JP5761775B2 - Diβ-methylglycidyl ether of bisphenol A propylene oxide adduct and curable resin composition using the same - Google Patents

Diβ-methylglycidyl ether of bisphenol A propylene oxide adduct and curable resin composition using the same Download PDF

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JP5761775B2
JP5761775B2 JP2010001663A JP2010001663A JP5761775B2 JP 5761775 B2 JP5761775 B2 JP 5761775B2 JP 2010001663 A JP2010001663 A JP 2010001663A JP 2010001663 A JP2010001663 A JP 2010001663A JP 5761775 B2 JP5761775 B2 JP 5761775B2
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bisphenol
propylene oxide
diβ
oxide adduct
phase transfer
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JP2011140458A (en
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小川　亮
亮 小川
光紀 井出
光紀 井出
健一 玉祖
健一 玉祖
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Adeka Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
    • C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/28—Ethers with hydroxy compounds containing oxirane rings
    • C07D303/30—Ethers of oxirane-containing polyhydroxy compounds in which all hydroxyl radicals are etherified with oxirane-containing hydroxy compounds

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Description

本発明はジβ−メチルグリシジルエーテルの製造方法に関し、特に、相間移動触媒の存在下に、ビスフェノールのプロピレンオキシド付加物、β−メチルエピクロルヒドリン及びアルカリを反応させる、塩素含有量の少ないジβ−メチルグリシジルエーテルに関する。 The present invention relates to a method of manufacturing a di beta-methyl glycidyl ether, in particular, in the presence of a phase transfer catalyst, propylene oxide adduct of bisphenol, beta-methyl epichlorohydrin and reacting the alkali, less di beta-methyl chlorine content It relates to glycidyl ether.

ポリエポキシ化合物から得られる硬化物は、各種基材に対する接着性、耐熱性、耐薬品性、電気特性、機械特性等に比較的優れているため、広い産業分野、特に、塗料や接着剤の分野で使用されている。   Cured products obtained from polyepoxy compounds are relatively excellent in adhesion to various substrates, heat resistance, chemical resistance, electrical properties, mechanical properties, etc., so they can be used in a wide range of industrial fields, especially paints and adhesives. Used in.

ビスフェノールのような多価アルコールとエピクロルヒドリンを、アルカリ及び相関移動触媒の存在下に反応させるポリグリシジルエーテルの製造方法はよく知られている（例えば特許文献１〜４）が、エピクロルヒドリンの代わりにβ-メチルエピクロルヒドリンを使用した場合に付いての詳細は知られていない。
そこで本発明者等は、エピクロルヒドリンの代わりにβ-メチルエピクロルヒドリンを使用した場合に付いて鋭意検討したところ、驚くべきことに、ビスフェノールのプロピレンオキシド付加物とβ−メチルエピクロルヒドリンから得られるジβ−メチルグリシジルエーテルが、カチオン硬化系で優れた硬化性を有し、接着性にも優れていることが判明した。 A method for producing a polyglycidyl ether in which a polyhydric alcohol such as bisphenol and epichlorohydrin are reacted in the presence of an alkali and a phase transfer catalyst is well known (for example, Patent Documents 1 to 4). However, instead of epichlorohydrin, β- Details regarding the use of methyl epichlorohydrin are not known.
Thus, the present inventors have conducted an extensive study on the use of β-methylepichlorohydrin instead of epichlorohydrin. Surprisingly, the present inventors surprisingly found that diβ-methyl obtained from a propylene oxide adduct of bisphenol and β -methylepichlorohydrin. It has been found that glycidyl ether has excellent curability in a cationic curing system and has excellent adhesion .

一方、例えば、多価フェノール化合物とβ−メチルエピクロルヒドリン及びエピクロルヒドリンとを水酸化ナトリウム水溶液の存在下で反応させる従来の方法（特許文献５）によって前記特定のポリグリシジルエーテルを製造しようとしても、目的物を得ることは困難である。また、１段目にルイス酸触媒等を用いる付加反応を実施し、続く２段目にアルカリを用いる鹸化反応を行わせるという一般的な高アルコール又はグリコールの製造方法を転用した場合には副反応が避けられず、塩素含有量が高くなるという欠点を有していた。 On the other hand, if example embodiment, even if an attempt is prepared polyhydric phenolic compound and β- methyl epichlorohydrin and the conventional method (Patent Document 5) Therefore the particular polyglycidyl ethers and epichlorohydrin are reacted in the presence of sodium hydroxide solution, It is difficult to obtain the object. In addition, when a general high alcohol or glycol production method in which an addition reaction using a Lewis acid catalyst or the like is performed in the first stage and a saponification reaction using an alkali is performed in the subsequent second stage is diverted, a side reaction Is unavoidable and has the disadvantage that the chlorine content is high.

特開昭５９−２０６４２９号公報JP 59-206429 A 特開平２−２０２８８３号公報JP-A-2-202883 特開平８−３３３３５６号公報JP-A-8-333356 特開平１０−７７６１号公報JP-A-10-7761 特許第３５７９９５９号公報Japanese Patent No. 3579959

そこで本発明者等は、ビスフェノールのプロピレンオキシド付加物とβ−メチルエピクロルヒドリンから得られるジβ−メチルグリシジルエーテルを製造すべく鋭意検討を重ねた結果、ビスフェノールのプロピレンオキシド付加物とβ−メチルエピクロルヒドリンとをアルカリで閉環させるに際し、相間移動触媒を用いた場合には、全塩素含有量が低減された上記ジβ−メチルグリシジルエーテルを収率良く製造することができ、また、得られたジβ−メチルグリシジルエーテルがカチオン硬化系で優れた硬化性を有するだけでなく、予想以上に強力な接着力を実現し得ることを見出し、本発明に到達した。
従って本発明の目的は、カチオン硬化系で優れた硬化性を有するだけでなく、強力な接着力を実現し得る、全塩素含有量が低減されたジβ−メチルグリシジルエーテルを提供することにある。 Therefore, the present inventors have conducted extensive studies to produce diβ -methylglycidyl ether obtained from propylene oxide adduct of bisphenol and β-methylepichlorohydrin . As a result, propylene oxide adduct of bisphenol and β-methylepichlorohydrin In the case of using a phase transfer catalyst when ring-closing with alkali, the diβ -methylglycidyl ether having a reduced total chlorine content can be produced with good yield, and the obtained diβ- The present inventors have found that methyl glycidyl ether not only has excellent curability in a cationic curing system but also can realize stronger adhesive force than expected .
An object of the present invention is therefore not only has excellent curability in cationic curing systems, can realize strong adhesion, the total chlorine content is in providing Hisage a reduced di β- methyl glycidyl ether .

即ち本発明は、下記一般式（I）で表される多価アルコール１００質量部に対して０．１〜１０．０質量部の相間移動触媒の存在下に、前記多価アルコールの水酸基１等量（モル）に対して、１．０〜１０．０等量のβ−メチルエピクロルヒドリン及び１．０〜２．０等量のアルカリを反応させてなることを特徴とする、下記一般式（II）で表されるビスフェノールＡ-プロピレンオキシド付加物のジβ−メチルグリシジルエーテルである。 That is, the present invention is the presence of a phase transfer catalyst from 0.1 to 10.0 parts by weight with respect to the polyhydric alcohol 100 parts by mass represented by the following formula (I), the polyhydric hydroxyl 1 or the like alcohol relative to the amount (moles), characterized by comprising reacting a 1.0-10.0 equivalent amounts of β- methyl epichlorohydrin and 1.0 to 2.0 equivalent amount of alkali, the following general formula (II ) di β- methyl Gurishijiruete Le bisphenol A- propylene oxide adduct represented by.

一般式（I）

Figure 0005761775
但し、式中のＲ１及びＲ２はそれぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表し、ｍ及びｎはそれぞれ独立に１〜１０の数を表す;
一般式（II）
Figure 0005761775
但し、式中のＲ１及びＲ２ 、並びに、ｍ及びｎはそれぞれ、一般式（I）中のＲ１及びＲ２ 、並びに、ｍ及びｎと同じである。
Formula (I)
Figure 0005761775
However, each of R 1 and R 2 in the formula independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m and n represents the number of independently 1 to 10;
Formula (II)
Figure 0005761775
However, R 1 and R 2 in the formula , and m and n are the same as R 1 and R 2 in the general formula (I) , and m and n , respectively.

本発明においては、前記相間移動触媒が第四級アンモニウム塩基又は第四級アンモニウム塩であることが好ましく、特に第四級アンモニウム塩が好ましい。   In the present invention, the phase transfer catalyst is preferably a quaternary ammonium base or a quaternary ammonium salt, and particularly preferably a quaternary ammonium salt.

本発明によれば、電子材料或いは電気絶縁材料への使用に適した、塩素含有率が極めて低く、また、エポキシ当量の小さいポリグリシジルエーテルを簡便な操作で容易に製造することができる。   According to the present invention, polyglycidyl ether having a very low chlorine content and a small epoxy equivalent suitable for use as an electronic material or an electrical insulating material can be easily produced by a simple operation.

以下、本発明のジβ−メチルグリシジルエーテルについて詳細に説明する。 It will be described in detail with di β- methyl Gurishijiruete Le of the present invention.

本発明において出発原料として用いられる前記一般式（Ｉ）で表される多価アルコールは、ビスフェノールにプロピレンオキシドを付加させる等の常法によって得ることができるものであり、また、市販品として容易に入手することもできる。 Polyhydric alcohol represented by the general formula to be used as Oite starting material present onset bright (I) are those can be obtained by conventional methods, such as for adding propylene oxide to bisphenol, also commercially available Can also be easily obtained.

本発明の前記一般式（II）で表されるジβ−メチルグリシジルエーテルは、上記多価アルコール、β−メチルエピクロルヒドリン及びアルカリを反応させて製造する。ここで、上記多価アルコールの水酸基１等量に対する上記β−メチルエピクロルヒドリンの使用比率は１．０〜１０．０当量であり、特に２．０〜８．０当量の範囲であることが好ましい。上記β−メチルエピクロルヒドリンの比率が１．０当量（等当量）未満であると、ジβ−メチルグリシジルエーテル化されない水酸基が残存して純度が低下する。また、１０．０当量を超えた場合にはβ−メチルエピクロルヒドリンが無駄となるばかりでなく、反応速度が低下したり、副反応によってエポキシ当量が大きくなったりするので好ましくない。 Di β- methyl glycidyl ether represented by the above general formula (II) of the present invention, the polyhydric alcohol, manufacture by reacting β- methyl epichlorohydrin and alkali. Here, the use ratio of the β-methylepichlorohydrin to 1 equivalent of the hydroxyl group of the polyhydric alcohol is 1 . It is 0-10.0 equivalent, It is especially preferable that it is the range of 2.0-8.0 equivalent. When the ratio of the β-methylepichlorohydrin is less than 1.0 equivalent (equal equivalent), a hydroxyl group that is not diβ -methylglycidyl ether remains and the purity is lowered. On the other hand, if it exceeds 10.0 equivalents, not only β-methylepichlorohydrin is wasted, but also the reaction rate is lowered and the epoxy equivalent is increased by side reactions, which is not preferable.

また前記アルカリとしては、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩等があげられる。本発明においてはこれらのアルカリの中でも、特に水酸化ナトリウムが好ましい。本発明においてはこれらのアルカリを水溶液として用いることが好ましいが、場合によっては粉末又は固形のアルカリを、水と同時に或いは別々に加えることもできる。   Examples of the alkali include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and the like. In the present invention, among these alkalis, sodium hydroxide is particularly preferable. In the present invention, these alkalis are preferably used as an aqueous solution, but in some cases, a powder or solid alkali can be added simultaneously with water or separately.

上記アルカリの使用量は、前記多価アルコールの水酸基に対して１．０〜２．０当量であり、特に１．０〜１．５当量の範囲であることが好ましい。アルカリの使用量が脂肪族多価アルコールの水酸基に対して当量未満であるとジβ−メチルグリシジルエーテル化されないクロルヒドリンエーテル基が残存して純度が低下し、また、２．０当量を超えても無駄となるばかりでなく、副反応によって製品の純度が低下するので好ましくない。 The amount of the alkali is with respect to the polyhydric alcohol hydroxyl groups 1. It is 0-2.0 equivalent, It is especially preferable that it is the range of 1.0-1.5 equivalent. If the amount of alkali used is less than the equivalent of the hydroxyl group of the aliphatic polyhydric alcohol, a chlorohydrin ether group that is not di-β-methylglycidyl etherified remains and the purity decreases, and exceeds 2.0 equivalents. However, not only is it wasted, but the purity of the product is reduced by side reactions, which is not preferable.

本発明の特徴は、前記多価アルコール、β−メチルエピクロルヒドリン及びアルカリの反応を、相間移動触媒の存在下に行わせる点にあり、この相間移動触媒は、水に不溶性の有機化合物と、有機溶媒に不溶性の試薬とを反応させるために使用される試薬として知られている。   A feature of the present invention is that the reaction of the polyhydric alcohol, β-methylepichlorohydrin, and alkali is performed in the presence of a phase transfer catalyst. The phase transfer catalyst includes an organic compound insoluble in water and an organic solvent. It is known as a reagent used for reacting with an insoluble reagent.

前記相間移動触媒としては、トリメチルアミン、トリオクチルアミン、トリデシルアミンのような第三級アミン、テトラメチルアンモニウム、メチルトリオトクチルアンモニウム、メチルトリデシルアンモニウム、ベンジルトリメチルアンモニウムのような第四級アンモニウム塩基、塩化テトラメチルアンモニウム、塩化メチルトリオクチルアンモニウム、塩化メチルトリデシルアンモニウム、塩化ベンジルトリメチルアンモニウムのような第四級アンモニウム塩があげられるが、本発明においては、特に第四級アンモニウム塩が好ましい。   Examples of the phase transfer catalyst include tertiary amines such as trimethylamine, trioctylamine and tridecylamine, quaternary ammonium bases such as tetramethylammonium, methyltrioctylammonium, methyltridecylammonium and benzyltrimethylammonium. Quaternary ammonium salts such as tetramethylammonium chloride, methyltrioctylammonium chloride, methyltridecylammonium chloride, and benzyltrimethylammonium chloride are exemplified. In the present invention, a quaternary ammonium salt is particularly preferable.

上記相間移動触媒の使用量は、多価アルコールの種類、β−メチルエピクロルヒドリンの過剰率、反応溶媒の使用量、反応温度等を考慮すると、多価アルコール１００質量部に対して０．１〜１０．０質量部であり、０．５〜５．０質量部の範囲であることが好ましい。相間移動触媒の使用量が０．１質量部未満であると反応速度が著しく遅くなったり、副反応が進行してエポキシ当量が小さくなったりするため実用的ではなく、また、１０．０質量部を超えても相間移動触媒が無駄となる上、場合によっては反応を阻害することすらあるので好ましくない。 The amount of the phase transfer catalyst, the type of polyhydric alcohol, excess of β- methyl epichlorohydrin, the amount of the reaction solvent, and to account Thus, polyhydric alcohol 100 parts by weight of the reaction temperature and the like 0. It is 1-10.0 mass parts, and it is preferable that it is the range of 0.5-5.0 mass parts. When the amount of the phase transfer catalyst used is less than 0.1 parts by mass, the reaction rate is remarkably slow or side reaction proceeds and the epoxy equivalent becomes small, which is not practical, and 10.0 parts by mass Above this, the phase transfer catalyst is wasted and, in some cases, the reaction may be hindered.

また、本発明においては、一段の反応で塩素含有率の著しく低いジβ−メチルグリシジルエーテルが得られるという利点もある。ここで、一段の反応とは、全ての原料及び触媒を一括して仕込んで反応させる方法のみならず、一般式（I)で表される多価アルコール、β−メチルエピクロルヒドリン並びに触媒を仕込み、次いでアルカリを添加して反応させる方法を包含する。本発明においては、反応制御の容易さの観点から、後者の方法が好ましい。 Further, Oite this onset Ming, there is an advantage that a significantly lower di β- methyl glycidyl ether of chlorine content is obtained by the reaction of one step. Here, the one-step reaction is not only a method in which all raw materials and catalysts are charged and reacted together, but also a polyhydric alcohol represented by the general formula (I) , β-methylepichlorohydrin and a catalyst are charged, It includes a method of reacting by adding an alkali. In the present invention, the latter method is preferable from the viewpoint of easy reaction control.

上記の反応は、約３０℃〜約１００℃で行われるが、約４０℃〜約８０℃で行うことが好ましい。また、反応に際しては、炭化水素、エーテル又はケトンのような反応に不活性な溶媒を用いることもできるが、β−メチルエピクロルヒドリンを過剰に用いた場合には、β−メチルエピクロルヒドリンが溶媒としても機能するため、上記したような、反応に不活性な溶媒を使用することは必須ではない。   The above reaction is carried out at about 30 ° C. to about 100 ° C., preferably about 40 ° C. to about 80 ° C. In the reaction, a solvent inert to the reaction such as hydrocarbon, ether or ketone can be used. However, when β-methylepichlorohydrin is excessively used, β-methylepichlorohydrin also functions as a solvent. Therefore, it is not essential to use a solvent inert to the reaction as described above.

反応終了後の、目的とするジβ−メチルグリシジルエーテルの単離は、例えば、過剰のβ−メチルエピクロルヒドリンを留去した後、必要に応じて炭化水素等の非水溶性溶媒を加えた後水洗し、生成した食塩、触媒及び未反応或いは副生するアルコール成分を除去する等の、通常操作によって行うことができる。 Isolation of the desired di-β-methyl glycidyl ether after completion of the reaction is carried out, for example, by distilling off excess β-methyl epichlorohydrin, and then adding a water-insoluble solvent such as hydrocarbon as necessary, followed by washing with water. The generated salt, catalyst, and unreacted or by-produced alcohol components can be removed by a normal operation.

本発明によって得られたジβ−メチルグリシジルエーテルは、電子・電気絶縁材料として用いられる他、種々の用途に使用することができる。 Di β- methyl glycidyl ether thus obtained to the onset Ming, except that used as the electronic and electrical insulating materials, can be used for various applications.

以下、実施例及び比較例によって本発明を更に詳細に説明するが、本発明はこれらによって制限を受けるものではない。尚、以下の実施例等において、エポキシ当量とはエポキシ基１個当たりのエポキシ化合物（樹脂）の分子量を表す。   EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not restrict | limited by these. In the following examples and the like, the epoxy equivalent represents the molecular weight of an epoxy compound (resin) per one epoxy group.

温度計、攪拌機及び冷却管を備えたガラス製フラスコに、水酸基価が３１４のビスフェノールＡのプロピレンオキシド付加物（株式会社ＡＤＥＫＡ製ＢＰＸ−１１）１７８．９ｇ（０．５モル）、β−メチルエピクロルヒドリン４６２．５ｇ（５．０モル）、塩化テトラメチルアンモニウム１．５ｇ（多価アルコール１００質量部に対して０．８４質量部）を仕込み、フラスコ内を６０℃に昇温し、内部圧力を１１．３ｋＰａに保って環流させた。   In a glass flask equipped with a thermometer, a stirrer and a condenser tube, 178.9 g (0.5 mol) of propylene oxide adduct of bisphenol A having a hydroxyl value of 314 (ADEKA BPX-11), β-methylepichlorohydrin 462.5 g (5.0 mol) and tetramethylammonium chloride 1.5 g (0.84 parts by mass with respect to 100 parts by mass of polyhydric alcohol) were charged, the temperature in the flask was raised to 60 ° C., and the internal pressure was 11 The mixture was refluxed at 3 kPa.

反応系の温度及び圧力を保ちながら、４８．５質量％の水酸化ナトリウム水溶液１０８．３ｇ（水酸化ナトリウムとして１．３モル）を９０分掛けて滴下し、６０℃で１５０分間熟成した後、反応系内に生成した塩を濾別した。濾液中の過剰なβ−メチルエピクロルヒドリンを減圧下の１２０℃で留去した後、トルエンを加えて十分に水洗し、次いで減圧下にトルエンを留去した後再度濾過して、淡黄色液体の生成物（ＭＥＰ−１：ビスフェノールＡ−プロピレンオキシド付加物のジβ−メチルグリシジルエーテル）２２２ｇを得た。   While maintaining the temperature and pressure of the reaction system, 108.3 g of a 48.5 mass% aqueous sodium hydroxide solution (1.3 mol as sodium hydroxide) was added dropwise over 90 minutes, and after aging at 60 ° C. for 150 minutes, The salt produced in the reaction system was filtered off. Excess β-methylepichlorohydrin in the filtrate was distilled off at 120 ° C under reduced pressure, and then toluene was added and washed thoroughly. Then, toluene was distilled off under reduced pressure and filtered again to form a pale yellow liquid. 222 g of a product (MEP-1: diβ-methylglycidyl ether of bisphenol A-propylene oxide adduct) was obtained.

分析の結果、全塩素含有率は０．２３質量％（内、可鹸化塩素０．０１質量％）と著しく低く、また、エポキシ当量は２８６（計算値２４２）であり、副反応による高分子量化が極めて少ないことが分かった。また、ビスフェノールＡ−プロピレンオキシド付加物を基準とした収率は９０％であった。   As a result of the analysis, the total chlorine content was as low as 0.23% by mass (including 0.01% by mass of saponifiable chlorine), and the epoxy equivalent was 286 (calculated value 242). Was found to be extremely small. The yield based on the bisphenol A-propylene oxide adduct was 90%.

比較例１
温度計、攪拌機及び冷却管を備えたガラス製フラスコに、水酸基価３１４のビスフェノールＡのプロピレンオキシド付加物（旭電化工業株式会社製ＢＰＸ−１１）１７８．９ｇ（０．５モル）及び四塩化錫水和物２．０ｇを仕込み、７０℃に加温した。７０〜７５℃に保ちながら、β−メチルエピクロルヒドリン１２７．８ｇ（１．２モル）を２時間掛けて滴下し、滴下終了後更に１時間、７０〜７５℃で攪拌してβ−メチルエピクロルヒドリンによるエーテル化を行った。この段階におけるβ−メチルエピクロルヒドリン付加エーテルの生成率は理論値通りであり、１００％（ビスフェノールＡのプロピレンオキシド付加物基準）であった。 Comparative Example 1
In a glass flask equipped with a thermometer, a stirrer, and a condenser tube, 178.9 g (0.5 mol) of propylene oxide adduct of bisphenol A having a hydroxyl value of 314 (BPX-11 manufactured by Asahi Denka Kogyo Co., Ltd.) and tin tetrachloride The hydrate 2.0g was prepared and it heated at 70 degreeC. While maintaining 70-75 [° C., was added dropwise over 2 hours β- methyl epichlorohydrin 127.8g (1.2 mol), further 1 hour after completion of the dropwise addition, by stirring to β- methyl-epi chlorohydrin at 70-75 [° C. Etherification was performed. Yield of β- methyl-epi chlorohydrin added ether at this stage are theoretical values as, was 100% (propylene oxide adducts criteria of bisphenol A).

次いでトルエン６０ｇを加え、６０〜６５℃に保ちながら、４８．５質量％の水酸化ナトリウム水溶液９１．６ｇ（水酸化ナトリウムとして１．１モル）を１時間掛けて滴下し、６０〜６５℃で３０分間攪拌した。更に１００ｇのトルエンを加え、十分に水洗した後、減圧下にトルエンを留去して淡黄色の液体生成物（ＭＥＰ−２：ビスフェノールＡ−プロピレンオキシド付加物のジβ−メチルグリシジルエーテル）２０９ｇを得た。得られた生成物の全塩素含有率は４．５５質量％（内、可鹸化塩素０．０５％）、エポキシ当量は３６５（計算値２６３）であり、副反応による高分子量化等が著しいものであった。 Then Toluene 60g was added, while maintaining the 60 to 65 ° C., was added dropwise over 1 hour (1.1 mol as sodium hydroxide) 48.5 mass% of aqueous sodium 91.6g hydroxide, 60 to 65 ° C. For 30 minutes. Further addition of toluene 100 g, sufficiently washed with water, a pale yellow liquid product was distilled off toluene under reduced pressure: a (MEP-2 Bisphenol A- di β- methyl glycidyl ethers of propylene oxide adducts) 209 g Obtained. The total chlorine content of the obtained product is 4.55% by mass (including 0.05% saponifiable chlorine), the epoxy equivalent is 365 (calculated value 263), and the high molecular weight due to side reaction is remarkable. Met.

〔表１〕に示した配合で調製した実施例及び比較例の組成物を用いて以下の試験を実施した。 The following tests were carried out using the compositions of Examples and Comparative Examples prepared with the formulations shown in [Table 1].

（ゲル化時間）
各測定温度に保たれた熱盤上に、得られた組成物を０．５ｇ滴下し、スパチュラ等でかき混ぜながら、流動性がなくなるまでの時間を測定した。 (Gel time)
0.5 g of the obtained composition was dropped on a hot plate maintained at each measurement temperature, and the time until fluidity was lost was measured while stirring with a spatula or the like.

（ガラス転移点、Ｔｇ）
SIIナノテクノロジーズ社製の示差走査熱量計ＤＳＣ６２２０を用いて、昇温速度１０℃/分、走査温度範囲２５〜３００℃としてＤＳＣチャートを得た。更に、２次昇温を同じ条件で行い、熱容量の変曲点からガラス転移点を測定した。 (Glass transition point, Tg)
A DSC chart was obtained using a differential scanning calorimeter DSC 6220 manufactured by SII Nano Technologies, Inc. with a heating rate of 10 ° C./min and a scanning temperature range of 25 to 300 ° C. Further, the secondary temperature increase was performed under the same conditions, and the glass transition point was measured from the inflection point of the heat capacity.

（剪断接着力）
ＪＩＳ Ｋ ６８５０に準拠した方法により、１００℃で１時間硬化させた、硬化後の鋼板/鋼板の剪断接着力を求めた。 (Shearing adhesive strength)
By the method according to JIS K 6850, the shear adhesive strength of the steel plate / steel plate after curing, which was cured at 100 ° C. for 1 hour, was determined.

Figure 0005761775
Figure 0005761775

上記の結果から明らかなように、脂肪族多価アルコールとβ−メチルエピクロルヒドリン相間移動触媒の存在下で、反応を一段で行わせた本発明の場合には、塩素含有率が低くエポキシ当量の小さいジβ−メチルグリシジルエーテルを高収率で製造できること、また、得られた樹脂は、反応性及び接着性に優れていることが実証された。 As is clear from the above results, in the case of the present invention in which the reaction is carried out in the presence of an aliphatic polyhydric alcohol and a β-methylepichlorohydrin phase transfer catalyst, the chlorine content is low and the epoxy equivalent is small. It was demonstrated that diβ -methylglycidyl ether can be produced in a high yield, and that the obtained resin is excellent in reactivity and adhesiveness.

これに対し、相間移動触媒を用いずに金属錯体触媒又はルイス酸触媒のみを用いた場合には、得られるジβ−メチルグリシジルエーテルの塩素含有率が高い上、エポキシ当量が大きく、純度が低下するので、反応性及び接着性が低下することが確認された。また、β位にメチル基を持たないエポキシ樹脂と比較しても（比較例２、３）、本発明で得られたジβ−メチルグリシジルエーテルはより高い反応性と接着性を有していることが実証された。

On the other hand, when only a metal complex catalyst or Lewis acid catalyst is used without using a phase transfer catalyst, the chlorine content of the obtained diβ-methylglycidyl ether is high, and the epoxy equivalent is large and the purity is lowered. Therefore, it was confirmed that the reactivity and the adhesiveness were lowered. Even when compared with an epoxy resin having no methyl group at the β-position (Comparative Examples 2 and 3), the diβ-methylglycidyl ether obtained in the present invention has higher reactivity and adhesiveness. It was proved.

本発明は、電子・電気絶縁材料に適した、塩素含有率が極めて低い上エポキシ当量の小さいポリグリシジルエーテルを簡便な操作で容易に製造することができるので、産業上極めて有意義である。   INDUSTRIAL APPLICATION Since this invention can manufacture easily polyglycidyl ether with a very low chlorine content and a small epoxy equivalent suitable for an electronic / electrical insulating material by simple operation, it is very significant industrially.

Claims (4)

下記一般式（I）で表される多価アルコール１００質量部に対して０．１〜１０．０質量部の相間移動触媒の存在下に、前記多価アルコールの水酸基１等量（モル）に対して、１．０〜１０．０等量のβ−メチルエピクロルヒドリン及び１．０〜２．０等量のアルカリを反応させてなることを特徴とする、下記一般式（II）で表されるビスフェノールＡ-プロピレンオキシド付加物のジβ−メチルグリシジルエーテル；
一般式（I）
Figure 0005761775
但し、式中のＲ１及びＲ２はそれぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表し、ｍ及びｎはそれぞれ独立に１〜１０の数を表す;
一般式（II）
Figure 0005761775
但し、式中のＲ１及びＲ２ 、並びに、ｍ及びｎはそれぞれ、一般式（I）中のＲ１及びＲ２ 、並びに、ｍ及びｎと同じである。 In the presence of 0.1 to 10.0 parts by mass of a phase transfer catalyst with respect to 100 parts by mass of the polyhydric alcohol represented by the following general formula (I), 1 equivalent (mol) of hydroxyl group of the polyhydric alcohol. In contrast, 1.0 to 10.0 equivalents of β-methylepichlorohydrin and 1.0 to 2.0 equivalents of alkali are reacted, represented by the following general formula (II) Diβ-methylglycidyl ether of bisphenol A-propylene oxide adduct;
Formula (I)
Figure 0005761775
However, each of R 1 and R 2 in the formula independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m and n represents the number of independently 1 to 10;
Formula (II)
Figure 0005761775
However, R 1 and R 2 in the formula , and m and n are the same as R 1 and R 2 in the general formula (I) , and m and n , respectively. 前記相間移動触媒が第四級アンモニウム塩基及び第四級アンモニウム塩から選択された少なくとも１種の化合物である、請求項１に記載されたビスフェノールＡ-プロピレンオキシド付加物のジβ−メチルグリシジルエーテル。   The diβ-methyl glycidyl ether of bisphenol A-propylene oxide adduct according to claim 1, wherein the phase transfer catalyst is at least one compound selected from a quaternary ammonium base and a quaternary ammonium salt. 前記相間移動触媒が第四級アンモニウム塩から選択された少なくとも１種の化合物である、請求項２に記載されたビスフェノールＡ-プロピレンオキシド付加物のジβ−メチルグリシジルエーテル。   The diβ-methyl glycidyl ether of bisphenol A-propylene oxide adduct according to claim 2, wherein the phase transfer catalyst is at least one compound selected from quaternary ammonium salts. 前記相間移動触媒が、塩化テトラメチルアンモニウム、塩化メチルトリオクチルアンモニウム、塩化メチルトリデシルアンモニウム、及び塩化ベンジルトリメチルアンモニウムから選択された少なくとも１種の化合物である、請求項２に記載されたビスフェノールＡ-プロピレンオキシド付加物のジβ−メチルグリシジルエーテル。   The bisphenol A- according to claim 2, wherein the phase transfer catalyst is at least one compound selected from tetramethylammonium chloride, methyltrioctylammonium chloride, methyltridecylammonium chloride, and benzyltrimethylammonium chloride. Diβ-methyl glycidyl ether of propylene oxide adduct.
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