the product was 5,5′-bis (chlorobenzoyl) -2,2′-diethoxybiphenyl. It turned out to be.
¹ H-NMR (300 MHz, CDCl ₃ ): 1.34 (6H, t, J = 6.9 Hz), 4.13 (4H, q, J = 6.9 Hz), 7.01 (2H, d, J = 8.4 Hz), 7.44 (4H, d, J = 8.4 Hz), 7.74 (4H, d, J = 8.4 Hz), 7.84 (2H, dd, J = 1.8, 8.4 Hz), 7.89 (2H, d, J = 1.8 Hz)

(Example 5)
An intermediate was obtained in the same manner as in Example 4 except that 2,2′-dihexyloxybiphenyl was used in place of 2,2′-diethoxybiphenyl. When the obtained product was analyzed by ¹ H-NMR, the δ value (ppm) was as shown below, and the product was 5,5′-bis (chlorobenzoyl) -2,2′-dihexane. It was found to be siloxybiphenyl.
¹ H-NMR (300 MHz, CDCl ₃ ): 0.87 (6H, t, J = 7.2 Hz), 1.19-1.34 (12H, m), 1.68 (4H, quint, J = 7) .2 Hz), 4.07 (4H, t, J = 7, 2 Hz), 7.00 (2H, d, J = 8.7 Hz), 7.46 (4H, d, J = 9.0 Hz), 7 .74 (4H, d, J = 9.0 Hz), 7.77 (2H, d, J = 1.8 Hz), 7.84 (2H, dd, J = 1.8, 8.7 Hz)
<Synthesis of aromatic polyketone>

  Using the intermediate obtained in Example 4, an aromatic polyketone was produced according to the reaction scheme represented by the above formula (11). That is, nickel bromide (0.2 mmol), zinc (1.2 mmol), triphenylphosphine (0.4 mmol), bipyridine (0.2 mmol), and 5 obtained in Example 4 were dried immediately under reduced pressure. 5′-bis (chlorobenzoyl) -2,2′-diethoxybiphenyl (0.4 mmol) was placed in a two-necked flask, and the inside of the flask was made a nitrogen atmosphere. A total amount of 0.8 mL of N, N-dimethylacetamide distilled immediately under reduced pressure was added little by little to the flask, and then the mixture in the flask was stirred at 100 ° C. for 2 hours.

After completion of the stirring, the reaction was stopped by charging the solution into a mixed solution of hydrochloric acid and methanol (volume ratio 1/9). A solid component was separated from the mixture after the reaction, and this was washed with acetone to obtain a product. The resulting product was poly [(2,2′-diethoxy-5,5′-biphenylene) carbonyl (4,4′-biphenylene) carbonyl].
[Manufacture of electric double layer capacitors]

(Manufacture of electrodes for electric double layer capacitors)
First, polyvinylidene fluoride (PVDF; KYNAR761EA, manufactured by Atofina) was dissolved in dimethylformamide, and 5% by mass of carbon black (manufactured by Denki Kagaku Kogyo Co., Ltd.) was dispersed in the mixed liquid to obtain a carbon black dispersion. . Next, the above-mentioned carbon black dispersion and activated carbon (FR25, manufactured by Kuraray Co., Ltd.) were charged into a granulating apparatus (newmalmerizer (trade name), manufactured by Dalton) to obtain granulated powder. In addition, content of each component in granulated powder was made to become PVDF 9 mass%, activated carbon 86 mass%, and carbon black 5 mass%.

  Moreover, an aluminum foil having a thickness of 20 μm was prepared as a current collector, and an undercoat layer for improving the adhesion between the electrode and the current collector was formed on one surface of the aluminum foil. In addition, as an undercoat layer, the layer which consists of a mixture (mass ratio 80:20) of PVDF (KYNAR761EA, made by Atofina) and carbon black was formed, and the thickness was 5-6 micrometers.

Next, the aluminum foil on which the undercoat layer was formed was cut into a circle having a diameter of 4 mm, and this was placed in a mold having a diameter of 4.3 mm. Then, the granulated powder mentioned above was filled on the undercoat layer of the aluminum foil, and pressed at a temperature of 190 ° C. and a pressure of 2 t / cm ² . Thus, an electrode was obtained in which an aluminum current collector having a diameter of 3 mm and an activated carbon electrode having a diameter of 4.3 mm were bonded.

(Example 6: Production of gasket for electric double layer capacitor)
The aromatic polyketone obtained in Example 1 was processed into a predetermined shape by an injection molding machine to produce an electric double layer capacitor gasket.

(Example 7: Production of separator for electric double layer capacitor)
The aromatic polyketone obtained in Example 1 was dissolved in chloroform as a solvent, and this solution was cast on a glass plate. Before all the solvent was evaporated from the cast film thus obtained, the cast film was immersed in water together with the glass plate. Thereafter, the glass plate on which the cast film was formed was taken out of water and dried at 60 ° C. The cast film thus obtained was used as a separator for an electric double layer capacitor. The obtained film was microporous.
<Manufacture of electric double layer capacitor and evaluation of its characteristics>

(Example 8)
The following components were prepared as components for a coin-type electric double layer capacitor. That is, a stainless steel (SUS316) negative electrode can and a positive electrode can, two electrodes obtained by the above-described method, a gasket obtained in Example 6, a non-woven fabric having a diameter of 4.5 mm used as a separator (Nippon Advanced Paper Industries Co., Ltd.) Manufactured, TF4550, thickness 50 μm), and an electrolyte solution containing triethylmethylammonium tetrafluoroborate as an electrolyte salt and propylene carbonate as a solvent.

  In manufacturing the electric double layer capacitor, first, the above-mentioned electrode was placed in a petri dish, an electrolytic solution was put, and this was evacuated to impregnate the two electrodes with the electrolytic solution. Next, after placing a gasket at a predetermined position of the negative electrode can, one electrode was placed so that the aluminum foil was in contact with the negative electrode can. Further, a separator was placed on this electrode, and 1 μL of an electrolysis solution was dropped. Thereafter, another electrode was placed on the separator so that the activated carbon layer was in contact with the separator. Then, the positive electrode can was covered from above the laminated structure, and the end portion of the positive electrode can was bent and caulked against the negative electrode can so as to sandwich the gasket. As a result, a coin-type electric double layer capacitor was obtained.

  When the resistance of the obtained electric double layer capacitor at 1 kHz was measured, it was 75Ω and the capacitance was 0.17F. Next, this electric double layer capacitor was put into a reflow furnace (Model FIR-150B, manufactured by Nippon Denki Keiki Co., Ltd.) having a peak temperature of 255 ° C. The residence time in this reflow furnace was 5 minutes. Thereafter, when the resistance and capacitance of the electric double layer capacitor were measured again, they were 76Ω and 0.16F, respectively. Thus, the electric double layer capacitor of Example 8 equipped with the gasket of the present invention has almost no change in resistance and capacitance before and after being put into the reflow furnace, and has excellent durability against reflow. Turned out to be.

Example 9
As the separator, the separator obtained in Example 7 was used instead of the nonwoven fabric, and the gasket was used except that the one formed by polyphenylene sulfone (PPS) was used instead of the one obtained in Example 6. A coin-type electric double layer capacitor was manufactured in the same manner as in Example 8. The obtained electric double layer capacitor was evaluated in the same manner as in Example 8. As a result, the resistance and capacitance before entering the reflow furnace were 75Ω and 0.17F, respectively. Moreover, the resistance and electrostatic capacitance after putting in the reflow furnace were 77Ω and 0.15F, respectively. Thus, it was found that the electric double layer capacitor of Example 9 provided with the separator of the present invention had excellent durability against reflow.
(Example 10)
A coin-type electric double layer capacitor was manufactured in the same manner as in Example 8, except that the separator obtained in Example 7 was used instead of the nonwoven fabric. The obtained electric double layer capacitor was evaluated in the same manner as in Example 8. As a result, the resistance and capacitance before entering the reflow furnace were 75Ω and 0.17F, respectively. Moreover, the resistance and electrostatic capacitance after putting in the reflow furnace were 75Ω and 0.17F, respectively. Thus, it was found that the electric double layer capacitor of Example 10 provided with the separator and gasket of the present invention had particularly excellent durability against reflow.
(Comparative Example 1)
A coin-type electric double layer capacitor was manufactured in the same manner as in Example 8, except that a gasket formed by PPS was used instead of the gasket obtained in Example 6. The obtained electric double layer capacitor was evaluated in the same manner as in Example 8. As a result, the resistance and capacitance before entering the reflow furnace were 75Ω and 0.17F, respectively, but the resistance and capacitance after entering the reflow furnace were 100Ω and 0.10F, respectively. . Thus, it was found that the electric double layer capacitor of Comparative Example 1 using PPS for the gasket and non-woven fabric for the separator had extremely low durability against reflow.

It is a figure which shows typically the cross-sectional structure of the electric double layer capacitor which is an example of an electrochemical element.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Electric double layer capacitor, 2 ... Positive electrode can, 4 ... Current collector, 6 ... Electrode, 8 ... Separator, 10 ... Electrode, 12 ... Current collector, 13 ... Capacitor body, 14 ... Negative electrode can, 16 ... Gasket .

Claims (9)

An aromatic polyketone comprising a repeating unit represented by the following general formula (3).

[Wherein, R ³¹ and R ³² each independently represent an alkyl group having 2 or more carbon atoms, and R ³³ and R ³⁴ each independently represent a hydrogen atom or an alkyl group. ] An aromatic polyketone intermediate represented by the following general formula (4).

[Wherein, R ³¹ and R ³² each independently represent an alkyl group having 2 or more carbon atoms, and R ³³ and R ³⁴ each independently represent a hydrogen atom or an alkyl group. ] The manufacturing method of aromatic polyketone which has the process of making the 2,2'- dialkoxy biphenyl compound represented by following General formula (6), and halobenzoic acid react, and obtaining an intermediate body.

[Wherein, R ³¹ and R ³² each independently represent an alkyl group having 2 or more carbon atoms, and R ³³ and R ³⁴ each independently represent a hydrogen atom or an alkyl group. ] The method for producing an aromatic polyketone according to claim 3 , further comprising a step of coupling the intermediate with a coupling agent. The separator for electrochemical devices containing the aromatic polyketone of Claim 1 . The gasket for electrochemical elements containing the aromatic polyketone of Claim 1 . A pair of electrodes;
A separator disposed between the pair of electrodes;
An electrolyte solution contained in the electrode and the separator;
A container for accommodating the electrode, the separator, and the electrolyte solution;
The said separator is an electrochemical element containing the aromatic polyketone of Claim 1 . A pair of electrodes;
A separator disposed between the pair of electrodes;
An electrolyte solution contained in the electrode and the separator;
A pair of metal container members for containing the electrodes, the separator and the electrolyte solution;
A gasket for electrically insulating between the pair of container members,
The said gasket is an electrochemical element containing the aromatic polyketone of Claim 1 . The separator contains an aromatic polyketone according to claim 1, the electrochemical device according to claim 8.

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