JP2003012796A - Oligomer of bifunctional phenylene ether and method for manufacturing the same - Google Patents
Oligomer of bifunctional phenylene ether and method for manufacturing the sameInfo
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- JP2003012796A JP2003012796A JP2001196569A JP2001196569A JP2003012796A JP 2003012796 A JP2003012796 A JP 2003012796A JP 2001196569 A JP2001196569 A JP 2001196569A JP 2001196569 A JP2001196569 A JP 2001196569A JP 2003012796 A JP2003012796 A JP 2003012796A
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- structural formula
- molecular weight
- phenol
- phenylene ether
- oligomer
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、両末端にフェノー
ル性水酸基を有する2官能性フェニレンエーテルのオリ
ゴマー体に関するもので、低誘電率、低誘電正接、高タ
フネスが要求される電子材料及びその中間体に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bifunctional phenylene ether oligomer having phenolic hydroxyl groups at both ends, which is an electronic material required to have a low dielectric constant, a low dielectric loss tangent and a high toughness and an intermediate thereof. It is about the body.
【０００２】[0002]
【従来の技術】電気・電子用途の材料には、高度情報化
社会での大量データを高速で処理するための低誘電特
性、熱衝撃等でマイクロクラックが発生しないための強
靭性が必要とされている。これに対し、ポリフェニレン
エーテル(PPE)などのエンジニアリングプラスチィクス
の利用が提案されている。しかし、PPEは優れた高周波
特性を有する反面、エポキシ樹脂やシアネート樹脂等の
熱硬化性樹脂との相溶性が悪いこと、溶融粘度が高く成
形加工性が悪いこと、溶解する溶媒がトルエン、ベンゼ
ン、キシレン等の芳香族炭化水素系あるいはメチレンク
ロライド、クロロホルム等のハロゲン化炭化水素系に限
定され作業性が悪いこと等の問題点をもつことが知られ
ている。2. Description of the Related Art Materials for electrical and electronic applications are required to have low dielectric properties for high-speed processing of a large amount of data in an advanced information society and toughness for preventing microcracks from being generated by thermal shock. ing. On the other hand, the use of engineering plastics such as polyphenylene ether (PPE) has been proposed. However, while PPE has excellent high-frequency characteristics, it has poor compatibility with thermosetting resins such as epoxy resins and cyanate resins, has a high melt viscosity and poor moldability, dissolves in toluene, benzene, It is known that it is limited to aromatic hydrocarbons such as xylene or halogenated hydrocarbons such as methylene chloride and chloroform, and has problems such as poor workability.
【０００３】相溶性改善のためには、相溶化剤として他
の樹脂とのブレンドにより改善する方法やPPEとシアネ
ート樹脂の擬似IPN構造化の検討(特開平11-21452等)等
がなされているが、成形加工性・耐熱性までは解決され
ていない。また、成形性改善のためには、高分子PPEを
低分子にする方法等の検討がなされている。例えば、高
分子PPEと2価のフェノールをラジカル触媒下で再分配さ
せる方法(特開平9-291148等)、あるいは2価のフェノー
ルと1価のフェノールを酸化重合する方法(特公平8-0117
47)等が知られている。いずれも高分子体が存在し、効
率良く２官能性低分子オリゴマー体を得ることができな
い。In order to improve the compatibility, a method of improving the compatibility by blending with another resin as a compatibilizing agent, a study on structuring a pseudo-IPN of PPE and a cyanate resin (Japanese Patent Laid-Open No. 11-21452, etc.) and the like have been conducted. However, molding processability and heat resistance have not been solved. Further, in order to improve the moldability, studies have been conducted on a method of converting a high molecular weight PPE into a low molecular weight. For example, a method of redistributing a polymer PPE and a divalent phenol under a radical catalyst (JP-A-9-291148, etc.), or a method of oxidatively polymerizing a divalent phenol and a monovalent phenol (Japanese Patent Publication No. 8-0117).
47) etc. are known. In both cases, a polymer is present, and a bifunctional low molecular weight oligomer cannot be obtained efficiently.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、PPEの優れ
た電気特性・強靭性を有し、他樹脂との相溶性、成形加
工性を改善した樹脂であり、加えて汎用ケトン系溶媒に
溶解し末端フェノール性水酸基の修飾が容易であるPPE
構造を有する２官能性フェニレンエーテルオリゴマーを
提供することである。DISCLOSURE OF THE INVENTION The present invention is a resin having excellent electrical characteristics and toughness of PPE, improved compatibility with other resins and moldability, and in addition to general-purpose ketone solvents. PPE that dissolves and is easy to modify the terminal phenolic hydroxyl groups
It is intended to provide a bifunctional phenylene ether oligomer having a structure.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、2官能性
フェニレンエーテルについて鋭意研究を重ねた結果、構
造式(1)で示される2官能性フェニレンエーテルを構造式
(2)の2価のフェノールと構造式(3)の1価のフェノールを
ケトン系溶剤中で酸化重合することで、効率よく構造式
(1)が製造できる事を発見し、本発明を完成するに至っ
た。以下に、本発明を詳細に説明する。Means for Solving the Problems As a result of intensive studies on the bifunctional phenylene ether, the present inventors have found that the bifunctional phenylene ether represented by the structural formula (1) has the structural formula
Efficient structural formula can be obtained by oxidative polymerization of divalent phenol (2) and monovalent phenol of structural formula (3) in a ketone solvent.
It was discovered that (1) can be manufactured, and the present invention has been completed. The present invention will be described in detail below.
【０００６】本発明の2価のフェノールとは、下記の構
造式(2)に示す様にR1,R2は同一または異なってもよく、
ハロゲン原子または炭素数6以下のアルキル基またはフ
ェニル基である。R3は同一または異なってもよく、水素
原子、ハロゲン原子または炭素数6以下のアルキル基ま
たはフェニル基であり、R1,R2が水素原子でないことが
必須の剛直なビフェニル骨格を有する2価のフェノール
である。The divalent phenol of the present invention may have the same or different R1 and R2 as shown in the following structural formula (2),
It is a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. R3 may be the same or different and is a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group, and R1 and R2 are divalent phenols having a rigid biphenyl skeleton which is essential not to be a hydrogen atom. is there.
【化４】 [Chemical 4]
【０００７】構造式(2)において、特に、2,2',3,3',5,
5'-ヘキサメチル-[1,1'-ビフェニル]-4,4'-ジオールが
好ましい。2位（構造式(2)のR2,R3）に置換基を有さな
い2価のフェノールを原料に用いた場合、2価のフェノー
ル自身の酸化速度が非常に高いため、2価のフェノール
がジフェノキノンとなり反応溶液から析出する。その結
果として、構造式(3)で示した1価のフェノールの単独重
合が優先され、片末端にのみフェノール性水酸基を有す
るフェニレンエーテルの生長が反応液から析出するまで
進む。したがって、メチルエチルケトンに可溶な2官能
性フェニレンエーテルを効率よく合成することができな
い。例えば、2位に置換基を有さない2価のフェノールと
して、3,3',5,5'-テトラメチル-[1,1'-ビフェニル]-4,
4'-ジオールが挙げられるが、これを用いて合成した場
合、析出物のGPCスペクトルは(図1)のようになり、高分
子量体の生成が確認できる。一方、2位（構造式(2)のR
2）に置換基を有する2価のフェノールとして、2,2',3,
3',5,5'-ヘキサメチル-[1,1'-ビフェニル]-4,4'-ジオー
ルが挙げられるが、この2価のフェノールを用いた場合
の反応中のGPCスペクトル変化(図2)、平均分子量の推移
(図3)より、得られる2官能性フェニレンエーテルの分子
量分布は反応の終始でほとんど同じであり、高分子量体
の生成は認められない。したがって、効率良く目的の2
官能性フェニレンエーテルのオリゴマー体を得ることが
できる。In the structural formula (2), especially 2,2 ', 3,3', 5,
5'-hexamethyl- [1,1'-biphenyl] -4,4'-diol is preferred. When a divalent phenol that does not have a substituent at the 2-position (R2, R3 in structural formula (2)) is used as the raw material, the oxidation rate of the divalent phenol itself is very high, It becomes diphenoquinone and precipitates from the reaction solution. As a result, the homopolymerization of the monovalent phenol represented by the structural formula (3) is prioritized and progresses until the growth of the phenylene ether having a phenolic hydroxyl group only at one terminal is precipitated from the reaction solution. Therefore, a bifunctional phenylene ether soluble in methyl ethyl ketone cannot be efficiently synthesized. For example, as a divalent phenol having no substituent at the 2-position, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,
4'-diol can be mentioned, but when synthesized using this, the GPC spectrum of the precipitate is as shown in (Fig. 1), confirming the formation of a high molecular weight product. On the other hand, the second position (R in structural formula (2)
2) as a divalent phenol having a substituent in 2, 2 ', 3,
3 ', 5,5'-hexamethyl- [1,1'-biphenyl] -4,4'-diol can be mentioned. GPC spectrum change during the reaction when using this divalent phenol (Fig. 2) , Transition of average molecular weight
From (FIG. 3), the molecular weight distribution of the obtained bifunctional phenylene ether is almost the same throughout the reaction, and formation of a high molecular weight compound is not observed. Therefore, you can efficiently
It is possible to obtain an oligomer of functional phenylene ether.
【０００８】このように2,3,5位に置換基を入れた2価の
フェノールを使うと、従来の3,5位に置換基を入れた原
料では予想もつかなかった、分子量分布の生成物ができ
た。したがって、本発明の課題を解決する為には、2価
のフェノール自身の酸化速度を緩和にすることが必要で
あり、2位（構造式(2)のＲ2）に置換基を有することが
必須である。As described above, when a divalent phenol having a substituent at the 2,3,5-position is used, a molecular weight distribution is unexpectedly generated in a conventional raw material having a substituent at the 3,5-position. I have a thing. Therefore, in order to solve the problems of the present invention, it is necessary to moderate the oxidation rate of the divalent phenol itself, and it is essential to have a substituent at the 2-position (R2 in the structural formula (2)). Is.
【０００９】本発明の１価のフェノールとは、構造式
(3)で示した1価のフェノールである。The monohydric phenol of the present invention has the structural formula
It is the monovalent phenol shown in (3).
【化５】
構造式(3)において、R1は同一または異なってもよく、
ハロゲン原子または炭素数6以下のアルキル基またはフ
ェニル基である。R3は同一または異なってもよく、水素
原子、ハロゲン原子または炭素数6以下のアルキル基ま
たはフェニル基である。特に、2, 6位に置換基を有する
もの単独、又はこれと3位あるいは3,5位に置換基を有す
るものが併用されることが好ましい。更に好ましくは、
単独では2,6-ジメチルフェノールがよく、併用では2,6-
ジメチルフェノールと2,3,6-トリメチルフェノールがよ
い。3位あるいは3,5位に置換基を有する1価のフェノー
ルを併用する場合の割合は、1価のフェノール全体の70m
ol%以下が好ましい。3位あるいは3,5位に置換基を有す
る1価のフェノールを併用する場合の割合が、1価のフェ
ノール全体の70mol%より多い場合、結晶性の化合物とな
り平均分子量1000程度でもメチルエチルケトンに不溶と
なる。なお、2,6-ジメチルフェノール単独のときよりも
2,6-ジメチルフェノールと2,3,6-トリメチルフェノール
を混合した時に、より低分子のオリゴマー体が得られ
る。これは2,3,6-トリメチルフェノールの3位のメチル
基が重合を抑制し、高分子量体の生成を抑えるためであ
る。[Chemical 5] In the structural formula (3), R1 may be the same or different,
It is a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. R3 may be the same or different and is a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. In particular, it is preferable to use one having a substituent at the 2- and 6-positions alone, or to use together with this one having a substituent at the 3- or 3,5-position. More preferably,
2,6-Dimethylphenol is better when used alone and 2,6-dimethylphenol when used in combination
Dimethylphenol and 2,3,6-trimethylphenol are good. When using a monovalent phenol having a substituent at the 3-position or the 3,5-position in combination, the ratio is 70 m of the total monovalent phenol.
It is preferably ol% or less. When using in combination with monovalent phenol having a substituent at the 3-position or the 3,5-position, if more than 70 mol% of the total monovalent phenol, it becomes a crystalline compound and is insoluble in methyl ethyl ketone even with an average molecular weight of about 1000. Become. It should be noted that, compared to the case of 2,6-dimethylphenol alone
When 2,6-dimethylphenol and 2,3,6-trimethylphenol are mixed, a lower molecular weight oligomer is obtained. This is because the methyl group at the 3-position of 2,3,6-trimethylphenol suppresses the polymerization and suppresses the formation of high molecular weight products.
【００１０】次に、本発明の製造法について説明する。
本発明の構造式(1)で示される2官能性フェニレンエーテ
ルのオリゴマー体は、構造式(2)で示される2価のフェノ
ールと構造式(3)で示される1価のフェノールを酸化重合
することによって得られる。酸化の方法については直接
酸素ガスあるいは空気を使用する方法がある。又、電極
酸化の方法もある。いずれの方法でも良く、特には限定
されない。安全性および設備投資が安価である事から空
気酸化が好ましい。空気で酸化する場合は、圧力は通常
大気圧から20kg/cm2までの圧力が選ばれる。Next, the manufacturing method of the present invention will be described.
The difunctional phenylene ether oligomer represented by the structural formula (1) of the present invention oxidatively polymerizes the divalent phenol represented by the structural formula (2) and the monovalent phenol represented by the structural formula (3). Obtained by As an oxidation method, there is a method of directly using oxygen gas or air. There is also a method of electrode oxidation. Either method may be used and is not particularly limited. Air oxidation is preferred because of its safety and inexpensive capital investment. When oxidizing with air, the pressure is usually selected from atmospheric pressure to 20 kg / cm 2 .
【００１１】酸素ガスあるいは、空気を用いて酸化重合
をする場合の触媒としては、CuCl、CuBr、Cu2SO4、CuCl
2、CuBr2、CuSO4、CuI等の銅塩等の一種または二種以上
が用いられ、上記触媒に加えて、モノ-及びジメチルア
ミン、モノ-及びジエチルアミン、モノ-及びジプロピル
アミン、モノ-及びジ-ｎ-ブチルアミン、モノ-及び-sec
-ジプロピルアミン、モノ-及びジベンジルアミン、モノ
-及びジシクロヘキシルアミン、モノ-及びジエタノール
アミン、エチルメチルアミン、メチルプロピルアミン、
アリルエチルアミン、メチルシクロヘキシルアミン、モ
ルホリン、メチル-ｎ-ブチルアミン、エチルイソプロピ
ルアミン、ベンジルメチルアミン、オクチルベンジルア
ミン、オクチル−クロロベンジルアミン、メチル（フェ
ニルエチル）アミン、ベンジルエチルアミン、ジ（クロ
ロフェニルエチル）アミン、１-メチルアミノ‐４‐ペ
ンテン、ピリジン、メチルピリジン、4-ジメチルアミノ
ピリジン、ピペリジン等を一種または二種以上のアミン
が併用される。銅塩及びアミンであれば、特にこれらに
限定されるものではない。特に、アミンとしては、ジ-
ｎ-ブチルアミンが好ましい。ジ-n-ブチルアミンを用い
る事で、構造式(3)で示した1価のフェノールの単独重合
が抑制され、高分子量体が生成しづらく、シャープな分
子量分布をもつ2官能性フェニレンエーテルのオリゴマ
ー体となる。As a catalyst for oxidative polymerization using oxygen gas or air, CuCl, CuBr, Cu2SO4, CuCl can be used.
2, CuBr2, CuSO4, CuI, and the like, one or more of copper salts and the like are used, and in addition to the above catalyst, mono- and dimethylamine, mono- and diethylamine, mono- and dipropylamine, mono- and di- -n-butylamine, mono- and -sec
-Dipropylamine, mono- and dibenzylamine, mono
-And dicyclohexylamine, mono- and diethanolamine, ethylmethylamine, methylpropylamine,
Allylethylamine, methylcyclohexylamine, morpholine, methyl-n-butylamine, ethylisopropylamine, benzylmethylamine, octylbenzylamine, octyl-chlorobenzylamine, methyl (phenylethyl) amine, benzylethylamine, di (chlorophenylethyl) amine, 1-methylamino-4-pentene, pyridine, methylpyridine, 4-dimethylaminopyridine, piperidine, etc. are used in combination with one or more amines. If it is a copper salt and an amine, it will not be limited to these. Especially, as amine, di-
N-butylamine is preferred. By using di-n-butylamine, homopolymerization of monohydric phenol represented by structural formula (3) is suppressed, it is difficult to form a high molecular weight product, and a difunctional phenylene ether oligomer having a sharp molecular weight distribution. Become a body.
【００１２】次に、本発明に使用される溶媒について説
明する。酸化重合において貧溶媒と考えられていて、従
来のPPEの酸化重合において使用できる割合が限られて
いたケトン系溶媒及びアルコール系溶媒を本発明では用
いることができる。従来この種の反応は、有機溶媒に溶
けずらいポリマーが生成するため、用いる反応溶媒のケ
トンやアルコールの割合を多くすることができなかった
が、本発明の生成物は、上記チャート(図2)に示す如く
低分子オリゴマーのみであることから、ケトン及びアル
コールにも容易に溶解し、使用できる溶媒の範囲が大き
く広がった。それらを単独、あるいは従来の溶媒である
トルエン、ベンゼン、キシレン等の芳香族炭化水素系溶
剤、エチレンクロライド、クロロホルム、四塩化炭素等
のハロゲン化炭化水素系溶剤等と併用することができ
る。ケトン系溶剤としては、アセトン、メチルエチルケ
トン、ジエチルケトン、メチルブチルケトン、メチルイ
ソブチルケトン等が挙げられ、アルコール系溶剤として
は、メタノール、エタノール、ブタノール、プロパノー
ル、メチルプロピレンジグリコール、ジエチレングリコ
ールエチルエーテル、ブチルプロピレングリコール、プ
ロピルプロピレングリコール等が挙げられるが、これら
に限定されるものではない。本発明の目的である比較的
低分子量でしかも分子量分布が鋭いピークを示すオリゴ
マーの生成は、特にケトン溶媒を使用した際にその効果
が顕著に現れる。さらに原料である２価のフェノールの
溶解性から、使用溶剤はメチルエチルケトン単独又はメ
チルエチルケトンを含んだ混合溶剤が最も好ましい。Next, the solvent used in the present invention will be described. In the present invention, a ketone solvent and an alcohol solvent, which are considered to be poor solvents in oxidative polymerization and whose proportions that can be used in conventional oxidative polymerization of PPE are limited, can be used in the present invention. Conventionally, this type of reaction produces a polymer that is difficult to dissolve in an organic solvent, so it was not possible to increase the ratio of the ketone or alcohol of the reaction solvent used, but the product of the present invention has the above-mentioned chart (Fig. 2). As shown in), since it is only a low molecular weight oligomer, it was easily dissolved in ketone and alcohol, and the range of usable solvents was greatly expanded. These may be used alone or in combination with conventional solvents such as aromatic hydrocarbon solvents such as toluene, benzene and xylene, halogenated hydrocarbon solvents such as ethylene chloride, chloroform and carbon tetrachloride. Examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, methyl butyl ketone, and methyl isobutyl ketone, and examples of the alcohol solvent include methanol, ethanol, butanol, propanol, methyl propylene diglycol, diethylene glycol ethyl ether, butyl propylene. Examples thereof include glycol and propyl propylene glycol, but are not limited thereto. The effect of forming an oligomer having a relatively low molecular weight and a sharp molecular weight distribution, which is the object of the present invention, is particularly remarkable when a ketone solvent is used. Furthermore, the solvent used is most preferably methyl ethyl ketone alone or a mixed solvent containing methyl ethyl ketone because of the solubility of the divalent phenol as the raw material.
【００１３】本発明の製造法における反応温度について
は、用いる溶媒の爆発限界に入らなければ、特には限定
されないが、25〜50℃が好ましい。酸化重合が発熱反応
のため、50℃以上では温度制御が困難で分子量制御がし
づらい。25℃以下では爆発限界の範囲に入り、安定な製
造ができない。The reaction temperature in the production method of the present invention is not particularly limited as long as it does not fall within the explosion limit of the solvent used, but is preferably 25 to 50 ° C. Since the oxidative polymerization is an exothermic reaction, it is difficult to control the temperature above 50 ° C and the molecular weight is difficult to control. Below 25 ° C, it falls into the range of explosion limit and stable production cannot be performed.
【００１４】次に、本発明の製造法におけるフェノール
濃度について説明する。構造式(2)に示した2価のフェノ
ールの濃度は、滴下する溶媒に対して2〜20wt％が好ま
しい。20wt%以上の場合、2価のフェノールが完全に溶媒
に溶解しない場合がある。一方、2wt%未満の場合、重合
の反応速度が低下する。又、構造式(3)で示した１価の
フェノールの濃度は、溶媒に対して6〜50 wt％が好まし
い。濃度が50wt%以上の場合、1価のフェノールが完全に
溶媒に溶解しない場合がある。一方、6wt%未満の場合、
重合の反応速度が低下する。Next, the phenol concentration in the production method of the present invention will be described. The concentration of the divalent phenol represented by the structural formula (2) is preferably 2 to 20 wt% with respect to the dropped solvent. If it is 20 wt% or more, the divalent phenol may not be completely dissolved in the solvent. On the other hand, if it is less than 2 wt%, the reaction rate of the polymerization will decrease. Further, the concentration of the monovalent phenol represented by the structural formula (3) is preferably 6 to 50 wt% with respect to the solvent. If the concentration is 50 wt% or more, the monohydric phenol may not be completely dissolved in the solvent. On the other hand, if less than 6 wt%,
The reaction rate of the polymerization decreases.
【００１５】本発明の製造法における構造式(2)で示し
た2価のフェノールと構造式(3)で示した1価のフェノー
ルのモル比率は、1：1から1：10までの範囲が好まし
い。特に、1:2〜1:8が好ましい。この範囲では1価のフ
ェノールの単独重合が生じにくく、分子量制御を行うこ
とが可能である。構造式(2)で示した2価のフェノールと
構造式(3)で示した1価のフェノールの比率を1：2より少
なくすると構造式(2)で示した2価のフェノールの残留が
多くなる。又、比率を1：10より多くすると構造式(3)で
示した1価のフェノールの単独重合が生じ、分子量が大
きくなり過ぎて、メチルエチルケトンに不溶なオリゴマ
ーとなってしまう。The molar ratio of the divalent phenol represented by the structural formula (2) to the monovalent phenol represented by the structural formula (3) in the production method of the present invention is in the range of 1: 1 to 1:10. preferable. Particularly, 1: 2 to 1: 8 is preferable. Within this range, homopolymerization of monohydric phenol is unlikely to occur, and it is possible to control the molecular weight. When the ratio of the divalent phenol shown in structural formula (2) and the monovalent phenol shown in structural formula (3) is less than 1: 2, the amount of divalent phenol shown in structural formula (2) remains large. Become. On the other hand, if the ratio is more than 1:10, homopolymerization of the monovalent phenol represented by the structural formula (3) occurs, the molecular weight becomes too large, and the oligomer becomes insoluble in methyl ethyl ketone.
【００１６】本発明の製造装置および製造方法について
説明する。攪拌装置、温度計、空気導入管、じゃま板の
ついた縦長反応器に銅触媒、アミン、溶媒を仕込み、40
℃にて攪拌を行い、あらかじめ溶媒に溶解させた2価の
フェノールと1価のフェノールの混合溶液を空気のバブ
リングを行いながら滴下する。滴下時間は50分から210
分の範囲が好ましい。滴下時間がこの範囲にない場合、
得られるオリゴマーの分子量分布の分散が大きくなる。
さらに滴下終了後5分から5時間攪拌を行うことが好まし
い。5時間以上攪拌を行っても、さらに分子量の増加は
起こらないので反応を終了すべきである。The manufacturing apparatus and manufacturing method of the present invention will be described. A vertical reactor equipped with a stirrer, a thermometer, an air inlet tube, and a baffle was charged with a copper catalyst, an amine, and a solvent.
The mixture is stirred at ℃, and a mixed solution of divalent phenol and monovalent phenol dissolved in a solvent in advance is added dropwise while bubbling air. Drip time from 50 minutes to 210
The range of minutes is preferred. If the drip time is not in this range,
The dispersion of the molecular weight distribution of the obtained oligomer becomes large.
Furthermore, it is preferable to carry out stirring for 5 minutes to 5 hours after the completion of dropping. Even if the mixture is stirred for 5 hours or more, the molecular weight does not increase further, so the reaction should be terminated.
【００１７】[0017]
【実施例】次に、本発明を実施例および比較例に基づい
て具体的に説明するが、本発明は以下の実施例により特
に限定されるものではない。なお、数平均分子量及び重
量平均分子量の測定にゲルパーミエーションクロマトグ
ラフィー(GPC)法により求めた。試料のGPC曲線と分子量
校正曲線よりデータ処理を行った。分子量校正曲線は、
標準ポリスチレンの分子量と溶出時間の関係を次の式に
近似して分子量校正曲線を得た。
LogＭ = Ａ0 Ｘ3+ Ａ1Ｘ2 ＋ Ａ2 Ｘ＋ Ａ3＋Ａ4／Ｘ2
ここで、Ｍ：分子量、Ｘ：溶出時間−１９、Ａ：係数で
ある。また、水酸基当量は2,6-ジメチルフェノールを標
準物質としてIR分析（液セル法）を行い、3600cm-1の吸
収強度より求めた。EXAMPLES Next, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to the following Examples. The number average molecular weight and the weight average molecular weight were measured by gel permeation chromatography (GPC) method. Data processing was performed from the GPC curve and molecular weight calibration curve of the sample. The molecular weight calibration curve is
The relationship between the molecular weight of standard polystyrene and the elution time was approximated to the following formula to obtain a molecular weight calibration curve. LogM = A 0 X 3 + A 1 X 2 + A 2 X + A 3 + A 4 / X 2 wherein, M: molecular weight, X: an elution time -19, A: a coefficient. The hydroxyl equivalent was determined from the absorption intensity at 3600 cm −1 by IR analysis (liquid cell method) using 2,6-dimethylphenol as a standard substance.
【００１８】(実施例1)攪拌装置、温度計、空気導入
管、じゃま板のついた2Ｌの縦長反応器にCuBr2 2.7g(0.
012 mol)、ジ-ｎ-ブチルアミン70.7ｇ（0.55 mol）、メ
チルエチルケトン 600ｇを仕込み、反応温度40℃にて攪
拌を行い、あらかじめ600ｇのメチルエチルケトンに溶
解させた2価のフェノール「2,2',3,3',5,5'-ヘキサメチ
ル-[1,1'-ビフェニル]-4,4'-ジオール」「イ」55.7ｇ
（0.21mol）と2,6-ジメチルフェノール50.4ｇ（0.41 mo
l）の混合溶液(構造式(2)で示される2価のフェノールと
構造式(3)で示される1価のフェノールのモル比率1:2)を
2 L/minの空気のバブリングを行いながら120分かけて滴
下し、さらに滴下終了後60分間、2 L/minの空気のバブ
リングを続けながら攪拌を行った。これにエチレンジア
ミン四酢酸二水素二ナトリウム水溶液を加え、反応を停
止した。その後、１Ｍの塩酸水溶液で3回洗浄を行った
後、イオン交換水で洗浄を行った。得られた溶液をエバ
ポレイタ−で濃縮し、さらに減圧乾燥を行い、100.3ｇ
を得た。このものの数平均分子量は650、重量平均分子
量810、水酸基当量が310であり、メチルエチルケトンに
可溶であった。（以下この樹脂を「ハ」と記す。）(Example 1) CuBr2 2.7 g (0. 0) in a 2 L vertical reactor equipped with a stirrer, a thermometer, an air inlet tube, and a baffle plate.
(012 mol), 70.7 g (0.55 mol) of di-n-butylamine and 600 g of methyl ethyl ketone were charged, stirred at a reaction temperature of 40 ° C., and the divalent phenol “2,2 ′, 3” was dissolved in 600 g of methyl ethyl ketone in advance. , 3 ', 5,5'-Hexamethyl- [1,1'-biphenyl] -4,4'-diol "" A "55.7g
(0.21 mol) and 2,6-dimethylphenol 50.4g (0.41 mo
l) mixed solution (molar ratio of divalent phenol represented by structural formula (2) to monovalent phenol represented by structural formula (3) 1: 2).
The mixture was added dropwise over 120 minutes while bubbling air at 2 L / min, and stirring was continued for 60 minutes after completion of the dropping while continuing bubbling air at 2 L / min. An aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogen was added thereto to stop the reaction. After that, it was washed three times with a 1 M aqueous hydrochloric acid solution and then washed with ion-exchanged water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain 100.3 g.
Got This product had a number average molecular weight of 650, a weight average molecular weight of 810 and a hydroxyl group equivalent of 310, and was soluble in methyl ethyl ketone. (Hereinafter, this resin is referred to as "C".)
【００１９】(実施例2)攪拌装置、温度計、空気導入
管、じゃま板のついた2Ｌの縦長反応器にCuCl 1.3g(0.0
13 mol)、ジ-ｎ-ブチルアミン79.5g（0.62 mol）、メチ
ルエチルケトン 600ｇを仕込み、反応温度40℃にて攪拌
を行い、あらかじめ600ｇのメチルエチルケトンに溶解
させた2価のフェノール「2,2',3,3',5,5'-ヘキサメチル
-[1,1'-ビフェニル]-4,4'-ジオール」「イ」41.8ｇ（0.
16mol）と2,6-ジメチルフェノール75.6ｇ（0.62mol）の
混合溶液(構造式(2)で示される2価のフェノールと構造
式(3)で示される1価のフェノールのモル比率1:4)を2 L/
minの空気のバブリングを行いながら120分かけて滴下
し、さらに滴下終了後30分間、2 L/minの空気のバブリ
ングを続けながら攪拌を行った。これにエチレンジアミ
ン四酢酸二水素二ナトリウム水溶液を加え、反応を停止
した。その後、１Ｍの塩酸水溶液で3回洗浄を行った
後、イオン交換水で洗浄を行った。得られた溶液をエバ
ポレイタ−で濃縮し、さらに減圧乾燥を行い、111.4ｇ
を得た。このものの数平均分子量は1110、重量平均分子
量1450、水酸基当量が580であり、メチルエチルケトン
に可溶であった。（以下この樹脂を「ニ」と記す。）Example 2 CuCl 1.3 g (0.0) was added to a 2 L vertical reactor equipped with a stirrer, a thermometer, an air inlet tube, and a baffle plate.
13 mol), di-n-butylamine 79.5 g (0.62 mol) and 600 g of methyl ethyl ketone were charged and stirred at a reaction temperature of 40 ° C., and the divalent phenol “2,2 ′, 3” was dissolved in 600 g of methyl ethyl ketone in advance. , 3 ', 5,5'-Hexamethyl
-[1,1'-Biphenyl] -4,4'-diol "" A "41.8g (0.
16mol) and 75.6 g (0.62mol) of 2,6-dimethylphenol (the molar ratio of the divalent phenol represented by the structural formula (2) to the monovalent phenol represented by the structural formula (3) is 1: 4. ) To 2 L /
The mixture was added dropwise over 120 minutes while bubbling air for min, and stirring was continued for 30 minutes after completion of the dropping while continuing bubbling of air at 2 L / min. An aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogen was added thereto to stop the reaction. After that, it was washed three times with a 1 M aqueous hydrochloric acid solution and then washed with ion-exchanged water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain 111.4 g.
Got This compound had a number average molecular weight of 11,10, a weight average molecular weight of 1,450 and a hydroxyl group equivalent of 580, and was soluble in methyl ethyl ketone. (Hereinafter, this resin is referred to as "D".)
【００２０】(実施例3)攪拌装置、温度計、空気導入
管、じゃま板のついた2Ｌの縦長反応器にCuCl 1.1g(0.0
11 mol)、ジ-ｎ-ブチルアミン66.3g（0.51 mol）、メチ
ルエチルケトン 500ｇを仕込み、反応温度40℃にて攪拌
を行い、あらかじめ600ｇのメチルエチルケトンに溶解
させた2価のフェノール「2,2',3,3',5,5'-ヘキサメチル
-[1,1'-ビフェニル]-4,4'-ジオール」「イ」20.9ｇ（0.
077mol）と2,6-ジメチルフェノール75.6ｇ（0.62 mol）
の混合溶液(構造式(2)で示される2価のフェノールと構
造式(3)で示される1価のフェノールのモル比率1:8)を2
L/minの空気のバブリングを行いながら120分かけて滴下
し、さらに滴下終了後30分間、2 L/minの空気のバブリ
ングを続けながら攪拌を行った。これにエチレンジアミ
ン四酢酸二水素二ナトリウム水溶液を加え、反応を停止
した。その後、１Ｍの塩酸水溶液で3回洗浄を行った
後、イオン交換水で洗浄を行った。得られた溶液をエバ
ポレイタ−で濃縮し、さらに減圧乾燥を行い、91.4ｇを
得た。このものの数平均分子量は1700、重量平均分子量
2300、水酸基当量が820であり、メチルエチルケトンに
可溶であった。（以下この樹脂を「ホ」と記す。）(Example 3) CuCl 1.1 g (0.0) was added to a 2 L vertical reactor equipped with a stirrer, a thermometer, an air inlet tube, and a baffle plate.
11 mol), 66.3 g (0.51 mol) of di-n-butylamine and 500 g of methyl ethyl ketone were charged, stirred at a reaction temperature of 40 ° C., and divalent phenol “2,2 ′, 3” dissolved in 600 g of methyl ethyl ketone in advance. , 3 ', 5,5'-Hexamethyl
-[1,1'-Biphenyl] -4,4'-diol "" A "20.9 g (0.
077 mol) and 2,6-dimethylphenol 75.6 g (0.62 mol)
Of the mixed solution of (the molar ratio of the divalent phenol represented by the structural formula (2) to the monovalent phenol represented by the structural formula (3) 1: 8).
The mixture was added dropwise over 120 minutes while bubbling air at L / min, and stirring was continued for 30 minutes after the completion of dropping while continuing bubbling air at 2 L / min. An aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogen was added thereto to stop the reaction. After that, it was washed three times with a 1 M aqueous hydrochloric acid solution and then washed with ion-exchanged water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain 91.4 g. The number average molecular weight of this product is 1700, weight average molecular weight
It had a hydroxyl group equivalent of 2300 and a hydroxyl equivalent of 820, and was soluble in methyl ethyl ketone. (Hereinafter, this resin is referred to as "e".)
【００２１】(実施例4)攪拌装置、温度計、空気導入
管、じゃま板のついた2Ｌの縦長反応器にCuCl 1.3g(0.0
13 mol)、ジ-ｎ-ブチルアミン79.5g（0.62 mol）、メチ
ルエチルケトン 600ｇを仕込み、反応温度40℃にて攪拌
を行い、あらかじめ600ｇのメチルエチルケトンに溶解
させた2価のフェノール「2,2',3,3',5,5'-ヘキサメチル
-[1,1'-ビフェニル]-4,4'-ジオール」「イ」41.8ｇ（0.
15mol）と2,6-ジメチルフェノール56.7ｇ（0.46 mol）
と2,3,6-トリメチルフェノール21.1ｇ（0.16mol）の混
合溶液(構造式(2)で示される2価のフェノールと構造式
(3)で示される1価のフェノールのモル比率1:4)を2 L/mi
nの空気のバブリングを行いながら120分かけて滴下し、
さらに滴下終了後30分間、2 L/minの空気のバブリング
を続けながら攪拌を行った。これにエチレンジアミン四
酢酸二水素二ナトリウム水溶液を加え、反応を停止し
た。その後、１Ｍの塩酸水溶液で3回洗浄を行った後、
イオン交換水で洗浄を行った。得られた溶液をエバポレ
イタ−で濃縮し、さらに減圧乾燥を行い、111.9ｇを得
た。このものの数平均分子量は1000、重量平均分子量13
50、水酸基当量が520であり、メチルエチルケトンに可
溶であった。（以下この樹脂を「ヘ」と記す。）Example 4 CuCl 1.3 g (0.0) was placed in a 2 L vertical reactor equipped with a stirrer, a thermometer, an air inlet tube, and a baffle plate.
13 mol), di-n-butylamine 79.5 g (0.62 mol) and 600 g of methyl ethyl ketone were charged and stirred at a reaction temperature of 40 ° C., and the divalent phenol “2,2 ′, 3” was dissolved in 600 g of methyl ethyl ketone in advance. , 3 ', 5,5'-Hexamethyl
-[1,1'-Biphenyl] -4,4'-diol "" A "41.8g (0.
15mol) and 5,6-dimethylphenol 56.7g (0.46mol)
And 2,3,6-trimethylphenol 21.1g (0.16mol) mixed solution (divalent phenol represented by structural formula (2) and structural formula
The molar ratio of monohydric phenol shown in (3) 1: 4) is 2 L / mi.
While bubbling n air, drop over 120 minutes,
Further, stirring was carried out for 30 minutes after completion of dropping while continuing bubbling of air at 2 L / min. An aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogen was added thereto to stop the reaction. After that, after washing 3 times with a 1 M hydrochloric acid aqueous solution,
It was washed with ion-exchanged water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain 111.9 g. This product has a number average molecular weight of 1,000 and a weight average molecular weight of 13
It had a hydroxyl group equivalent of 50 and a hydroxyl group equivalent of 520 and was soluble in methyl ethyl ketone. (Hereinafter, this resin is referred to as "F".)
【００２２】(比較例1)攪拌装置、温度計、空気導入
管、じゃま板のついた2Ｌの縦長反応器にCuCl 1.3g(0.0
13 mol)、ジ-ｎ-ブチルアミン79.5g（0.62 mol）、メチ
ルエチルケトン 600ｇを仕込み、反応温度40℃にて攪拌
を行い、あらかじめ520ｇのメチルエチルケトンに溶解
させた2価のフェノール「3,3',5,5'-テトラメチル-[1,
1'-ビフェニル]-4,4'-ジオール」「ロ」37.4ｇ（0.16mo
l）と2,6-ジメチルフェノール75.6ｇ（0.62 mol）の混
合溶液(構造式(2)で示される2価のフェノールと構造式
(3)で示される1価のフェノールのモル比率1:4)を2 L/mi
nの空気のバブリングを行いながら120分かけて滴下し、
さらに滴下終了後30分間、2 L/minの空気のバブリング
を続けながら攪拌を行ったところ、反応溶液に多量の沈
殿物が得られた。これにエチレンジアミン四酢酸二水素
二ナトリウム水溶液を加え、反応を停止し、固形物をろ
過した。その後、得られた固形物をメタノールで３回洗
浄を行った。得られた溶液をエバポレイタ−で濃縮し、
さらに減圧乾燥を行い、80.1ｇを得た。このものの数平
均分子量は5300、重量平均分子量9000、水酸基当量が38
00であり、メチルエチルケトンに不溶であった。以下こ
の樹脂を「ト」と記す。）(Comparative Example 1) 1.3 g of CuCl (0.0 g) was added to a 2 L vertical reactor equipped with a stirrer, a thermometer, an air inlet tube, and a baffle plate.
13 mol), 79.5 g (0.62 mol) of di-n-butylamine, and 600 g of methyl ethyl ketone were stirred and stirred at a reaction temperature of 40 ° C., and the divalent phenol “3,3 ′, 5” was dissolved in 520 g of methyl ethyl ketone in advance. , 5'-Tetramethyl- [1,
1'-biphenyl] -4,4'-diol "" ro "37.4g (0.16mo
l) and 75.6 g (0.62 mol) of 2,6-dimethylphenol (the divalent phenol represented by the structural formula (2) and the structural formula
The molar ratio of monohydric phenol shown in (3) 1: 4) is 2 L / mi.
While bubbling n air, drop over 120 minutes,
Further, stirring was performed for 30 minutes after completion of the dropping while continuing bubbling of air at 2 L / min, and a large amount of precipitate was obtained in the reaction solution. An aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogen was added thereto to stop the reaction, and the solid matter was filtered. Then, the obtained solid was washed with methanol three times. The resulting solution was concentrated with an evaporator,
Further, it was dried under reduced pressure to obtain 80.1 g. The number average molecular weight of this product is 5,300, the weight average molecular weight is 9,000, and the hydroxyl equivalent is 38.
And was insoluble in methyl ethyl ketone. Hereinafter, this resin is referred to as "to". )
【００２３】(比較例2)攪拌装置、温度計、空気導入
管、じゃま板のついた2Ｌの縦長反応器にCuCl 1.3g(0.0
13 mol)、ピリジン48.7g（0.62 mol）、メチルエチルケ
トン 600ｇを仕込み、反応温度40℃にて攪拌を行い、あ
らかじめ520ｇのメチルエチルケトンに溶解させた2価の
フェノール「2,2',3,3',5,5'-ヘキサメチル-[1,1'-ビフ
ェニル]-4,4'-ジオール」「イ」41.8ｇ（0.16 mol）と
2,6-ジメチルフェノール75.6ｇ（0.62 mol）の混合溶液
(構造式(2)で示される2価のフェノールと構造式(3)で示
される1価のフェノールのモル比率1:4)を2 L/minの空気
のバブリングを行いながら120分かけて滴下し、さらに
滴下終了後30分間、2 L/minの空気のバブリングを続け
ながら攪拌を行った。これにエチレンジアミン四酢酸二
水素二ナトリウム水溶液を加え、反応を停止した。その
後、１Ｍの塩酸水溶液で3回洗浄を行った後、イオン交
換水で洗浄を行った。得られた溶液をエバポレイタ−で
濃縮し、さらに減圧乾燥を行い、110.2ｇを得た。この
ものの数平均分子量は1100、重量平均分子量1820、水酸
基当量が600であった。（以下この樹脂を「チ」と記
す。）(Comparative Example 2) 1.3 g of CuCl (0.0 g) was placed in a 2 L vertical reactor equipped with a stirrer, a thermometer, an air inlet tube, and a baffle plate.
13 mol), 48.7 g (0.62 mol) of pyridine, and 600 g of methyl ethyl ketone were charged, stirred at a reaction temperature of 40 ° C., and the divalent phenol “2,2 ′, 3,3 ′, dissolved in 520 g of methyl ethyl ketone in advance” was added. 5,5'-hexamethyl- [1,1'-biphenyl] -4,4'-diol "" a "41.8 g (0.16 mol)
Mixed solution of 2,6-dimethylphenol 75.6g (0.62mol)
(Molar ratio of divalent phenol represented by structural formula (2) and monovalent phenol represented by structural formula (3) 1: 4) was added dropwise over 120 minutes while bubbling 2 L / min of air. Then, stirring was continued for 30 minutes after completion of the dropping while continuing bubbling of air at 2 L / min. An aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogen was added thereto to stop the reaction. After that, it was washed three times with a 1 M aqueous hydrochloric acid solution and then washed with ion-exchanged water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain 110.2 g. This product had a number average molecular weight of 1,100, a weight average molecular weight of 18,20 and a hydroxyl group equivalent of 600. (Hereinafter, this resin is referred to as "chi".)
【００２４】以上の結果を表１にまとめた。実施例1、
2、3から2価のフェノールのモル比を多くすることによ
り数平均分子量及び重量平均分子量が大きくなり、モル
比を変えることにより望みの分子量分布を有する2官能
オリゴマーを得ることができる。実施例2と比較例1の結
果から2価のフェノールの3位に置換基を有さないビフェ
ニルのフェノール「3,3',5,5'-テトラメチル-[1,1'-ビ
フェニル]-4,4'-ジオール」を原料に用いると平均分子
量5000以上のオリゴマーが生成し、メチルエチルケトン
に可溶な2官能性フェニレンエーテルを効率よく合成す
ることができない。The above results are summarized in Table 1. Example 1,
The number-average molecular weight and the weight-average molecular weight are increased by increasing the molar ratio of the dihydric phenol from 2, 3 or more, and the bifunctional oligomer having a desired molecular weight distribution can be obtained by changing the molar ratio. From the results of Example 2 and Comparative Example 1, biphenyl phenol "3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl]-having no substituent at the 3-position of divalent phenol" When 4,4'-diol "is used as a raw material, an oligomer having an average molecular weight of 5000 or more is produced, and a bifunctional phenylene ether soluble in methyl ethyl ketone cannot be efficiently synthesized.
【００２５】すなわち、2価のフェノールの3位に置換基
を有することがメチルエチルケトンに可溶な2官能性フ
ェニレンエーテルを効率よく合成することに必須であ
る。実施例2と比較例2の結果からアミンにジ-ｎ-ブチル
アミンを用いるとピリジンを用いた時よりシャープな分
子量分布を有するオリゴマーが得られる。実施例2と実
施例4の結果から1価のフェノールに2,6-ジメチルフェノ
ール単独を用いた時よりも2,6-ジメチルフェノールと2,
3,6-トリメチルフェノールを混合した時に、より低分子
のオリゴマーが得られる。これは2,3,6-トリメチルフェ
ノールの３位のメチル基が重合を抑制し、高分子体の生
成を抑えているためである。That is, having a substituent at the 3-position of the dihydric phenol is essential for efficiently synthesizing a bifunctional phenylene ether soluble in methyl ethyl ketone. From the results of Example 2 and Comparative Example 2, when di-n-butylamine is used as the amine, an oligomer having a sharper molecular weight distribution is obtained when pyridine is used. 2,6-Dimethylphenol and 2, from the results of Example 2 and Example 4 than when using 2,6-dimethylphenol alone in monovalent phenol
Lower molecular weight oligomers are obtained when 3,6-trimethylphenol is mixed. This is because the methyl group at the 3-position of 2,3,6-trimethylphenol suppresses the polymerization and suppresses the formation of polymer.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【発明の効果】本発明の2官能性フェニレンエーテルの
オリゴマー体は、ケトン系の溶媒に充分に可溶であり、
熱硬化性樹脂との相溶性がよく、例えば、積層板用のワ
ニスが容易に調整でき、成形加工性に優れる積層材料を
製造する事ができる。基本骨格が低誘電特性・強靭性を
あわせもつエンジニアプラスチィクスの一つポリフェニ
レンエーテルであるため、PPEポリマーと同様な特性を
有する電気・電子材料となる。更には、ケトン系溶媒中
で末端フェノール性水酸基の変性反応が容易に行う事が
できる。The bifunctional phenylene ether oligomer of the present invention is sufficiently soluble in a ketone solvent,
The compatibility with the thermosetting resin is good, and for example, a varnish for a laminate can be easily prepared, and a laminate material having excellent moldability can be produced. Since the basic skeleton is polyphenylene ether, which is one of the engineering plastics that has both low dielectric properties and toughness, it becomes an electrical / electronic material with properties similar to PPE polymers. Further, the modification reaction of the terminal phenolic hydroxyl group can be easily carried out in the ketone solvent.
【図１】比較例1における生成物のＧＰＣスペクトル。FIG. 1 is a GPC spectrum of the product in Comparative Example 1.
【図２】実施例2における生成物のＧＰＣスペクトル。FIG. 2 is a GPC spectrum of the product in Example 2.
【図３】ＧＰＣスペクトルの反応時間変化(実施例2)FIG. 3 Changes in reaction time of GPC spectrum (Example 2)
───────────────────────────────────────────────────── フロントページの続き (72)発明者 平松 聖生 東京都葛飾区新宿６丁目１番１号 三菱瓦 斯化学株式会社東京研究所内 (72)発明者 宮本 真 東京都葛飾区新宿６丁目１番１号 三菱瓦 斯化学株式会社東京研究所内 Ｆターム(参考） 4H006 AA01 AA02 AB84 AB91 AC43 BB16 GN02 GP06 GP12 4J005 AA26 BB01 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Seisei Hiramatsu 6-1, 1-1 Shinjuku, Katsushika-ku, Tokyo Mitsubishi tile The Chemical Research Institute Tokyo Research Center (72) Inventor Makoto Miyamoto 6-1, 1-1 Shinjuku, Katsushika-ku, Tokyo Mitsubishi tile The Chemical Research Institute Tokyo Research Center F-term (reference) 4H006 AA01 AA02 AB84 AB91 AC43 BB16 GN02 GP06 GP12 4J005 AA26 BB01
Claims (8)
造式(3)で示した1価のフェノールとの酸化重合で得られ
る以下の構造式(1) 【化１】 【化２】 【化３】 (式中、R1,R2は、同一または異なってもよく、ハロゲン
原子または炭素数6以下のアルキル基またはフェニル基
である。R3は、同一または異なってもよく、水素原子、
ハロゲン原子または炭素数6以下のアルキル基またはフ
ェニル基である。m, nは、少なくともいずれか一方が0
でない、0〜100の整数を示す。)で示したR1,R2が水素原
子でないことが必須の2官能性フェニレンエーテルのオ
リゴマー体。1. The following structural formula (1) obtained by oxidative polymerization of the divalent phenol represented by the structural formula (2) and the monovalent phenol represented by the structural formula (3): [Chemical 2] [Chemical 3] (In the formula, R1 and R2 may be the same or different, and are a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. R3 may be the same or different, a hydrogen atom,
It is a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. At least one of m and n is 0
Not an integer from 0 to 100. An oligomeric body of a bifunctional phenylene ether in which it is essential that R1 and R2 shown in) are not hydrogen atoms.
2官能性フェニレンエーテルのオリゴマー体。2. In the above structural formula (1), R1 and R2 are methyl groups.
An oligomer of bifunctional phenylene ether.
されたオリゴマー体。3. The oligomeric body according to claim 1, which has a weight average molecular weight of 5000 or less.
求項1に示されたオリゴマー体。4. The oligomeric body according to claim 1, which has a molecular weight distribution (Mw / Mn) of 1.6 or less.
2',3,3',5,5'-ヘキサメチル-[1,1'-ビフェニル]-4,4'-
ジオールである製造法。5. The divalent phenol represented by the structural formula (2) is 2,
2 ', 3,3', 5,5'-Hexamethyl- [1,1'-biphenyl] -4,4'-
A manufacturing method that is a diol.
が、2,6-ジメチルフェノール単独かこれと2,3,6-トリメ
チルフェノールの混合系で用いられ、2,3,6-トリメチル
フェノールの割合が1価のフェノール(3)の70mol%以下の
1価のフェノールである製造法。6. The monohydric phenol represented by the structural formula (3) is used as 2,6-dimethylphenol alone or in a mixed system of 2,6-dimethylphenol and 2,3,6-trimethylphenol. -The proportion of trimethylphenol is less than 70mol% of monovalent phenol (3)
A manufacturing method that is a monohydric phenol.
造式(3)に示される1価のフェノールのモル比率が1:1〜1
0である2官能性フェニレンエーテルのオリゴマー体の製
造法。7. The molar ratio of the divalent phenol represented by the structural formula (2) to the monovalent phenol represented by the structural formula (3) is 1: 1 to 1.
A method for producing an oligomer of a bifunctional phenylene ether having 0.
造法。8. A production method, wherein the solvent is a ketone system.
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| US10/180,507 US6794481B2 (en) | 2001-06-28 | 2002-06-27 | Bifunctional phenylene ether oligomer, its derivatives, its use and process for the production thereof |
| TW91114155A TW591054B (en) | 2001-06-28 | 2002-06-27 | Bifunctional phenylene ether oligomer, derivatives and process for the production thereof |
| KR1020020037051A KR100874723B1 (en) | 2001-06-28 | 2002-06-28 | 2 functional phenylene ether oligomer, derivatives thereof and preparation method thereof |
| US10/851,290 US6962744B2 (en) | 2001-06-28 | 2004-05-24 | Bifunctional phenylene ether oligomer, its derivatives, its use and process for the production thereof |
| US11/110,917 US7247682B2 (en) | 2001-06-28 | 2005-04-21 | Bifunctional phenylene ether oligomer, its derivatives, its use and process for the production thereof |
| US11/812,892 US7388057B2 (en) | 2001-06-28 | 2007-06-22 | Di(meth)acrylate of epoxy-terminated polyphenylene ether |
| US12/068,925 US7446154B2 (en) | 2001-06-28 | 2008-02-13 | Carboxylic acid-modified biphenyl epoxy diacrylate |
| KR1020080055418A KR100919943B1 (en) | 2001-06-28 | 2008-06-12 | Bifunctional phenylene ether oligomer, its derivatives, its use and process for the production thereof |
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