JP4334044B2 - Method for producing liquid epoxy resin - Google Patents
Method for producing liquid epoxy resin Download PDFInfo
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- JP4334044B2 JP4334044B2 JP00835199A JP835199A JP4334044B2 JP 4334044 B2 JP4334044 B2 JP 4334044B2 JP 00835199 A JP00835199 A JP 00835199A JP 835199 A JP835199 A JP 835199A JP 4334044 B2 JP4334044 B2 JP 4334044B2
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- epoxy resin
- formula
- water
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Description
【0001】
【発明の属する技術分野】
本発明は耐熱性、耐水性に優れる硬化物を与え、しかも粘度が低く加水分解性塩素量の少ない液状エポキシ樹脂の簡便な製造方法に関する。
【0002】
【従来の技術】
エポキシ樹脂は種々の硬化剤で硬化させることにより、一般的に機械的性質、耐水性、耐薬品性、耐熱性、電気的性質などに優れた硬化物となり、接着剤、塗料、積層板、成形材料、注型材料などの幅広い分野に利用されている。従来、液状エポキシ樹脂組成物において、エポキシ樹脂としては液状のビスフェノ−ルA型エポキシ樹脂が最も一般的に使用されている。更に低粘度が要求される分野等においては水添化されたビスフェノールAをジグリシジルエーテル化した液状エポキシ樹脂が広く知られている。
水添化ビスフェノールA型エポキシ樹脂は、原料の水添化ビスフェノールAの結晶性が高く、更にそのエピハロヒドリンに対する反応性が極めて低く、溶剤溶解性も非常に低いため、例えば三フッ化ホウ素錯体などのルイス酸触媒を用いてエピハロヒドリンをアルコール性水酸基に付加させた後、アルカリ金属水酸化物を添加し、脱塩酸反応により製造するといった方法が従来採用されていた。
【0003】
【発明が解決しようとする課題】
しかしながら、前記したような製法では三フッ化ホウ素錯体のような酸化力の強い触媒を用いるために危険性を伴い、更に得られたエポキシ樹脂は、加水分解性塩素量が1N水酸化カリウム のエタノール溶液中で30分間還流して0.01N硝酸銀水溶液で滴定した場合、2〜5%と非常に高いため、高信頼性を要求される電気・電子部品の分野での使用は極めて限定されたものにならざるを得なかった。
【0004】
【課題を解決するための手段】
本発明者らはこうした実状に鑑み、加水分解性塩素量が低く低粘度の水添化ビスフェノールA型エポキシ樹脂の簡便な製造方法を求めて鋭意研究した結果、本発明を完成させるに到った。
【0005】
すなわち本発明は
(1)式(1)
【0006】
【化2】
【0007】
で表される化合物とエピハロヒドリンを4級アンモニウム塩及び固形のアルカリ金属水酸化物の共存下で20〜70℃で撹拌し反応させた後、反応系内に比重が水よりも軽く、水に対する溶解性の低い有機溶剤と水とを加え、式(1)で表される化合物のジグリシジルエーテルを抽出する工程を含むエポキシ樹脂の製造方法、
(2)有機溶剤がメチルイソブチルケトン或いはトルエンである上記(1)記載のエポキシ樹脂の製造方法
を提供するものである。
【0008】
【発明の実施の形態】
本発明のエポキシ樹脂の製造方法において、固形のアルカリ金属水酸化物としては水酸化ナトリウム、或いは水酸化カリウム等が挙げられるが、特に水酸化ナトリウムが好ましい。その形状としてはフレーク状、マーブル状などがあるがフレーク状が好ましい。該アルカリ金属水酸化物の使用量は式(1)で表されるアルコール性水酸基1当量に対し通常1〜6モルであるが、1〜5モルが好ましく、1.2〜4モルがより好ましい。
【009】
また、触媒として用いられる4級アンモニウム塩としてはテトラメチルアンモニウムクロライド、テトラメチルアンモニウムブロマイド、トリメチルベンジルアンモニウムクロライド、トリエチルベンジルアンモニウムクロライド等が挙げられる。4級アンモニウム塩の使用量は式(1)で表される化合物の量に対し通常0.1〜5重量%、より好ましくは0.2〜3重量%である。
【0010】
これらの反応において使用されるエピハロヒドリンの量は式(1)で表される化合物の水酸基1当量に対し通常1〜5モル、好ましくは1.2〜3モルである。エピハロヒドリンの使用量は少なければ少ないほど反応を迅速に行うことができるが、余り少ないと系全体の粘度が高くなりすぎ、撹拌が困難になる恐れがある。
【0011】
反応はこれらの成分を反応器に同時に仕込み、一定時間撹拌して行う。個々の固形成分は始めは溶解せずに不均一の状態だが、徐々に一部が溶解し始め反応が進行する。反応時間としては通常1〜30時間であるが、3〜25時間が好ましく、5〜20時間がより好ましい。反応温度としては通常15〜80℃であるが、20〜70℃が好ましく、25〜65℃がより好ましい。
【0012】
反応終了後、これらのエポキシ化反応の反応液中に比重が水よりも軽く、水に対する溶解性の低い有機溶剤と水とを加え、式(1)で表される化合物のジグリシジルエーテルを有機溶媒層に抽出する。使用する有機溶剤としてはメチルイソブチルケトン、メチルエチルケトン、トルエン、ベンゼン等が挙げられ、このうちメチルイソブチルケトン、トルエンが好ましい。有機溶剤の量としては通常目的物の理論収量の0.8〜10倍であるが、1〜5倍が好ましく、特に1.2〜4倍が好ましい。
【0013】
更に水を加えて水洗を行う。使用する水の量は通常有機溶剤の0.5〜1.0倍であるが、好ましくは、0.2〜0.9倍である。この水洗により生成塩、未反応のアルカリ金属水酸化物等を除去し、更に加熱減圧下、添加した有機溶剤を留去することにより目的とするエポキシ樹脂が得られる。
【0014】
また更に高純度のエポキシ樹脂を得るために水洗後の有機溶剤溶液中に、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の水溶液を加えて更に反応を行い、閉環を確実なものにすることもできる。この場合アルカリ金属水酸化物の使用量はエポキシ化に使用した式(1)で表される化合物の水酸基1当量に対して通常0.005〜0.5モルであるが、好ましくは0.01〜0.3モル、特に好ましくは0.05〜0.2モルである。反応温度は50〜120℃、反応時間は通常0.5〜2時間である。
反応終了後、生成した塩などを水洗などにより除去し、更に加熱減圧下、添加した有機溶剤を留去することにより加水分解性塩素量の少ないエポキシ樹脂が得られる。
このように精製処理したエポキシ樹脂の加水分解塩素量は通常1800ppm以下、好ましい条件下で得られたものは1500ppm以下となる。
【0015】
こうして得られたエポキシ樹脂は、通常のエポキシ樹脂と同様、例えばアミン系化合物、酸無水物系化合物、アミド系化合物、フェノ−ル系化合物などの硬化剤、並びに必要により硬化促進剤、無機充填材及び各種配合材とを必要に応じて押出機、ニ−ダ、ロ−ル等を用いて均一になるまで充分に混合してエポキシ樹脂組成物とすることができる。更に得られたエポキシ樹脂組成物を溶融後注型あるいはトランスファ−成形機などを用いて成形し、さらに80〜200℃で2〜10時間加熱することにより硬化物を得ることができる。
【0016】
【実施例】
次に本発明を実施例、比較例により更に具体的に説明するが、以下において部は特に断わりのない限りすべて重量部であるものとする。
【0017】
実施例1
温度計、滴下ロート、冷却管、撹拌器を取り付けたフラスコに前記式(1)で表される結晶性化合物120部、フレーク状水酸化ナトリウム100部、テトラメチルアンモニウムクロライド1.2部及びエピクロルヒドリン185部を同時に仕込み40℃に加熱し、その後10時間40℃で撹拌を続けた。反応終了後、352部のメチルイソブチルケトン及び200部の水を加え撹拌後静置し、完全に2層に相分離した後、水層のみを除去した。
【0018】
更にこのメチルイソブチルケトンの溶液を70℃に加熱し30重量%の水酸化ナトリウム水溶液10部を添加し1時間反応させた後、水洗を3回繰り返し水層のpHを中性とした。更に水層は分離除去し、ロータリエバポレーターを使用して油層から加熱減圧下メチルイソブチルケトンを留去し、前記式(1)で表される化合物のジグリシジルエーテル156部を得た。得られたエポキシ樹脂は液状であり25℃での粘度は25℃で2000cps、エポキシ当量は221g/eqであった。また加水分解性塩素量に関しては、1Nの水酸化カリウム /エタノール溶液で30分間還流下で加水分解した後、0.01Nの硝酸銀水溶液で滴定を行い測定したところ580ppmであった。
【0019】
【発明の効果】
本発明の製造方法によれば一般的に困難とされてきた高純度の水添ビスフェノールAのジグリシジルエーテル化を極めて容易に、しかも安全に行うことが出来る。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a simple method for producing a liquid epoxy resin which gives a cured product excellent in heat resistance and water resistance and has a low viscosity and a small amount of hydrolyzable chlorine.
[0002]
[Prior art]
Epoxy resins are generally cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., adhesives, paints, laminates, moldings It is used in a wide range of fields such as materials and casting materials. Conventionally, in a liquid epoxy resin composition, a liquid bisphenol A type epoxy resin is most commonly used as an epoxy resin. Further, in fields where low viscosity is required, liquid epoxy resins obtained by dihydridyl etherification of hydrogenated bisphenol A are widely known.
The hydrogenated bisphenol A type epoxy resin has high crystallinity of the raw material hydrogenated bisphenol A, and also has extremely low reactivity with epihalohydrin and very low solvent solubility. A method in which epihalohydrin is added to an alcoholic hydroxyl group using a Lewis acid catalyst, followed by addition of an alkali metal hydroxide and production by a dehydrochlorination reaction has been conventionally employed.
[0003]
[Problems to be solved by the invention]
However, the production method as described above is dangerous because it uses a catalyst having a strong oxidizing power such as a boron trifluoride complex. Further, the obtained epoxy resin is ethanol having a hydrolyzable chlorine content of 1N potassium hydroxide. When it is refluxed in a solution for 30 minutes and titrated with a 0.01N silver nitrate aqueous solution, it is very high at 2 to 5%, so its use in the field of electrical and electronic parts requiring high reliability is extremely limited. I had to be.
[0004]
[Means for Solving the Problems]
In light of these circumstances, the present inventors have intensively studied for a simple method for producing a hydrogenated bisphenol A type epoxy resin having a low hydrolyzable chlorine content and a low viscosity, and as a result, the present invention has been completed. .
[0005]
That is, the present invention relates to (1) formula (1)
[0006]
[Chemical formula 2]
[0007]
After stirring and reacting the compound represented by the formula and epihalohydrin at 20 to 70 ° C. in the presence of a quaternary ammonium salt and a solid alkali metal hydroxide, the specific gravity in the reaction system is lighter than that of water and dissolving in water. A method for producing an epoxy resin comprising a step of adding an organic solvent having low property and water and extracting the diglycidyl ether of the compound represented by the formula (1),
(2) The method for producing an epoxy resin according to the above (1), wherein the organic solvent is methyl isobutyl ketone or toluene.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
In the method for producing an epoxy resin of the present invention, examples of the solid alkali metal hydroxide include sodium hydroxide and potassium hydroxide, and sodium hydroxide is particularly preferable. The shape includes a flake shape and a marble shape, but a flake shape is preferable. Although the usage-amount of this alkali metal hydroxide is 1-6 mol normally with respect to 1 equivalent of alcoholic hydroxyl groups represented by Formula (1), 1-5 mol is preferable and 1.2-4 mol is more preferable. .
[009]
Examples of the quaternary ammonium salt used as a catalyst include tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, and triethylbenzylammonium chloride. The amount of the quaternary ammonium salt used is usually 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, based on the amount of the compound represented by formula (1).
[0010]
The amount of epihalohydrin used in these reactions is usually 1 to 5 mol, preferably 1.2 to 3 mol, relative to 1 equivalent of the hydroxyl group of the compound represented by formula (1). The smaller the amount of epihalohydrin used, the faster the reaction can be carried out. However, if the amount used is too small, the viscosity of the entire system becomes too high and stirring may become difficult.
[0011]
In the reaction, these components are charged into a reactor at the same time and stirred for a predetermined time. The individual solid components do not dissolve at first but are in a non-uniform state, but some of them gradually begin to dissolve and the reaction proceeds. The reaction time is usually 1 to 30 hours, preferably 3 to 25 hours, more preferably 5 to 20 hours. The reaction temperature is usually 15 to 80 ° C, preferably 20 to 70 ° C, more preferably 25 to 65 ° C.
[0012]
After completion of the reaction, an organic solvent having a specific gravity lighter than water and having a low solubility in water and water are added to the reaction solution of these epoxidation reactions, and the diglycidyl ether of the compound represented by the formula (1) is organically added. Extract into solvent layer. Examples of the organic solvent to be used include methyl isobutyl ketone, methyl ethyl ketone, toluene, and benzene. Among these, methyl isobutyl ketone and toluene are preferable. The amount of the organic solvent is usually 0.8 to 10 times the theoretical yield of the target product, but is preferably 1 to 5 times, and particularly preferably 1.2 to 4 times.
[0013]
Add more water and wash. The amount of water used is usually 0.5 to 1.0 times that of the organic solvent, but preferably 0.2 to 0.9 times. The product salt, unreacted alkali metal hydroxide, and the like are removed by this water washing, and the added organic solvent is distilled off under heating and reduced pressure to obtain the desired epoxy resin.
[0014]
In addition, in order to obtain a higher purity epoxy resin, an aqueous solution of alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to the organic solvent solution after washing to further carry out the reaction to ensure ring closure. You can also In this case, the amount of alkali metal hydroxide used is usually 0.005 to 0.5 mol, preferably 0.01 to 1 equivalent of the hydroxyl group of the compound represented by formula (1) used for epoxidation. It is -0.3 mol, Most preferably, it is 0.05-0.2 mol. The reaction temperature is 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
After completion of the reaction, the generated salt and the like are removed by washing and the like, and the added organic solvent is distilled off under reduced pressure by heating to obtain an epoxy resin having a small amount of hydrolyzable chlorine.
The amount of hydrolyzed chlorine in the epoxy resin thus purified is usually 1800 ppm or less, and that obtained under preferred conditions is 1500 ppm or less.
[0015]
The epoxy resin thus obtained is the same as a normal epoxy resin, for example, a curing agent such as an amine compound, an acid anhydride compound, an amide compound, a phenol compound, and a curing accelerator, an inorganic filler, if necessary. The various compounding materials can be sufficiently mixed using an extruder, a kneader, a roll or the like as necessary until uniform, to obtain an epoxy resin composition. Further, the obtained epoxy resin composition is melted and then molded using a casting or transfer molding machine, and further heated at 80 to 200 ° C. for 2 to 10 hours to obtain a cured product.
[0016]
【Example】
Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following, all parts are parts by weight unless otherwise specified.
[0017]
Example 1
In a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer, 120 parts of the crystalline compound represented by the above formula (1), 100 parts of flaky sodium hydroxide, 1.2 parts of tetramethylammonium chloride, and epichlorohydrin 185 The parts were charged simultaneously and heated to 40 ° C., and then stirred at 40 ° C. for 10 hours. After completion of the reaction, 352 parts of methyl isobutyl ketone and 200 parts of water were added, and the mixture was stirred and allowed to stand. After complete phase separation into two layers, only the aqueous layer was removed.
[0018]
Further, this methyl isobutyl ketone solution was heated to 70 ° C., 10 parts of a 30% by weight aqueous sodium hydroxide solution was added and allowed to react for 1 hour. Further, the aqueous layer was separated and removed, and methyl isobutyl ketone was distilled off from the oil layer using a rotary evaporator under heating and reduced pressure to obtain 156 parts of diglycidyl ether of the compound represented by the formula (1). The resulting epoxy resin was liquid and had a viscosity at 25 ° C. of 2000 cps at 25 ° C. and an epoxy equivalent of 221 g / eq. The amount of hydrolyzable chlorine was 580 ppm as measured by titration with 0.01 N aqueous silver nitrate solution after hydrolysis with 1 N potassium hydroxide / ethanol solution for 30 minutes under reflux.
[0019]
【The invention's effect】
According to the production method of the present invention, diglycidyl etherification of high-purity hydrogenated bisphenol A, which has been generally considered difficult, can be carried out very easily and safely.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP00835199A JP4334044B2 (en) | 1999-01-14 | 1999-01-14 | Method for producing liquid epoxy resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP00835199A JP4334044B2 (en) | 1999-01-14 | 1999-01-14 | Method for producing liquid epoxy resin |
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JP2000204136A JP2000204136A (en) | 2000-07-25 |
JP4334044B2 true JP4334044B2 (en) | 2009-09-16 |
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JP00835199A Expired - Fee Related JP4334044B2 (en) | 1999-01-14 | 1999-01-14 | Method for producing liquid epoxy resin |
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JP2002128771A (en) * | 2000-10-26 | 2002-05-09 | Sakamoto Yakuhin Kogyo Co Ltd | New method for producing epoxy compound, and epoxy resin composition containing the epoxy compound produced by the method |
JP2002194056A (en) * | 2000-12-27 | 2002-07-10 | Nippon Kayaku Co Ltd | Epoxy resin composition and its cured product |
JP4945958B2 (en) * | 2005-08-23 | 2012-06-06 | 三菱化学株式会社 | Method for producing purified epoxy resin |
CN104558517A (en) * | 2014-12-23 | 2015-04-29 | 安徽助成信息科技有限公司 | Synthesis method of bisphenol A epoxy resin |
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