JP4196164B2 - Method for producing bifunctional phenylene ether oligomer - Google Patents

Description

【００１０】
（上記式中、R¹、R²、R³、R⁷、R⁸、R⁹、R¹⁰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を示す。R⁴、R⁵、R⁶、R¹¹、R¹²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を示す。ｍ、ｎは、少なくともいずれか一方が0でない0〜25の整数を示す。）
【００１１】
本発明の2価のフェノール体とは、下記構造式(2)で表される2価のフェノールである。
【化３】

【００１２】
ここで、構造式(2)の2価のフェノール体とは、R¹、R²、R³、R⁷、R⁸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。R⁴、R⁵、R⁶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、R³、R⁷、R⁸が水素原子でないことが必須の2価のフェノールであり、2,3,3',5,5'-ペンタメチル-(1,1'-ビフェニル)-4,4'-ジオール、2,2',3,3',5,5'-ヘキサメチル-(1,1'-ビフェニル)-4,4'-ジオールなどが好ましい。
【００１３】
本発明の１価のフェノール体とは、下記構造式(3)で表される1価のフェノールである。
【化４】

【００１４】
構造式(3)において、R⁹、R¹⁰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。R¹¹、R¹²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、またはこれと2,3,6位あるいは2,3,5,6位に置換基を有するものが併用されることが好ましい。更には、単独では2,6-ジメチルフェノールが好ましく、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好ましい。
【００１５】
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オリゴマー体は、構造式(2)で表される2価のフェノール体と、構造式(3)で表される1価のフェノール体と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、空気を使用する方法がある。また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。設備投資が安価である事から空気酸化が好ましいが、安全性から反応器中の酸素濃度を爆発限界の限界酸素濃度以下で酸化重合反応を実施することが更に好ましい。限界酸素濃度以下での酸化重合反応方法としては、気相中に不活性ガスを供給しながら空気で酸化重合反応を行う方法、または不活性ガス等と空気を混合して酸素濃度を3〜15%に調整した混合ガスで酸化重合反応を行う方法がある。酸化重合反応を実施するには、圧力は通常大気圧から20kg/cm²までの圧力が選ばれる。
【００１６】
酸化重合反応を実施する場合の触媒としては、CuCl、CuBr、Cu₂SO₄、CuCl₂、CuBr₂、CuSO₄、CuI等の銅塩等の一種または二種以上が用いられるが、特にこれらに限定されるものではない。上記触媒に加えて、ジイソプロピルアミン、ジ-sec-ブチルアミン、ジ-ｔ-ブチルアミン、ジ-ｔ-アミルアミン、ジシクロペンチルアミン、ジシクロヘキシルアミン、ジフェニルアミン、p,p'-ジトリルアミン、m,m'-ジトリルアミン、エチル-t-ブチルアミン、N,N'-ジ-t-ブチルエチレンジアミン、メチルシクロヘキシルアミン、メチルフェニルアミン、トリエチルアミン、メチルジエチルアミン、n-ブチルジメチルアミン、ベンジルジメチルアミン、フェニルジメチルアミン、N,N-ジメチル-p-トルイジン、トリフェニルアミン、N,N'-ジメチルピペラジン、2,6-ジメチルピリジン等から一種または二種以上が併用される。3級アミン及び2級アルキル基、3級アルキル基あるいはアリール基を有する2級アミンであれば、特にこれらに限定されるものではない。上記のアミンを使用することで、アミン付加体のない2官能性フェニレンエーテルオリゴマー体を得ることができる。このアミン付加体のない2官能性フェニレンエーテルオリゴマー体は、付加したアミンに官能基変換を阻害されることがないので、フェノール性水酸基を他の官能基へ容易かつ効率的に変換することができる。
【００１７】
本発明では、構造式(2)で表される2価のフェノール体と構造式(3)で表される1価のフェノール体とを一定のモル比で供給して反応させることで、所望する数平均分子量を有する構造式(1)で表される2官能性フェニレンエーテルオリゴマー体を効率的に製造することが出来る。例えば、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、1価のフェノールとして2,6-ジメチルフェノールを選び、1：3のモル比とした場合には数平均分子量が600〜700、1：5のモル比とした場合には数平均分子量が850〜950、1：10のモル比とした場合には数平均分子量が1,450〜1,550の2官能性フェニレンエーテルオリゴマー体をそれぞれ得ることができる。
【００１８】
本発明では、原料フェノールの供給終了後も未反応のフェノールが残存している間は、酸化重合反応を継続することは可能である。但し、原料フェノールが全て反応した後も酸化重合反応を継続することは、反応時間が長くなり経済的でない。
【００１９】
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、有機溶媒に溶け難いポリマーが生成するため、反応溶媒としてケトンやアルコールを用いることができなかったが、本発明の生成物は、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、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、プロパノール、イソプロパノール、ブタノール、エチレングリコール、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。
【００２０】
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、30〜50℃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難しくなり、分子量制御が困難となる。30℃以下では使用する溶媒によっては爆発限界の範囲に入り、安全な製造ができない。
【００２１】
【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は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 = A₀X³+ A₁X² + A₂X + A₃ + A₄/X²
ここで、M：分子量、X：溶出時間−19(分)、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；セル長＝1mm）を行い、3,600cm^-1の吸収強度より求めた。
【００２２】
（実施例1） 攪拌装置、温度計、空気導入管、じゃま板のついた12Ｌの縦長反応器にCuBr₂ 2.77g(12.5mmol)、N,N'-ジ-ｔ-ブチルエチレンジアミン0.54g(3.1mmol)、n-ブチルジメチルアミン20.03g(198.3mmol)、トルエン 2,600gを仕込み、反応温度40℃にて攪拌を行い、あらかじめ2,300gのメタノールに溶解させた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(以下HMBPと記す) 129.32g(0.48mol)、2,6-ジメチルフェノール175.31g(1.44mol)、N,N'-ジ-ｔ-ブチルエチレンジアミン0.36g(2.1mmol)、n-ブチルジメチルアミン7.79g(77.1mmol)、の混合溶液(構造式(2)で表される2価のフェノール体と構造式(3)で表される1価のフェノールのモル比率1:3)を、窒素と空気とを混合して酸素濃度8%に調整した混合ガスを5.2 L/minの流速でバブリングを行いながら230分かけて滴下し、攪拌を行った。滴下終了後、エチレンジアミン四酢酸四ナトリウム14.20g(37.4mmol)を溶解した水1,500gを加え、反応を停止した。水層と有機層を分液し、有機層を1.0Nの塩酸水溶液、次いで純水で洗浄した。得られた溶液をエバポレーターで濃縮し、さらに減圧乾燥を行い、2官能性フェニレンエーテルオリゴマー体295.6gを得た。このものの数平均分子量は650、重量平均分子量は1,040、水酸基当量が325であった。尚、¹H-NMRを測定したところ、アミンに相当するピークは検出されず、アミン付加体は生成していないことが確認された。
【００２３】
（実施例2） 攪拌装置、温度計、空気導入管、じゃま板のついた12Ｌの縦長反応器にCuBr₂ 3.88g(17.4mmol)、N,N'-ジ-ｔ-ブチルエチレンジアミン0.75g(4.4mmol)、n-ブチルジメチルアミン28.04g(277.6mmol)、トルエン 2,600gを仕込み、反応温度40℃にて攪拌を行い、あらかじめ2,300gのメタノールに溶解させたHMBP 129.32g(0.48mol)、2,6-ジメチルフェノール292.19g(2.40mol)、N,N'-ジ-ｔ-ブチルエチレンジアミン0.51g(2.9mmol)、n-ブチルジメチルアミン10.90g(108.0mmol)の混合溶液(構造式(2)で表される2価のフェノール体と構造式(3)で表される1価のフェノール体のモル比率1:5)を、窒素と空気とを混合して酸素濃度8%に調整した混合ガスを5.2 L/minの流速でバブリングを行いながら230分かけて滴下し、攪拌を行った。滴下終了後、エチレンジアミン四酢酸四ナトリウム19.89g(52.3mmol)を溶解した水1,500gを加え、反応を停止した。水層と有機層を分液し、有機層を1.0Nの塩酸水溶液、次いで純水で洗浄した。得られた溶液をエバポレーターで濃縮し、さらに減圧乾燥を行い、2官能性フェニレンエーテルオリゴマー体414.2gを得た。このものの数平均分子量は930、重量平均分子量は1,460、水酸基当量が465であった。尚、¹H-NMRを測定したところ、アミンに相当するピークは検出されず、アミン付加体は生成していないことが確認された。
【００２４】
（実施例3） 攪拌装置、温度計、空気導入管、じゃま板のついた12Ｌの縦長反応器にCuBr₂ 6.64g(29.9mmol)、N,N'-ジ-ｔ-ブチルエチレンジアミン1.29g(7.5mmol)、n-ブチルジメチルアミン48.07g(475.9mmol)、トルエン 2,600gを仕込み、反応温度40℃にて攪拌を行い、あらかじめ2,300gのメタノールに溶解させたHMBP 129.32g(0.48mol)、2,6-ジメチルフェノール584.38g(4.79mol)、N,N'-ジ-ｔ-ブチルエチレンジアミン0.87g(5.1mmol)、n-ブチルジメチルアミン18.69g(185.1mmol)の混合溶液(構造式(2)で表される2価のフェノール体と構造式(3)で表される1価のフェノール体のモル比率1:10)を、窒素と空気とを混合して酸素濃度8%に調整した混合ガスを5.2 L/minの流速でバブリングを行いながら230分かけて滴下し、攪拌を行った。滴下終了後、エチレンジアミン四酢酸四ナトリウム34.09g(89.7mmol)を溶解した水1,500gを加え、反応を停止した。水層と有機層を分液し、有機層を1.0Nの塩酸水溶液、次いで純水で洗浄した。得られた溶液をエバポレーターで濃縮し、さらに減圧乾燥を行い、2官能性フェニレンエーテルオリゴマー体702.2gを得た。このものの数平均分子量は1,490、重量平均分子量は2,320、水酸基当量が750であった。尚、¹H-NMRを測定したところ、アミンに相当するピークは検出されず、アミン付加体は生成していないことが確認された。
【００２５】
（実施例4） 攪拌装置、温度計、空気導入管、じゃま板のついた12Ｌの縦長反応器にCuBr₂ 3.88g(17.4mmol)、N,N'-ジ-ｔ-ブチルエチレンジアミン0.75g(4.4mmol)、n-ブチルジメチルアミン28.04g(277.6mmol)、メチルエチルケトン 2,600gを仕込み、反応温度40℃にて攪拌を行い、あらかじめ2,300gのメチルエチルケトンに溶解させたHMBP 129.32g(0.48mol)、2,6-ジメチルフェノール292.19g(2.40mol)、N,N'-ジ-ｔ-ブチルエチレンジアミン0.51g(2.9mmol)、n-ブチルジメチルアミン10.90g(108.0mmol)の混合溶液(構造式(2)で表される2価のフェノール体と構造式(3)で表される1価のフェノール体のモル比率1:5)を3.5 L/minの空気のバブリングを行いながら95分かけて滴下し、攪拌を行った。この際、気相中に3.5L/minの窒素ガスを流通させた。滴下終了後、エチレンジアミン四酢酸四ナトリウム19.89g(52.3mmol)を溶解した水1,500gを加え、反応を停止した。水層と有機層を分液し、有機層を1.0Nの塩酸水溶液、次いで純水で洗浄した。得られた溶液をエバポレーターで濃縮し、さらに減圧乾燥を行い、フェニレンエーテルオリゴマー体413.1gを得た。このものの数平均分子量は920、重量平均分子量は1,440、水酸基当量が460であった。尚、¹H-NMRを測定したところ、アミンに相当するピークは検出されず、アミン付加体は生成していないことが確認された。
【００２６】
（比較例1） 攪拌装置、温度計、空気導入管、じゃま板のついた12Ｌの縦長反応器にCuBr₂ 3.88g(17.4mmol)、N,N'-ジ-ｔ-ブチルエチレンジアミン0.85g(4.9mmol)、n-ブチルジメチルアミン10.40g(102.8mmol)、ジ-n-ブチルアミン8.21g(63.5mmol)、トルエン 2,600gを仕込み、反応温度40℃にて攪拌を行い、あらかじめ2,300gのメタノールに溶解させたHMBP 129.32g(0.48mol)、2,6-ジメチルフェノール292.19g(2.40mol)、N,N'-ジ-ｔ-ブチルエチレンジアミン1.70g(9.9mmol)、n-ブチルジメチルアミン20.80g(205.6mmol)、ジ-n-ブチルアミン16.43g(127.1mmol)の混合溶液(構造式(2)で表される2価のフェノール体と構造式(3)で表される1価のフェノール体のモル比率1:5)を、窒素と空気とを混合して酸素濃度8%に調整した混合ガスを5.2 L/minの流速でバブリングを行いながら230分かけて滴下し、攪拌を行った。滴下終了後、エチレンジアミン四酢酸四ナトリウム19.84g(52.2mmol)を溶解した水1,500gを加え、反応を停止した。水層と有機層を分液し、有機層を1.0Nの塩酸水溶液、次いで純水で洗浄した。得られた溶液をエバポレーターで濃縮し、さらに減圧乾燥を行い、2官能性フェニレンエーテルオリゴマー体408.4gを得た。このものの数平均分子量は930、重量平均分子量は1,370、水酸基当量が470であった。尚、H¹-NMRを測定したところ、ジ-n-ブチルアミンに相当するピークが検出され、そのメチル基のピーク(0.89ppm)の積分比からアミン付加体が22%存在することが確認された。
【００２７】
（比較例2） 攪拌装置、温度計、空気導入管、じゃま板のついた12Ｌの縦長反応器にCuBr₂ 10.85g(48.8mmol)、ジ-n-ブチルアミン286.83g(2.22mol)、トルエン 2,600gを仕込み、反応温度40℃にて攪拌を行い、あらかじめ2,300gのメタノールに溶解させたHMBP 129.32g(0.48mol)、2,6-ジメチルフェノール292.19g(2.40mol)の混合溶液(構造式(2)で表される2価のフェノール体と構造式(3)で表される1価のフェノール体のモル比率1:5)を、窒素と空気とを混合して酸素濃度8%に調整した混合ガスを5.2 L/minの流速でバブリングを行いながら230分かけて滴下し、攪拌を行った。滴下終了後、エチレンジアミン四酢酸四ナトリウム55.68g(146.5mmol)を溶解した水1,500gを加え、反応を停止した。水層と有機層を分液し、有機層を1.0Nの塩酸水溶液、次いで純水で洗浄した。得られた溶液をエバポレーターで濃縮し、さらに減圧乾燥を行い、2官能性フェニレンエーテルオリゴマー体404.6gを得た。このものの数平均分子量は910、重量平均分子量は1,310、水酸基当量が455であった。尚、H¹-NMRを測定したところ、ジ-n-ブチルアミンに相当するピークが検出され、そのメチル基のピーク(0.89ppm)の積分比からアミン付加体が15%存在することが確認された。
【００２８】
【表１】

【００２９】
【発明の効果】
本発明の製造法により、所望する分子量を有し、アミン付加体のない2官能性フェニレンエーテルのオリゴマー体を効率的に製造することが可能となる。本発明で得られる2官能性フェニレンエーテルのオリゴマー体は、アミンが付加していないので、末端フェノール性水酸基を容易に他の官能基に誘導できる。更に基本骨格がポリフェニレンエーテル構造であるので、耐熱性、誘電特性等に優れ、電気・電子材料に応用することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a bifunctional phenylene ether oligomer having a phenolic hydroxyl group at both ends, and to a method for producing a bifunctional phenylene ether oligomer having no amine adduct.
[0002]
[Prior art]
Materials for electrical and electronic applications are required to have low dielectric properties for processing large amounts of data in an advanced information society at high speed and toughness to prevent microcracks from being generated due to thermal shock. On the other hand, the use of engineering plastics such as polyphenylene ether (PPE) has been proposed.
[0003]
However, PPE has excellent high-frequency characteristics, but has poor compatibility with thermosetting resins such as epoxy resins and cyanate resins, has high melt viscosity and poor moldability, and dissolves solvents such as 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.
[0004]
In order to improve the compatibility, a method of improving the compatibility by blending with other resins as a compatibilizing agent, and examination of pseudo-IPN structuring of PPE and cyanate resin (for example, see Patent Document 1) have been made. Molding processability and heat resistance have not been solved. In order to improve moldability, methods such as making polymer PPE into low molecules have been studied. For example, polymer PPE and divalent phenol are redistributed under a radical catalyst (for example, see Patent Document 2), or divalent phenol and monovalent phenol are oxidatively polymerized (for example, Patent Document 3). Etc.) are known. However, in any of the methods, a polymer was present, and a bifunctional phenylene ether oligomer having a desired molecular weight could not be obtained efficiently.
[0005]
In addition, polyphenylene ether resins obtained by oxidative polymerization of phenols are widely known to add an aliphatic secondary amine used in the oxidative polymerization reaction to the benzyl position at the ortho position of the terminal phenol (for example, (See Patent Document 4). When the terminal phenolic hydroxyl group of the polyphenylene ether resin is derived to another functional group, there is a problem that the added amine inhibits the reaction or decreases the stability of the functional group. As a method for reducing the amount of amine adduct produced, a method using a specific amine has been proposed (for example, see Patent Document 5), but the effect was insufficient. Furthermore, although a method for replacing the amine added to the polyphenylene ether resin with an alcohol has been proposed (see, for example, Patent Document 6), there are problems such as an increase in the number of steps.
[0006]
[Patent Document 1]
JP 11-21452 A (page 1-6)
[Patent Document 2]
JP-A-9-291148 (page 1-3)
[Patent Document 3]
Japanese Patent Publication No. 8-011747 (page 1-3)
[Patent Document 4]
JP 52-897 A (pages 1-7)
[Patent Document 5]
JP 62-131022 (page 1-4)
[Patent Document 6]
JP 5-148357 A (page 1-5)
[0007]
[Problems to be solved by the invention]
The present invention has been made in view of the above-mentioned facts, and its object is to have excellent electrical properties and toughness of PPE, and improve compatibility with thermosetting resins and moldability. Another object of the present invention is to provide a method for producing a bifunctional phenylene ether oligomer having no amine adduct, which is easily dissolved in a general-purpose ketone solvent and can easily be modified with a terminal phenolic hydroxyl group.
[0008]
[Means for Solving the Problems]
As a result of intensive research on a method for producing a bifunctional phenylene ether oligomer, the present inventors have obtained a copper-based catalyst and a secondary amine having a tertiary amine or a secondary alkyl group, a tertiary alkyl group or an aryl group. Alternatively, by using a mixed system of both, by performing an oxidative polymerization reaction of the divalent phenol represented by the following structural formula (2) and the monovalent phenol represented by the following structural formula (3), It was discovered that a bifunctional phenylene ether oligomer represented by the following structural formula (1) without an amine adduct can be stably and efficiently produced, and the present invention has been completed. The present invention is described in detail below.
[0009]
[Chemical 2]

[0010]
(In the above formula, R ¹ , R ² , R ³ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different, and represent a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R ⁴ , R ⁵ , R ⁶ , R ¹¹ and R ¹² may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and m and n are at least one of (One indicates an integer from 0 to 25 that is not 0.)
[0011]
The divalent phenol compound of the present invention is a divalent phenol represented by the following structural formula (2).
[Chemical 3]

[0012]
Here, the divalent phenol form of the structural formula (2), R ¹ , R ² , R ³ , R ⁷ , R ⁸ may be the same or different, a halogen atom or an alkyl group having 6 or less carbon atoms or It is a phenyl group. R ⁴ , R ⁵ , and R ⁶ may be the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and R ¹ , R ² , R ³ , R ⁷ , R ⁸ Is a divalent phenol that is not a hydrogen atom, and 2,3,3 ′, 5,5′-pentamethyl- (1,1′-biphenyl) -4,4′-diol, 2,2 ′, 3,3 ′, 5,5′-hexamethyl- (1,1′-biphenyl) -4,4′-diol and the like are preferable.
[0013]
The monovalent phenol compound of the present invention is a monovalent phenol represented by the following structural formula (3).
[Formula 4]

[0014]
In the structural formula (3), R ⁹ and R ¹⁰ may be the same or different, and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R ¹¹ and R ¹² may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. In particular, those having a substituent at the 2,6 position alone or those having a substituent at the 2,3,6 position or the 2,3,5,6 position are preferably used in combination. Furthermore, 2,6-dimethylphenol is preferable alone, and 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable in combination.
[0015]
The bifunctional phenylene ether oligomer represented by the structural formula (1) of the present invention includes a divalent phenol represented by the structural formula (2) and a monovalent phenol represented by the structural formula (3). Is obtained by oxidative polymerization. As for the oxidation method, there is a method of directly using oxygen gas or air. There is also an electrode oxidation method. Any method may be used and is not particularly limited. Air oxidation is preferable because the capital investment is inexpensive, but it is more preferable to carry out the oxidative polymerization reaction with the oxygen concentration in the reactor below the critical oxygen concentration at the explosion limit for safety. As a method for oxidative polymerization reaction at a critical oxygen concentration or less, a method of performing an oxidative polymerization reaction with air while supplying an inert gas in the gas phase, or an oxygen concentration of 3 to 15 by mixing air with an inert gas or the like. There is a method of performing an oxidative polymerization reaction with a mixed gas adjusted to%. In order to carry out the oxidative polymerization reaction, the pressure is usually selected from atmospheric pressure to 20 kg / cm ² .
[0016]
As the catalyst for carrying out the oxidative polymerization reaction, one or more of copper salts such as CuCl, CuBr, Cu ₂ SO ₄ , CuCl ₂ , CuBr ₂ , CuSO ₄ , CuI, etc. are used. It is not limited. In addition to the above catalysts, diisopropylamine, di-sec-butylamine, di-t-butylamine, di-t-amylamine, dicyclopentylamine, dicyclohexylamine, diphenylamine, p, p'-ditolylamine, m, m'-ditolylamine, Ethyl-t-butylamine, N, N'-di-t-butylethylenediamine, methylcyclohexylamine, methylphenylamine, triethylamine, methyldiethylamine, n-butyldimethylamine, benzyldimethylamine, phenyldimethylamine, N, N-dimethyl One or more of -p-toluidine, triphenylamine, N, N'-dimethylpiperazine, 2,6-dimethylpyridine and the like are used in combination. A secondary amine having a tertiary amine and a secondary alkyl group, tertiary alkyl group or aryl group is not particularly limited thereto. By using the above amine, a bifunctional phenylene ether oligomer without an amine adduct can be obtained. This bifunctional phenylene ether oligomer without an amine adduct is capable of easily and efficiently converting a phenolic hydroxyl group to another functional group because the added amine does not inhibit the functional group conversion. .
[0017]
In the present invention, the divalent phenol compound represented by the structural formula (2) and the monovalent phenol compound represented by the structural formula (3) are supplied at a constant molar ratio to cause a reaction. A bifunctional phenylene ether oligomer represented by the structural formula (1) having a number average molecular weight can be efficiently produced. For example, 2,2 ', 3,3', 5,5'-hexamethyl- (1,1'-biphenyl) -4,4'-diol as divalent phenol, 2,6-dimethyl as monovalent phenol When phenol is selected and the molar ratio is 1: 3, the number average molecular weight is 600 to 700, and when the molar ratio is 1: 5, the number average molecular weight is 850 to 950 and the molar ratio is 1:10. In this case, bifunctional phenylene ether oligomers having a number average molecular weight of 1,450 to 1,550 can be obtained.
[0018]
In the present invention, the oxidative polymerization reaction can be continued while the unreacted phenol remains even after the supply of the raw material phenol. However, it is not economical to continue the oxidative polymerization reaction even after all the raw material phenols have reacted, because the reaction time becomes longer.
[0019]
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 are limited in use in conventional oxidative polymerization of PPE, can be used in the present invention. Conventionally, since this kind of reaction produces a polymer that is hardly soluble in an organic solvent, ketone or alcohol cannot be used as a reaction solvent. However, the product of the present invention is easily dissolved in ketone and alcohol, The range of solvents that can be used has greatly expanded. They can 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 methylene chloride and chloroform. Examples of ketone solvents include acetone, methyl ethyl ketone, diethyl ketone, methyl butyl ketone, and methyl isobutyl ketone. Examples of alcohol solvents include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, and propylene glycol. However, it is not limited to these.
[0020]
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 to be used, but is preferably 30 to 50 ° C. Since oxidative polymerization is an exothermic reaction, temperature control becomes difficult at 50 ° C. or higher, and molecular weight control becomes difficult. Below 30 ° C, depending on the solvent used, it is within the explosion limit range, and safe production is not possible.
[0021]
【Example】
EXAMPLES Next, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not specifically limited by a following example. The number average molecular weight and the weight average molecular weight were determined 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 was obtained by approximating the relationship between the molecular weight of standard polystyrene and the elution time to the following equation.
LogM = A ₀ X ³ + A ₁ X ² + A ₂ X + A ₃ + A ₄ / X ²
Here, M: molecular weight, X: elution time -19 (min), A: coefficient. The hydroxyl group equivalent was determined from the absorption intensity of 3,600 cm ⁻¹ by performing IR analysis (liquid cell method; cell length = 1 mm) using 2,6-dimethylphenol as a standard substance.
[0022]
(Example 1) CuBr ₂ 2.77 g (12.5 mmol), N, N′-di-t-butylethylenediamine 0.54 g (3.1) in a 12-liter vertical reactor equipped with a stirrer, a thermometer, an air introduction tube, and a baffle plate mmol), 20.03 g (198.3 mmol) of n-butyldimethylamine, 2,600 g of toluene, stirred at a reaction temperature of 40 ° C., and 2,2 ′, 3,3 ′, dissolved in 2,300 g of methanol in advance. 5,5'-hexamethyl- (1,1'-biphenyl) -4,4'-diol (hereinafter referred to as HMBP) 129.32 g (0.48 mol), 2,6-dimethylphenol 175.31 g (1.44 mol), N, A mixed solution of N'-di-t-butylethylenediamine 0.36 g (2.1 mmol) and n-butyldimethylamine 7.79 g (77.1 mmol) (the divalent phenol compound represented by the structural formula (2) and the structural formula ( While mixing a mixture of nitrogen and air to adjust the oxygen concentration to 8% by mixing the molar ratio of monohydric phenol represented by 3) with a flow rate of 5.2 L / min for 230 minutes. The mixture was added dropwise and stirred. After completion of the dropwise addition, 1,500 g of water in which 14.20 g (37.4 mmol) of ethylenediaminetetraacetic acid tetrasodium was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with 1.0N hydrochloric acid aqueous solution and then with pure water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain 295.6 g of a bifunctional phenylene ether oligomer. This had a number average molecular weight of 650, a weight average molecular weight of 1,040, and a hydroxyl group equivalent of 325. When ¹ H-NMR was measured, no peak corresponding to the amine was detected, confirming that no amine adduct was formed.
[0023]
(Example 2) CuBr ₂ 3.88 g (17.4 mmol), N, N′-di-t-butylethylenediamine 0.75 g (4.4 g) in a 12 L vertical reactor equipped with a stirrer, a thermometer, an air introduction tube, and a baffle plate mmol), 28.04 g (277.6 mmol) of n-butyldimethylamine, 2,600 g of toluene, stirred at a reaction temperature of 40 ° C., and 129.32 g (0.48 mol) of HMBP previously dissolved in 2,300 g of methanol, 2, A mixed solution of 292.19 g (2.40 mol) of 6-dimethylphenol, 0.51 g (2.9 mmol) of N, N′-di-t-butylethylenediamine and 10.90 g (108.0 mmol) of n-butyldimethylamine (in the structural formula (2) A mixed gas in which the molar ratio of the divalent phenol compound represented by the structural formula (3) and the monovalent phenol compound represented by the structural formula (3) is adjusted to an oxygen concentration of 8% by mixing nitrogen and air. While bubbling at a flow rate of 5.2 L / min, the solution was added dropwise over 230 minutes and stirred. After completion of the dropwise addition, 1,500 g of water in which 19.89 g (52.3 mmol) of ethylenediaminetetraacetic acid tetrasodium was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with 1.0N hydrochloric acid aqueous solution and then with pure water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain 414.2 g of a bifunctional phenylene ether oligomer. This had a number average molecular weight of 930, a weight average molecular weight of 1,460, and a hydroxyl group equivalent of 465. When ¹ H-NMR was measured, no peak corresponding to the amine was detected, confirming that no amine adduct was formed.
[0024]
(Example 3) CuBr ₂ 6.64 g (29.9 mmol), N, N′-di-t-butylethylenediamine 1.29 g (7.5 kg) were added to a 12 L vertical reactor equipped with a stirrer, a thermometer, an air introduction tube, and a baffle plate. mmol), 48.07 g (475.9 mmol) of n-butyldimethylamine, 2,600 g of toluene, stirred at a reaction temperature of 40 ° C., and 129.32 g (0.48 mol) of HMBP previously dissolved in 2,300 g of methanol, 2, A mixed solution of 58.38 g (4.79 mol) of 6-dimethylphenol, 0.87 g (5.1 mmol) of N, N′-di-t-butylethylenediamine and 18.69 g (185.1 mmol) of n-butyldimethylamine (in the structural formula (2) A mixed gas in which the molar ratio of the divalent phenol compound represented by the structural formula (3) and the monovalent phenol compound represented by the structural formula (3) is adjusted to an oxygen concentration of 8% by mixing nitrogen and air. While bubbling at a flow rate of 5.2 L / min, the solution was added dropwise over 230 minutes and stirred. After completion of the dropwise addition, 1,500 g of water in which 34.09 g (89.7 mmol) of ethylenediaminetetraacetic acid tetrasodium was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with 1.0N hydrochloric acid aqueous solution and then with pure water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain 702.2 g of a bifunctional phenylene ether oligomer. This had a number average molecular weight of 1,490, a weight average molecular weight of 2,320, and a hydroxyl group equivalent of 750. When ¹ H-NMR was measured, no peak corresponding to the amine was detected, confirming that no amine adduct was formed.
[0025]
(Example 4) CuBr ₂ 3.88 g (17.4 mmol), N, N′-di-t-butylethylenediamine 0.75 g (4.4 g) were added to a 12 L vertical reactor equipped with a stirrer, a thermometer, an air introduction tube and a baffle plate. mmol), n-butyldimethylamine 28.04 g (277.6 mmol), methyl ethyl ketone 2,600 g, stirred at a reaction temperature of 40 ° C., HMBP 129.32 g (0.48 mol), A mixed solution of 292.19 g (2.40 mol) of 6-dimethylphenol, 0.51 g (2.9 mmol) of N, N′-di-t-butylethylenediamine and 10.90 g (108.0 mmol) of n-butyldimethylamine (in the structural formula (2) Molar ratio 1: 5) of the divalent phenol compound represented by the structural formula (3) and the monovalent phenol compound represented by the structural formula (3) was added dropwise over 95 minutes while bubbling 3.5 L / min of air, and stirred. Went. At this time, 3.5 L / min of nitrogen gas was circulated in the gas phase. After completion of the dropwise addition, 1,500 g of water in which 19.89 g (52.3 mmol) of ethylenediaminetetraacetic acid tetrasodium was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with 1.0N hydrochloric acid aqueous solution and then with pure water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain 413.1 g of a phenylene ether oligomer. This had a number average molecular weight of 920, a weight average molecular weight of 1,440, and a hydroxyl group equivalent of 460. When ¹ H-NMR was measured, no peak corresponding to the amine was detected, confirming that no amine adduct was formed.
[0026]
(Comparative Example 1) CuBr ₂ 3.88 g (17.4 mmol), N, N′-di-t-butylethylenediamine 0.85 g (4.9 g) in a 12 L vertical reactor equipped with a stirrer, thermometer, air introduction tube, baffle plate mmol), 10.40 g (102.8 mmol) of n-butyldimethylamine, 8.21 g (63.5 mmol) of di-n-butylamine and 2,600 g of toluene, stirred at a reaction temperature of 40 ° C., and dissolved in 2,300 g of methanol in advance. HMBP 129.32 g (0.48 mol), 2,6-dimethylphenol 292.19 g (2.40 mol), N, N′-di-t-butylethylenediamine 1.70 g (9.9 mmol), n-butyldimethylamine 20.80 g (205.6 mmol), a mixed solution of 16.43 g (127.1 mmol) of di-n-butylamine (molar ratio of the divalent phenol compound represented by the structural formula (2) and the monovalent phenol compound represented by the structural formula (3) 1: 5) was added dropwise over 230 minutes while bubbling at a flow rate of 5.2 L / min with a mixed gas adjusted to an oxygen concentration of 8% by mixing nitrogen and air and stirred. After completion of the dropwise addition, 1,500 g of water in which 19.84 g (52.2 mmol) of ethylenediaminetetraacetic acid tetrasodium was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with 1.0N hydrochloric acid aqueous solution and then with pure water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain 408.4 g of a bifunctional phenylene ether oligomer. This had a number average molecular weight of 930, a weight average molecular weight of 1,370, and a hydroxyl group equivalent of 470. When H ¹ -NMR was measured, a peak corresponding to di-n-butylamine was detected, and it was confirmed that 22% of the amine adduct was present from the integration ratio of the peak of the methyl group (0.89 ppm). .
[0027]
(Comparative example 2) CuBr ₂ 10.85 g (48.8 mmol), di-n-butylamine 286.83 g (2.22 mol), toluene 2,600 g in a 12 L vertical reactor equipped with a stirrer, thermometer, air inlet tube and baffle plate Was stirred at a reaction temperature of 40 ° C., and a mixed solution of 129.32 g (0.48 mol) HMBP and 292.19 g (2.40 mol) 2,6-dimethylphenol previously dissolved in 2,300 g methanol (structural formula (2 The molar ratio of the divalent phenolic compound represented by the formula (3) and the monovalent phenolic compound represented by the structural formula (3) 1: 5) was mixed with nitrogen and air to adjust the oxygen concentration to 8%. Gas was added dropwise over 230 minutes while bubbling at a flow rate of 5.2 L / min, and stirring was performed. After completion of the dropwise addition, 1,500 g of water in which 55.68 g (146.5 mmol) of ethylenediaminetetraacetic acid tetrasodium was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with 1.0N hydrochloric acid aqueous solution and then with pure water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain 404.6 g of a bifunctional phenylene ether oligomer. This had a number average molecular weight of 910, a weight average molecular weight of 1,310, and a hydroxyl group equivalent of 455. When H ¹ -NMR was measured, a peak corresponding to di-n-butylamine was detected, and it was confirmed that 15% of the amine adduct was present from the integration ratio of the peak of the methyl group (0.89 ppm). .
[0028]
[Table 1]

[0029]
【The invention's effect】
The production method of the present invention makes it possible to efficiently produce an oligomer of a bifunctional phenylene ether having a desired molecular weight and having no amine adduct. Since the oligomer of the bifunctional phenylene ether obtained in the present invention has no added amine, the terminal phenolic hydroxyl group can be easily derived to another functional group. Furthermore, since the basic skeleton has a polyphenylene ether structure, it has excellent heat resistance and dielectric properties, and can be applied to electrical and electronic materials.

Claims (7)

Copper-based catalyst and triethylamine, methyl diethylamine, n- butyl dimethylamine, benzyldimethylamine, N, N '- dimethylpiperazine, one or more tertiary amines and diisopropylamine selected from 2,6-dimethylpyridine , di -sec- butylamine, di - selected di -t- butyl ethylenediamine, methyl cyclohexylamine - t - butylamine, di - t - amylamine, di cyclopentylamine, dicyclohexylamine, ethyl -t- butylamine, N, N ' using a mixed system consisting of one or more secondary amine, a monovalent phenol compound represented by the following structural formula bivalent phenol compound and the following structural formula represented by (2) (3) A process for producing a bifunctional phenylene ether oligomer represented by the following structural formula (1) without an amine adduct by an oxidative polymerization reaction.

(In the above formula, R ¹ , R ² , R ³ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are the same and have an alkyl group having 6 or less carbon atoms. R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ¹² are the same or different, .m hydrogen atoms frame other represents an alkyl group having 6 or less carbon atoms, n is an integer of 0 to 25 at least one is not 0.) Monovalent phenol, the preparation of a bifunctional phenylene ether oligomer of claim 1, wherein is 2,6-dimethylphenol alone represented by the structural formula (3). Above structural formula ( 2 ) 2 Valent phenolic body 2,2 ’ , 3,3 ’ , 5,5 ’ - Hexamethyl -(1,1 ’ - Biphenyl ) -4,4 ’ - The diol according to claim 1, which is a diol. 2 A method for producing a functional phenylene ether oligomer. The molar ratio of the divalent phenol compound represented by the structural formula (2) and the monovalent phenol compound represented by the structural formula (3) is 1: 1 to 1:15. Production method of bifunctional phenylene ether oligomer. the above 2 Secondary amine N, N ’ - The -t- The butylethylenediamine according to any one of claims 1 to 4, which is butylethylenediamine. 2 A method for producing a functional phenylene ether oligomer. the above Three The primary amine is triethylamine, methyldiethylamine, n- Butyldimethylamine, N, N ’ - Selected from dimethylpiperazine 1 Seed or 2 The species according to any one of claims 1 to 4, which is a species or more. 2 A method for producing a functional phenylene ether oligomer. the above Three N is a secondary amine - The butyldimethylamine according to claim 6, which is butyldimethylamine. 2 A method for producing a functional phenylene ether oligomer.