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JP3125018B2 - Method for producing low molecular weight condensate of phenol - Google Patents

Method for producing low molecular weight condensate of phenol

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Publication number
JP3125018B2
JP3125018B2 JP10213176A JP21317698A JP3125018B2 JP 3125018 B2 JP3125018 B2 JP 3125018B2 JP 10213176 A JP10213176 A JP 10213176A JP 21317698 A JP21317698 A JP 21317698A JP 3125018 B2 JP3125018 B2 JP 3125018B2
Authority
JP
Japan
Prior art keywords
phenol
water
solvent
peroxide
condensate
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.)
Expired - Lifetime
Application number
JP10213176A
Other languages
Japanese (ja)
Other versions
JP2000041691A (en
Inventor
四郎 小林
浩 宇山
秀之 東村
Original Assignee
工業技術院長
財団法人 化学技術戦略推進機構
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Publication of JP2000041691A publication Critical patent/JP2000041691A/en
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Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明はフェノール二量体
合物の製造方法に関する。
The present invention relates to a method for producing a phenol dimer condensate.

【0002】[0002]

【従来の技術】フェノール類の酸化カツプリングによる
得られる縮合物は、エンジニアリングプラスチック、エ
ポキシ樹脂、フォトレジスト、酸化防止剤等として幅広
い分野に応用されている。その中でもフェノール酸化縮
合物は、有害なホルマリンを発生しない等の理由から近
年特に注目されている。
2. Description of the Related Art Condensates obtained by oxidative coupling of phenols are widely used in engineering plastics, epoxy resins, photoresists, antioxidants and the like. Among them, phenol oxidized condensates have been receiving particular attention in recent years because they do not generate harmful formalin.

【0003】フェノールの酸化カップリング法としては
種々の方法が知られているが、特開平7−126354
号公報には、酵素触媒とパーオキサイドを用いて有機溶
媒と水からなる均一系混合溶媒中で高分子量フェノール
樹脂を製造する方法が記載されている。この方法は、生
体内に存在する酵素を触媒として用いるため、触媒由来
の有害な廃棄物を生じない点で優れている。しかし、こ
の方法では、低分子量フェノール縮合物、特にフェノー
ル二量体縮合物を高収率で製造することが困難であっ
た。
Various methods have been known as oxidative coupling methods for phenol, but are disclosed in JP-A-7-126354.
Japanese Patent Application Laid-Open Publication No. H11-176,086 describes a method for producing a high molecular weight phenol resin in a homogeneous mixed solvent composed of an organic solvent and water using an enzyme catalyst and a peroxide. Since this method uses an enzyme present in a living body as a catalyst, it is excellent in that no harmful waste derived from the catalyst is generated. However, in this method, it was difficult to produce a low molecular weight phenol condensate, particularly a phenol dimer condensate, in high yield.

【0004】[0004]

【発明が解決しようとする課題】本発明は、フェノール
二量体縮合物を高収率で製造することのできるフェノー
二量体縮合物の製造方法を提供することをその課題と
する。
DISCLOSURE OF THE INVENTION The present invention relates to a phenol
An object of the present invention is to provide a method for producing a phenol dimer condensate, which can produce a dimer condensate in high yield.

【0005】[0005]

【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を行った結果、酵素触媒とパーオ
キサイドを用いてフェノールを酸化カップリングする際
に、難水溶性ないし非水溶性有機溶媒と水からなる混合
溶媒を用いることにより前記課題を解決し得ることを見
出し、本発明を完成するに至った。即ち、本発明は、酵
素触媒存在下、パーオキサイドを分割添加して、フェノ
ールを溶媒中で酸化カップリングする際に、該溶媒とし
て、難水溶性ないし非水溶性有機溶媒と水からなる混合
溶媒を用いることを特徴とするフェノール二量体縮合物
の製造方法である。
Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, when oxidatively coupling phenol with an enzyme catalyst and a peroxide, it is hardly water-soluble or non-soluble. The inventors have found that the above problem can be solved by using a mixed solvent composed of a water-soluble organic solvent and water, and have completed the present invention. That is, in the present invention, a peroxide is dividedly added in the presence of an enzyme catalyst, and when phenol is oxidatively coupled in a solvent, a mixed solvent comprising a poorly water-soluble or water-insoluble organic solvent and water is used as the solvent. And a method for producing a phenol dimer condensate.

【0006】[0006]

【発明の実施の形態】本発明においては、触媒としては
酵素を使用するが、好ましい酵素としてペルオキシダー
ゼ、オキシダーゼを挙げることができる。より好ましく
はペルオキシダーゼであり、さらに好ましくは植物由
来、細菌由来、坦子菌類由来のペルオキシダーゼであ
る。特に好ましくは西洋わさび由来、大豆由来のペルオ
キシダーゼである。本発明において、該酵素触媒は任意
の量で用いることができるが、一般的にはフェノールに
対して0.001〜50重量%が好ましく、0.0l〜
20重量%がより好ましい。特に好ましくは、フェノー
ルに対して0.1〜10重量%である。
BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, an enzyme is used as a catalyst. Preferred enzymes include peroxidase and oxidase. More preferred are peroxidases, and even more preferred are peroxidases derived from plants, bacteria, and carriers. Particularly preferred are horseradish-derived and soybean-derived peroxidases. In the present invention, the enzyme catalyst can be used in any amount, but is generally preferably 0.001 to 50% by weight based on phenol, and
20% by weight is more preferred. Particularly preferably, it is 0.1 to 10% by weight based on phenol.

【0007】本発明では、酸化剤としてはパーオキサイ
ドを使用する。好ましくはハイドロパーオキサイドであ
り、より好ましくは過酸化水素、t−ブチルハイドロパ
ーオキサイド、クメンハイドロパーオキサイドである。
特に好ましくは過酸化水素である。
In the present invention, peroxide is used as the oxidizing agent. Hydroperoxides are preferred, and hydrogen peroxide, t-butyl hydroperoxide and cumene hydroperoxide are more preferred.
Particularly preferred is hydrogen peroxide.

【0008】発明において、該パーオキサイドの使用
量に特に制限はないが、一般にはフェノールに対して
0.05〜5倍モルが好ましく、0.1〜3倍モルがよ
り好ましい。特に好ましくはフェノールに対して0.2
〜1倍モルである。なお、過酸化水素の場合、任意の濃
度のものが使用できるが、好ましくは1〜70wt%、
より好ましくは3〜60wt%のものである。本発明に
おいて、該パーオキサイドは分割して反応系に添加す
る。該パーオキサイドを一括して添加すると、酵素が失
活し反応が進行しなくなるので好ましくない。該パーオ
キサイドの添加速度は、好ましくはフェノールに対して
0.0l〜20モル%/分であり、より好ましくはフェ
ノールに対して0.05〜l0モル%/分である。特に
好ましくはフェノールに対して0.1〜2モル%/分で
ある。
In the present invention, the amount of the peroxide to be used is not particularly limited, but is generally preferably from 0.05 to 5 moles, more preferably from 0.1 to 3 moles, based on phenol. Particularly preferably 0.2 to phenol
11 times mol. In the case of hydrogen peroxide, any concentration can be used, but preferably 1 to 70 wt%.
More preferably, it is 3 to 60 wt%. In the present invention, the peroxide is divided and added to the reaction system. It is not preferable to add the peroxide all at once because the enzyme is inactivated and the reaction does not proceed. The addition rate of the peroxide is preferably from 0.01 to 20 mol% / min with respect to phenol, more preferably from 0.05 to 10 mol% / min with respect to phenol. Particularly preferably, it is 0.1 to 2 mol% / min with respect to phenol.

【0009】本発明の特徴は、反応溶媒として有機溶媒
と水の二相系混合溶媒を用いる点にある。反応溶媒とし
て水溶性有機溶媒と水の均一系混合溶媒を用いる場合、
フェノール二量体縮合物の収率が低くなるので好ましく
ない。反応溶媒として難水溶性ないし非水溶性有機溶媒
と水とからなる二相系混合溶媒を用いることにより、フ
ェノール縮合物の高分子量化を抑制し、フェノール二量
体縮合物の収率を高めることができる。本発明におい
て、該混合溶媒は任意の量で用いることができるが、フ
ェノールの濃度が0.0l〜500g/Lとなるのが好
ましく、0.05〜200g/Lとなるのがより好まし
い。特に好ましくは、フェノールの濃度が0.5〜10
g/Lとなる量である。
A feature of the present invention resides in that a two-phase mixed solvent of an organic solvent and water is used as a reaction solvent. When using a homogeneous mixed solvent of water-soluble organic solvent and water as the reaction solvent,
It is not preferable because the yield of the phenol dimer condensate decreases. By using a two-phase mixed solvent composed of a poorly water-soluble or water-insoluble organic solvent and water as a reaction solvent, it is possible to suppress the increase in the molecular weight of the phenol condensate and increase the yield of the phenol dimer condensate. Can be. In the present invention, the mixed solvent can be used in any amount, but the phenol concentration is preferably from 0.01 to 500 g / L, more preferably from 0.05 to 200 g / L. Particularly preferably, the concentration of phenol is 0.5 to 10
g / L.

【0010】前記混合溶媒における難水溶性ないし非水
溶性有機溶媒とは、水と任意の割合で相溶することのな
い有機溶媒のことであり、その水100gに対する溶解
度(25℃)が100g以下、好ましくは50g以下、
より好ましくは40g以下のものである。その溶解度の
下限値は0gである。その好ましい例としては、酢酸メ
チル、酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸フ
ェニル、プロピオン酸メチル、安息香酸メチル等のエス
テル化合物類;ジエチルエーテル、ジプロピルエーテ
ル、メトキシベンゼン等のエーテル化合物類;メチルエ
チルケトン、ジエチルケトン、シクロペンタノン、シク
ロヘキサノン等のケトン化合物類;ジクロロメタン、ク
ロロホルム、四塩化炭素、クロロベンゼン、ジクロロベ
ンゼン、クロロナフタレン等のハロゲン化炭化水素化合
物類;ニトロベンゼン等のニトロ化合物類;ベンゾニト
リル等のニトリル化合物類;ベンゼン、ナフタレン、ト
ルエン、キシレン、エチルベンゼン、クメン等の芳香族
炭化水素化合物類;ヘキサン、シクロヘキサン等の鎖状
及び環状の脂肪族炭化水素類等が挙げられる。より好ま
しくはエステル化合物類、エ−テル化合物類、ケトン化
合物類、ハロゲン化炭化水素化合物類、芳香族炭化水素
化合物類である。特に好ましくはエステル化合物類、エ
ーテル化合物類、ケトン化合物類、ハロゲン化炭化水素
化合物類である。これらは単独あるいは混合物として使
用される。
[0010] The poorly water-soluble or water-insoluble organic solvent in the above-mentioned mixed solvent is an organic solvent which is incompatible with water at an arbitrary ratio, and has a solubility (25 ° C.) in 100 g of water of 100 g or less. , Preferably 50 g or less,
More preferably, it is 40 g or less. The lower limit of the solubility is 0 g. Preferred examples thereof include ester compounds such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, phenyl acetate, methyl propionate, and methyl benzoate; ether compounds such as diethyl ether, dipropyl ether and methoxybenzene; methyl ethyl ketone Ketone compounds such as benzene, diethyl ketone, cyclopentanone, cyclohexanone; halogenated hydrocarbon compounds such as dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, chloronaphthalene; nitro compounds such as nitrobenzene; benzonitrile Nitrile compounds; aromatic hydrocarbon compounds such as benzene, naphthalene, toluene, xylene, ethylbenzene and cumene; and linear and cyclic aliphatic hydrocarbons such as hexane and cyclohexane. . More preferred are ester compounds, ether compounds, ketone compounds, halogenated hydrocarbon compounds, and aromatic hydrocarbon compounds. Particularly preferred are ester compounds, ether compounds, ketone compounds, and halogenated hydrocarbon compounds. These are used alone or as a mixture.

【0011】該混合溶媒における水には有機塩、無機塩
を含んでいてもよい。また、この混合溶媒における非水
溶性有機溶媒の割合に特に制限はないが、1〜99体積
%が好ましく、20〜98体積%がより好ましい。特に
好ましくは、50〜96体積%である。
The water in the mixed solvent may contain an organic salt or an inorganic salt. The proportion of the water-insoluble organic solvent in the mixed solvent is not particularly limited, but is preferably 1 to 99% by volume, more preferably 20 to 98% by volume. Particularly preferably, it is 50 to 96% by volume.

【0012】本発明を実施する反応温度は、酵素を不活
性化しない温度が望ましい。好ましい温度範囲は0℃〜
100℃であり、より好ましくは5℃〜60℃である。
特に好ましくは、10℃〜40℃である。
The reaction temperature for carrying out the present invention is preferably a temperature at which the enzyme is not inactivated. The preferred temperature range is 0 ° C.
The temperature is 100 ° C, more preferably 5 ° C to 60 ° C.
Particularly preferably, it is 10 ° C to 40 ° C.

【0013】[0013]

【実施例】以下に、実施例を挙げて本発明を更に詳細に
説明するが、本発明はこれらの実施例によりその範囲を
限定されるものではない。
The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited by these examples.

【0014】実施例1 電磁撹拌機を備えた100mフラスコ中で西洋わさび由
来ペルオキシダーゼ(HRP)5mgを水5m1に溶解
し、これにフェノール94mg(1mmol)の溶解し
た酢酸エチル5mlを加えた。この二層反応系を室温で
激しく撹拌しながら、3wt%過酸化水素水0.5m1
(0.44mmo1)をシリンジポンプを用いて0.2
5m1/hrの速度で2hr滴下し、さらにlhr撹拌
した。反応終了後、ジフェニルエーテル60mg及びメ
タノール100mlを加え、不溶物をろ過し、そのろ液
を高速液体クロマトグラフィー(ポンプ:東ソー社製S
C8020システム、検出器:東ソー社製PD−802
0、検出波長:278nm、カラム:YMC社製ODS
−AM、展開溶媒:メタノール/水)で分析した。フェ
ノールの転化率はジフェニルエーテルを内部標準として
定量した。フェノール二量体:p,p’−ビフェノール
(p,p−2)、p,o’−ビフェノール(p,o−
2)、o,o’−ビフェノール(o,o−2)、p−フ
ェノキシフェノール(p−2)、o−フェノキシフェノ
ール(o−2)は、J.Chem.Soc.Perki
n Trans、,II,563(1983)を参考にし
て、ジフェニルエーテルを内部標準として定量し、各々
の収率および総収率をフェノール転化率を基準として求
めた。その結果を表2に示す。また、反応に使用した酵
素及び混合溶媒について、表1にまとめて示す。
Example 1 In a 100-m flask equipped with a magnetic stirrer, 5 mg of horseradish peroxidase (HRP) was dissolved in 5 ml of water, and 5 ml of ethyl acetate in which 94 mg (1 mmol) of phenol was dissolved was added. While stirring this two-layer reaction system vigorously at room temperature, 0.5 ml of 3 wt% hydrogen peroxide solution was added.
(0.44 mmol) using a syringe pump to 0.2
The mixture was added dropwise at a rate of 5 ml / hr for 2 hours, and further stirred for 1 hour. After the completion of the reaction, 60 mg of diphenyl ether and 100 ml of methanol were added, insolubles were filtered, and the filtrate was subjected to high performance liquid chromatography (pump: S by Tosoh Corporation).
C8020 system, detector: Tosoh PD-802
0, detection wavelength: 278 nm, column: ODS manufactured by YMC
-AM, developing solvent: methanol / water). The conversion of phenol was determined using diphenyl ether as an internal standard. Phenol dimer: p, p'-biphenol (p, p-2), p, o'-biphenol (p, o-
2), o, o'-biphenol (o, o-2), p-phenoxyphenol (p-2) and o-phenoxyphenol (o-2) are described in J. Am. Chem. Soc. Perki
With reference to n Trans ,, II, 563 (1983), diphenyl ether was quantified as an internal standard, and each yield and total yield were determined based on the phenol conversion. Table 2 shows the results. Table 1 shows the enzymes and mixed solvents used in the reaction.

【0015】実施例2〜8、比較例1 有機溶媒、有機溶媒量、酵素を表1に示すように変えた
以外は、実施例1と同様にして重合を実施した。表2に
その結果を示す。なお、SBPは大豆由来ペルオキシダ
ーゼを示す。
Examples 2 to 8, Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that the organic solvent, the amount of the organic solvent and the enzyme were changed as shown in Table 1. Table 2 shows the results. SBP indicates soybean-derived peroxidase.

【0016】[0016]

【表1】 [Table 1]

【0017】[0017]

【表2】 [Table 2]

【0018】表2に示した結果から、本発明による二相
系混合溶媒を用いると、比較例の均一系混合溶媒を用い
る場合よりも、二量体総収率がはるかに高かくなること
がわかる。
From the results shown in Table 2, it can be seen that the total dimer yield is much higher when the two-phase mixed solvent according to the present invention is used than when the homogeneous mixed solvent of the comparative example is used. Understand.

【0019】[0019]

【発明の効果】本発明は、酵素触媒とパーオキサイドに
よるフェノールの酸化カップリングにおいて、難水溶性
ないし非水溶性有機溶媒と水とからなる混合溶媒を用い
るもので、これにより、フェノール二量体縮合物を非常
に高い収率で合成することができる。
According to the present invention, in the oxidative coupling of phenol with an enzyme catalyst and a peroxide, a mixed solvent composed of a poorly water-soluble or water-insoluble organic solvent and water is used. Condensates can be synthesized in very high yields.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 東村 秀之 茨城県つくば市梅園2丁目13−1 住友 化学梅園社宅3−201 審査官 高堀 栄二 (56)参考文献 特開 平8−302007(JP,A) 特開 平7−126354(JP,A) 特開 平9−12710(JP,A) Macromol.Chem.Phy s.,Vol.199,No.5(1998. May)p.777−782 Polym.J.,Vol.30,N o.6(1998.Jun.)p.526−529 (58)調査した分野(Int.Cl.7,DB名) C12P 7/22 BIOSIS(DIALOG) CA(STN) JICSTファイル(JOIS) REGISTRY(STN) WPI(DIALOG)──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hideyuki Higashimura 2-13-1, Umezono, Tsukuba, Ibaraki Pref. 3-201 House of Sumitomo Chemical Umezono Examiner Eiji Takahori (56) References A) JP-A-7-126354 (JP, A) JP-A-9-12710 (JP, A) Macromol. Chem. Phys. , Vol. 199, no. 5 (1998. May) p. 777-782 Polym. J. , Vol. 30, No. 6 (1998. Jun.) P. 526-529 (58) Fields surveyed (Int. Cl. 7 , DB name) C12P 7/22 BIOSIS (DIALOG) CA (STN) JICST file (JOIS) REGISTRY (STN) WPI (DIALOG)

Claims (4)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 酵素触媒存在下、パーオキサイドを分割
添加して、フェノールを溶媒中で酸化カップリングする
際に、該溶媒として、難水溶性ないし非水溶性有機溶媒
と水からなる混合溶媒を用いることを特徴とするフェノ
ール二量体縮合物の製造方法。
When a peroxide is dividedly added in the presence of an enzyme catalyst and phenol is oxidatively coupled in a solvent, a mixed solvent comprising a poorly water-soluble or water-insoluble organic solvent and water is used as the solvent. A method for producing a phenol dimer condensate, which is used.
【請求項2】 混合溶媒中の有機溶媒の割合が1〜99
体積%であることを特徴とする請求項1記載のフェノー
二量体縮合物の製造方法。
2. The method according to claim 1, wherein the ratio of the organic solvent in the mixed solvent is 1 to 99.
The method for producing a phenol dimer condensate according to claim 1, wherein the content is% by volume.
【請求項3】 パーオキサイドを分割添加する速度が、
フェノールに対して0.01〜20モル%/分であるこ
とを特徴とする請求項1または2記載のフェノール二量
縮合物の製造方法。
3. The rate at which the peroxide is dividedly added,
The phenol dimer according to claim 1 or 2, wherein the amount is 0.01 to 20 mol% / min with respect to phenol .
Method of manufacturing the body condensate.
【請求項4】 酵素がペルオキシダーゼまたはオキシダ
ーゼであり、パーオキサイドがハイドロパーオキサイド
であることを特徴とする請求項1〜3のいずれかに記載
のフェノール二量体縮合物の製造方法。
4. The method for producing a phenol dimer condensate according to claim 1, wherein the enzyme is peroxidase or oxidase, and the peroxide is hydroperoxide.
JP10213176A 1998-07-28 1998-07-28 Method for producing low molecular weight condensate of phenol Expired - Lifetime JP3125018B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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JP4507067B2 (en) * 2004-02-20 2010-07-21 国立大学法人九州大学 Method for producing dialkoxyphenol dimer
JP4507069B2 (en) * 2004-03-17 2010-07-21 国立大学法人九州大学 Method for producing dialkylphenol dimer
JP5257725B2 (en) * 2005-08-03 2013-08-07 Dic株式会社 Epoxy resin, epoxy resin composition, cured product, semiconductor device, epoxy resin manufacturing method
ES2585483T3 (en) 2008-02-13 2016-10-06 The Cleveland Clinic Foundation Molecular improvement of the extracellular matrix and methods of use
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Polym.J.,Vol.30,No.6(1998.Jun.)p.526−529

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