JP2003231749A - Method for producing poly(oxyphenylene) having substituted phenyl ether as side chain - Google Patents
Method for producing poly(oxyphenylene) having substituted phenyl ether as side chainInfo
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- JP2003231749A JP2003231749A JP2003006408A JP2003006408A JP2003231749A JP 2003231749 A JP2003231749 A JP 2003231749A JP 2003006408 A JP2003006408 A JP 2003006408A JP 2003006408 A JP2003006408 A JP 2003006408A JP 2003231749 A JP2003231749 A JP 2003231749A
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- JP
- Japan
- Prior art keywords
- poly
- phenyl ether
- oxyfluorophenylene
- oxyphenylene
- substituted phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【0001】[0001]
【発明の属する技術分野】この出願の発明は、側鎖に置
換フェニルエーテルを有するポリ(オキシフェニレン)
類の製造方法に関するものである。さらに詳しくは、こ
の出願の発明は、ポリ(オキシフルオロフェニレン)類
に置換フェノールを反応させ、フルオロ基を置換フェニ
ルエーテル基で置き換えることを特徴とする側鎖に置換
フェニルエーテルを有するポリ(オキシフェニレン)類
の製造方法に関するものである。TECHNICAL FIELD The invention of this application relates to poly (oxyphenylene) having a substituted phenyl ether in the side chain.
The present invention relates to a manufacturing method of a class. More specifically, the invention of this application is characterized in that poly (oxyfluorophenylene) s are reacted with a substituted phenol, and a fluoro group is replaced with a substituted phenyl ether group. ) Related to the manufacturing method.
【0002】[0002]
【従来の技術とその課題】ポリオキシフェニレン類は、
高い機械的強度と耐熱性を有する材料として、自動車用
等の機械部品、ガス分離膜、導電性樹脂、機能性ゴム等
として、種々の産業分野で用いられている。2. Description of the Related Art Polyoxyphenylenes are
As a material having high mechanical strength and heat resistance, it is used in various industrial fields such as mechanical parts for automobiles, gas separation membranes, conductive resins, functional rubbers, and the like.
【0003】フェニレン電子供与性置換基を有するフェ
ノール類を重合してなるポリアリーレンエーテルの合成
については、これまで種々の報告がある。例えば、ポリ
(オキシ−2,6−ジメチル−1,4−フェニレン)
は、第3級アミン(ピリジン、テトラメチルエチレンジ
アミン、トリエチルアミンなど)と、これらの化合物と
錯形成できる銅(I)塩(例えば塩化第一銅)を触媒とす
る2,6−ジメチルフェノールの酸化カップリングによ
って合成される。このような合成法は、酸化剤として溶
存酸素を利用し、水を生成する反応系であることから、
安価な反応系として利用されている。There have been various reports on the synthesis of polyarylene ethers obtained by polymerizing phenols having a phenylene electron-donating substituent. For example, poly (oxy-2,6-dimethyl-1,4-phenylene)
Is an oxidation cup of 2,6-dimethylphenol catalyzed by a tertiary amine (pyridine, tetramethylethylenediamine, triethylamine, etc.) and a copper (I) salt (eg cuprous chloride) capable of complexing with these compounds. Synthesized by the ring. Since such a synthetic method is a reaction system that utilizes dissolved oxygen as an oxidant and produces water,
It is used as an inexpensive reaction system.
【0004】さらに、弗素置換されたポリ(オキシフェ
ニレン)が実現されれば、例えば500℃以上というよ
り高い耐熱性や機械強度、さらには耐薬品性等をも示す
と考えられ、耐久性の高い材料等として、これまで以上
に多くの用途が期待される。また、このようなポリマー
は、非晶質であり、フィルム等の成型が容易であるとい
う利点も期待される。Furthermore, if a fluorine-substituted poly (oxyphenylene) is realized, it is considered that it will have higher heat resistance and mechanical strength of, for example, 500 ° C. or higher, and further chemical resistance, and thus has high durability. As a material, etc., it is expected to have more uses than ever before. Further, such a polymer is amorphous and is expected to have an advantage that a film or the like can be easily molded.
【0005】また、弗素のような電子吸引性置換基を有
するフェノール類に各種の特徴的な置換基を導入できれ
ば、用途に応じた様々な物性を制御できることが期待さ
れる。Further, if various characteristic substituents can be introduced into phenols having an electron-withdrawing substituent such as fluorine, it is expected that various physical properties can be controlled according to the application.
【0006】そこで、この出願の発明は、以上のとおり
の事情に鑑みてなされたものであり、ポリ(オキシフル
オロフェニレン)類の物性を制御する方法として、ポリ
(オキシフルオロフェニレン)類に置換フェニルエーテ
ルを導入する方法を提供することを課題としている。Therefore, the invention of this application was made in view of the above circumstances, and as a method for controlling the physical properties of poly (oxyfluorophenylene) s, poly (oxyfluorophenylene) s substituted phenyl It is an object to provide a method for introducing ether.
【0007】[0007]
【課題を解決するための手段】この出願の発明は、上記
の課題を解決するものとして、第1には、次の一般式
(I)Means for Solving the Problems The invention of this application is intended to solve the above problems. Firstly, the following general formula (I)
【0008】[0008]
【化2】 [Chemical 2]
【0009】(ただし、Oは酸素原子を表し、R1、
R2、R3、およびR4は、水素原子または弗素原子で、
少なくとも1つが弗素原子であり、nは重合度を示す2
以上の整数である)で表されるポリ(オキシフルオロフ
ェニレン)類に置換フェノールを反応させ、フルオロ基
を置換フェニルエーテル基で置き換えることを特徴とす
る側鎖に置換フェニルエーテルを有するポリ(オキシフ
ェニレン)類の製造方法を提供する。(However, O represents an oxygen atom, and R 1 ,
R 2 , R 3 and R 4 are hydrogen atoms or fluorine atoms,
At least one is a fluorine atom, and n is the degree of polymerization. 2
Poly (oxyphenylene) having a substituted phenyl ether in the side chain, characterized in that a substituted phenol is reacted with poly (oxyfluorophenylene) s represented by ) Is provided.
【0010】また、この出願の発明は、第2には、置換
フェノールがp−フェノールスルホン酸である前記の製
造方法をも提供する。Secondly, the invention of this application also provides the above-mentioned production method, wherein the substituted phenol is p-phenolsulfonic acid.
【0011】[0011]
【発明の実施の形態】以下にこの出願の発明を詳細に説
明する。BEST MODE FOR CARRYING OUT THE INVENTION The invention of this application will be described in detail below.
【0012】この出願の発明の、側鎖に置換フェニルエ
ーテルを有するポリ(オキシフェニレン)類の製造方法
において、使用されるポリ(オキシフルオロフェニレ
ン)類は、次の一般式(I)In the method for producing poly (oxyphenylene) s having a substituted phenyl ether in the side chain of the invention of this application, the poly (oxyfluorophenylenes) used have the following general formula (I):
【0013】[0013]
【化3】 [Chemical 3]
【0014】(ただし、Oは酸素原子を表し、R1、
R2、R3、およびR4は、水素原子または弗素原子で、
少なくとも1つが弗素原子であり、nは重合度を示す2
以上の整数である)で表されるものである。(However, O represents an oxygen atom, and R 1 ,
R 2 , R 3 and R 4 are hydrogen atoms or fluorine atoms,
At least one is a fluorine atom, and n is the degree of polymerization. 2
The above is an integer).
【0015】この出願の発明において、上記一般式
(I)で表されるポリ(オキシフルオロフェニレン)類
は、重合度nが2以上であればよく、nの値が20未満
の比較的低分子量なオリゴマーであっても、重合度nの
値が20以上のポリマーであってもよい。In the invention of this application, the poly (oxyfluorophenylene) s represented by the above general formula (I) may have a polymerization degree n of 2 or more, and the value of n is less than 20, which is a relatively low molecular weight. The oligomer may be a polymer having a degree of polymerization n of 20 or more.
【0016】この出願の発明のポリ(オキシフルオロフ
ェニレン)類は、どのような方法で合成されるものであ
ってもよく、触媒、溶媒、反応温度、反応触媒等はどの
ようなものであってもよい。好ましくは次の一般式(I
I)The poly (oxyfluorophenylene) s of the invention of this application may be synthesized by any method, and the catalyst, solvent, reaction temperature, reaction catalyst, etc. may be any one. Good. Preferably, the following general formula (I
I)
【0017】[0017]
【化4】 [Chemical 4]
【0018】(ただし、Oは酸素原子を表し、R1、
R2、R3、およびR4は、水素原子または弗素原子で、
少なくとも1つが弗素原子である)で表されるフルオロ
フェノールを酸化重合して得られるものである。(However, O represents an oxygen atom, and R 1 ,
R 2 , R 3 and R 4 are hydrogen atoms or fluorine atoms,
At least one of which is a fluorine atom) is obtained by oxidative polymerization of fluorophenol.
【0019】このとき、フルオロフェノールとしては、
例えば2−フルオロフェノール、3−フルオロフェノー
ル、2,6−ジフルオロフェノール、2,5−ジフルオ
ロフェノール、2,3−ジフルオロフェノール、2,
3,5−トリフルオロフェノール、2,3,6−トリフ
ルオロフェノール、2,3,5,6−テトラフルオロフ
ェノール等が挙げられる。At this time, as fluorophenol,
For example, 2-fluorophenol, 3-fluorophenol, 2,6-difluorophenol, 2,5-difluorophenol, 2,3-difluorophenol, 2,
3,5-trifluorophenol, 2,3,6-trifluorophenol, 2,3,5,6-tetrafluorophenol and the like can be mentioned.
【0020】また、この出願の発明において使用される
ポリ(オキシフルオロフェニレン)類は、上記のフルオ
ロフェノールを酸化重合して得られるオリゴマーを、再
重合して得られるものであってもよい。Further, the poly (oxyfluorophenylene) s used in the invention of this application may be obtained by repolymerizing an oligomer obtained by oxidative polymerization of the above fluorophenol.
【0021】また、ポリ(オキシフルオロフェニレン)
類の製造においては、酸化重合触媒として、銅錯体、よ
り好ましくは、脂肪族環状アミン系多座配位子を有する
単核銅錯体、またはアルキレンジアミン配位子を有する
単核銅錯体、さらには、脂肪族環状アミン系多座配位子
やアルキレンジアミン配位子がアルキル鎖により連結さ
れた複核化配位子を有する二核銅錯体のいずれかを用い
てもよい。Further, poly (oxyfluorophenylene)
In the production of the class, as the oxidation polymerization catalyst, a copper complex, more preferably a mononuclear copper complex having an alicyclic amine polydentate ligand, or a mononuclear copper complex having an alkylenediamine ligand, and further Any of the binuclear copper complexes having a polynuclear ligand in which an aliphatic cyclic amine-based polydentate ligand or an alkylenediamine ligand is linked by an alkyl chain may be used.
【0022】以上のような銅錯体触媒としては、(1,
4,7−トリメチル−1,4,7−トリアザシクロノナ
ン銅(II))クロリド、(1,4,7−トリイソプロピル
−1,4,7−トリアザシクロノナン銅(II))クロリ
ド、(1,4,7−トリプロピル−1,4,7−トリア
ザシクロノナン銅(II))ブロミド、(エチレンジアミン
銅(II))クロリド、(N,N’−ジメチルエチレンジア
ミン銅(II))ブロミド、(N,N,N’,N’−テトラ
エチルエチレンジアミン銅(II))ブロミド、(N,N,
N’,N’−テトラプロピルエチレンジアミン銅(II))
ブロミド、(N,N’−ビス(2−アミノエチル)−
1,4−n−ブタンジアミン)ビス銅(II))クロリド、
(N,N’−ビス(2−ジ−t−ブチルアミノシクロヘ
キシル−t−ブチル)−1,6−n−ヘキサンジアミ
ン)ビス銅(II))テトラフルオロホウ酸塩などが例示さ
れる。As the copper complex catalyst as described above, (1,
4,7-trimethyl-1,4,7-triazacyclononane copper (II)) chloride, (1,4,7-triisopropyl-1,4,7-triazacyclononane copper (II)) chloride, (1,4,7-Tripropyl-1,4,7-triazacyclononane copper (II)) bromide, (ethylenediamine copper (II)) chloride, (N, N'-dimethylethylenediamine copper (II)) bromide , (N, N, N ', N'-tetraethylethylenediamine copper (II)) bromide, (N, N,
N ', N'-tetrapropylethylenediamine copper (II))
Bromide, (N, N'-bis (2-aminoethyl)-
1,4-n-butanediamine) biscopper (II)) chloride,
Examples include (N, N'-bis (2-di-t-butylaminocyclohexyl-t-butyl) -1,6-n-hexanediamine) biscopper (II)) tetrafluoroborate.
【0023】また、溶媒は、とくに限定されないが、ベ
ンゼン、トルエン、o−キシレン、m−キシレン、モノ
クロロベンゼン、o−ジクロロベンゼン、ニトロベンゼ
ン、1,2−ジクロロプロパン、1,1,2,2−テト
ラクロロプロパン等の種々の有機溶媒が好ましく例示さ
れる。反応温度もとくに限定されないが、室温付近では
触媒活性が高く、反応系も扱いやすいため好ましい。さ
らに、反応は、酸素雰囲気下で行うことにより酸素が酸
化剤として作用し、好ましい。また、助触媒として塩基
を用いることにより、反応が促進されてより好ましい。
このような塩基としては、水酸化ナトリウム、水酸化カ
リウム、トリメチルアミン、N,N−ジメチルアミン、
N−メチルピロリジン、2,6−ジフェニルピリジン等
が好ましく例示される。The solvent is not particularly limited, but benzene, toluene, o-xylene, m-xylene, monochlorobenzene, o-dichlorobenzene, nitrobenzene, 1,2-dichloropropane, 1,1,2,2- Various organic solvents such as tetrachloropropane are preferably exemplified. The reaction temperature is also not particularly limited, but it is preferable because the catalytic activity is high near room temperature and the reaction system is easy to handle. Furthermore, the reaction is preferably performed in an oxygen atmosphere because oxygen acts as an oxidant. Further, the use of a base as a cocatalyst is more preferable because the reaction is promoted.
Such bases include sodium hydroxide, potassium hydroxide, trimethylamine, N, N-dimethylamine,
Preferable examples include N-methylpyrrolidine and 2,6-diphenylpyridine.
【0024】この出願の発明では、以上のとおりのポリ
(オキシフルオロフェニレン)を原料として、これに置
換フェノールを反応させ、フルオロ基を置換フェニルエ
ーテル基で置き換えることにより、側鎖に置換フェニル
エーテルを有するポリ(オキシフェニレン)類が得られ
る。このような製造方法としては、以下の化学式(II
I)In the invention of this application, poly (oxyfluorophenylene) as described above is used as a raw material, and this is reacted with a substituted phenol to replace the fluoro group with a substituted phenyl ether group, whereby a substituted phenyl ether is formed in the side chain. Poly (oxyphenylene) s having are obtained. As such a manufacturing method, the following chemical formula (II
I)
【0025】[0025]
【化5】 [Chemical 5]
【0026】が例示される。つまり、化学式(III)に
おいては、前記一般式(I)のR2およびR4がFである
ポリ(オキシフルオロフェニレン)を出発物質とし、置
換基Rを有するフェノールを反応させるものである。Is exemplified. That is, in the chemical formula (III), poly (oxyfluorophenylene) in which R 2 and R 4 in the general formula (I) are F is used as a starting material, and a phenol having a substituent R is reacted.
【0027】出発物質のポリ(オキシフルオロフェニレ
ン)類は、化学式(III)に記載のものに限定されず、
Fが1〜4個のものであってもよく、またそれらの位置
も2,6−に限定されない。ポリ(2−モノフルオロ−
1,4−フェニレンオキシド)、ポリ(3−モノフルオ
ロ−1,4−フェニレンオキシド)、ポリ(2,5−ジ
フルオロ−1,4−フェニレンオキシド)、ポリ(3,
5−ジフルオロ−1,4−フェニレンオキシド)、ポリ
(2,3,5−トリフルオロ−1,4−フェニレンオキ
シド)、ポリ(2,3,6−トリフルオロ−1,4−フ
ェニレンオキシド)、ポリ(2,3,5,6−テトラフ
ルオロ−1,4−フェニレンオキシド)等、種々のもの
が原料となりうる。The starting poly (oxyfluorophenylene) s are not limited to those represented by the chemical formula (III),
The number of F may be 1 to 4, and their positions are not limited to 2,6-. Poly (2-monofluoro-
1,4-phenylene oxide), poly (3-monofluoro-1,4-phenylene oxide), poly (2,5-difluoro-1,4-phenylene oxide), poly (3,3
5-difluoro-1,4-phenylene oxide), poly (2,3,5-trifluoro-1,4-phenylene oxide), poly (2,3,6-trifluoro-1,4-phenylene oxide), Various materials such as poly (2,3,5,6-tetrafluoro-1,4-phenylene oxide) can be used as a raw material.
【0028】また、反応させる置換フェノールは、Rの
位置が、オルト位、メタ位、パラ位のどこにあるもので
もよく、さらには、2,4−、2,5−、3,5−位
等、OH基に対して2〜6位のいずれかの2箇所以上に
各々同一または別異の置換基を有するものであってもよ
い。置換基Rは、ハロゲン原子、O、S、Nを有する種
々の置換基、アルキル基、置換アルキル基等、どのよう
なものであってもよい。このような置換フェノールとし
ては、具体的には、p−フェノールスルホン酸、o−ニ
トロフェノール、m−クロロフェノール、などが例示さ
れる。The substituted phenol to be reacted may have the R position at any of the ortho position, the meta position and the para position, and further, the 2,4-, 2,5-, 3,5-position and the like. , OH group may have the same or different substituents at any two or more positions of 2 to 6 positions. The substituent R may be any of various substituents having a halogen atom, O, S, N, an alkyl group, a substituted alkyl group, and the like. Specific examples of such a substituted phenol include p-phenol sulfonic acid, o-nitrophenol, m-chlorophenol, and the like.
【0029】もちろん、この出願の発明の側鎖に置換フ
ェニルエーテルを有するポリ(オキシフェニレン)類の
製造方法においては、出発物質のポリ(オキシフルオロ
フェニレン)類や置換フェノールは、上に例示されるも
のに限定されず、種々の置換基を有するフェニルエーテ
ル基を導入することができる。種々のフェニルエーテル
基の導入により、ポリ(オキシフェニレン)類の機械的
性質や物理的性質を制御することが可能となる。Of course, in the method for producing poly (oxyphenylene) s having a substituted phenyl ether in the side chain of the invention of this application, the poly (oxyfluorophenylene) s and the substituted phenol as the starting materials are exemplified above. However, the phenyl ether group having various substituents is not limited thereto. The introduction of various phenyl ether groups makes it possible to control the mechanical and physical properties of poly (oxyphenylene) s.
【0030】化学式(III)において、フェニルエーテ
ルは、つまり、原料となるポリ(オキシフルオロフェニ
レン)類(化学式(I))における、弗素原子と置換フ
ェノールの置き換えによって導入されるものである。こ
のような反応の条件等はとくに限定されず、導入する置
換フェノールや出発物質となるポリ(オキシフルオロフ
ェニレン)類に応じて、触媒、溶媒、反応温度、反応時
間を選択してもよい。以下、実施例を示し、この出願の
発明をより詳しく説明する。なお、この出願の発明は以
下の実施例に限定されるものではないことはいうまでも
ない。In the chemical formula (III), the phenyl ether is introduced by replacing the fluorine atom with the substituted phenol in the raw material poly (oxyfluorophenylene) s (chemical formula (I)). The conditions of such reaction are not particularly limited, and a catalyst, a solvent, a reaction temperature, and a reaction time may be selected depending on the substituted phenol to be introduced and the poly (oxyfluorophenylene) as a starting material. Hereinafter, the invention of this application will be described in more detail with reference to examples. Needless to say, the invention of this application is not limited to the following examples.
【0031】[0031]
【実施例】実施例1
次の化学式(IV)にしたがって、ポリ(2,6−ジフル
オロ−1,4−フェニレンオキシド)にスルホン酸基を
導入した。 Example 1 A sulfonic acid group was introduced into poly (2,6-difluoro-1,4-phenylene oxide) according to the following chemical formula (IV).
【0032】[0032]
【化6】 [Chemical 6]
【0033】ポリ(2,6−ジフルオロ−1,4−フェ
ニレンオキシド)0.260g(0.002mol)と
p−フェノールスルホン酸7.68g(0.04mo
l)をガラス容器に導入し、10mlのジメチルアセト
アミドを溶媒として、無水炭酸カリウム5.54g
(0.04mol)、ヨウ化銅0.4g(0.002m
ol)を添加し、窒素雰囲気下で、160℃で48時間
加熱した。0.260 g (0.002 mol) of poly (2,6-difluoro-1,4-phenylene oxide) and 7.68 g (0.04 mo) of p-phenolsulfonic acid.
1) was introduced into a glass container, 10 ml of dimethylacetamide was used as a solvent, and 5.54 g of anhydrous potassium carbonate was used.
(0.04 mol), 0.4 g of copper iodide (0.002 m)
ol) was added and the mixture was heated at 160 ° C. for 48 hours under a nitrogen atmosphere.
【0034】反応液を300mlのメタノールに溶解
し、可溶部を濾過して回収した後、濾液を蒸発乾固し
た。残渣の固体を50mlの水に溶解し、3lの純粋中
で透析膜を用いて低分子量成分を除去した(1時間
後)。透析後の溶液を蒸発乾固し、茶色固体の生成物が
得られた。The reaction solution was dissolved in 300 ml of methanol, the soluble portion was collected by filtration, and the filtrate was evaporated to dryness. The residual solid was dissolved in 50 ml of water and the low molecular weight components were removed (after 1 hour) using a dialysis membrane in 3 l of pure. The solution after dialysis was evaporated to dryness to obtain a brown solid product.
【0035】[0035]
【発明の効果】以上詳しく説明した通り、この発明によ
って、ポリ(オキシフルオロフェニレン)類に置換フェ
ニルエーテルを導入する方法が提供される。これによ
り、ポリ(オキシフルオロフェニレン)類の物性を用途
に応じて制御することが可能となる。As described in detail above, the present invention provides a method for introducing a substituted phenyl ether into poly (oxyfluorophenylene) s. This makes it possible to control the physical properties of poly (oxyfluorophenylene) s according to the application.
Claims (2)
びR4は、水素原子または弗素原子で、少なくとも1つ
が弗素原子であり、nは重合度を示す2以上の整数であ
る)で表されるポリ(オキシフルオロフェニレン)類に
置換フェノールを反応させ、フルオロ基を置換フェニル
エーテル基で置き換えることを特徴とする側鎖に置換フ
ェニルエーテルを有するポリ(オキシフェニレン)類の
製造方法。1. The following general formula (I): (However, O represents an oxygen atom, R 1 , R 2 , R 3 , and R 4 are hydrogen atoms or fluorine atoms, at least one is a fluorine atom, and n is an integer of 2 or more, which indicates the degree of polymerization. The production of poly (oxyphenylene) s having a substituted phenyl ether in the side chain, characterized in that a substituted phenol is reacted with poly (oxyfluorophenylene) s represented by Method.
ホン酸である請求項1の側鎖に置換フェニルエーテルを
有するポリ(オキシフェニレン)類の製造方法。2. The method for producing poly (oxyphenylene) s having a substituted phenyl ether in the side chain according to claim 1, wherein the substituted phenol is p-phenolsulfonic acid.
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JP2003006408A JP3744902B2 (en) | 2003-01-14 | 2003-01-14 | Process for producing poly (oxyphenylene) s having substituted phenyl ether in the side chain |
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JP2000263849A Division JP2002069175A (en) | 1999-09-22 | 2000-08-31 | Poly(oxyfluorophenylene)s |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009263595A (en) * | 2008-04-30 | 2009-11-12 | Tokyo Institute Of Technology | Functionalized new linear polymer and method for producing it |
EP2202261A1 (en) * | 2008-12-16 | 2010-06-30 | Samsung Electronics Co., Ltd. | Hyper-branched polymer, electrode for fuel cell including the hyper-branched polymer, electrolyte membrane for fuel cell including the hyper-branched polymer, and fuel cell including at least one of the electrode and the electrolyte membrane |
JP2017105977A (en) * | 2015-11-26 | 2017-06-15 | 旭化成株式会社 | Sulfone group-containing polyphenylene ether and proton conductive film |
-
2003
- 2003-01-14 JP JP2003006408A patent/JP3744902B2/en not_active Expired - Fee Related
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009263595A (en) * | 2008-04-30 | 2009-11-12 | Tokyo Institute Of Technology | Functionalized new linear polymer and method for producing it |
EP2202261A1 (en) * | 2008-12-16 | 2010-06-30 | Samsung Electronics Co., Ltd. | Hyper-branched polymer, electrode for fuel cell including the hyper-branched polymer, electrolyte membrane for fuel cell including the hyper-branched polymer, and fuel cell including at least one of the electrode and the electrolyte membrane |
US8722280B2 (en) | 2008-12-16 | 2014-05-13 | Samsung Electronics Co., Ltd. | Hyper-branched polymer, electrode for fuel cell including the hyper-branched polymer, electrolyte membrane for fuel cell including the hyper-branched polymer, and fuel cell including at least one of the electrode and the electrolyte membrane |
JP2017105977A (en) * | 2015-11-26 | 2017-06-15 | 旭化成株式会社 | Sulfone group-containing polyphenylene ether and proton conductive film |
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