JPS6231728B2 - - Google Patents
Info
- Publication number
- JPS6231728B2 JPS6231728B2 JP55105140A JP10514080A JPS6231728B2 JP S6231728 B2 JPS6231728 B2 JP S6231728B2 JP 55105140 A JP55105140 A JP 55105140A JP 10514080 A JP10514080 A JP 10514080A JP S6231728 B2 JPS6231728 B2 JP S6231728B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy compound
- hydrolyzable chlorine
- added
- crude
- quaternary ammonium
- 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
Links
- 239000004593 Epoxy Substances 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 28
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 26
- 229910052801 chlorine Inorganic materials 0.000 description 26
- 239000000460 chlorine Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 7
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006798 ring closing metathesis reaction Methods 0.000 description 5
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000003021 water soluble solvent Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ASHVGNGFCXYXBN-UHFFFAOYSA-M 1-benzyl-2-methylpyridin-1-ium;chloride Chemical compound [Cl-].CC1=CC=CC=[N+]1CC1=CC=CC=C1 ASHVGNGFCXYXBN-UHFFFAOYSA-M 0.000 description 1
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- -1 tetraalkylammonium halide Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Organic Insulating Materials (AREA)
Description
【発明の詳細な説明】
本発明は、加水分解性塩素含有率を低下させ、
しかも効率よく粗製エポキシ化合物を後処理する
方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention reduces the hydrolyzable chlorine content,
Moreover, the present invention relates to a method for efficiently post-treating a crude epoxy compound.
多価フエノールとエピハロヒドリンからエポキ
シ化合物を製造する方法は、古くから種々知られ
ているが、基本的には水酸化アルカリ金属の存在
下にハロヒドリンエーテル化とそれに続く脱ハロ
ゲン化水素を同一反応系で行なう方法である。こ
の反応をハロゲンとして塩素をアルカリ金属とし
てナトリウムを例にとつて１つの反応式にまとめ
ると次の通りである。 Various methods for producing epoxy compounds from polyhydric phenols and epihalohydrins have been known for a long time, but basically they involve the same reaction of halohydrin etherification and subsequent dehydrohalogenation in the presence of an alkali metal hydroxide. This is a system-based method. This reaction can be summarized into one reaction formula using halogen, chlorine, alkali metal, and sodium as an example, as follows.
この場合、エピクロルヒドリンは、フエノール
性水酸基に対し過剰に使用され、水酸化ナトリウ
ムはフエノール性水酸基１当量に対し通常0.9〜
1.1当量使用される。しかし、このようにして得
られた粗製エポキシ化合物中には、使用した水酸
化ナトリウムの量がフエノール性水酸基より少い
場合はもちろんのこと、過剰であつても微量のク
ロルヒドリンエーテル基が閉環されずにそのまま
残存しており、水酸化ナトリウムの使用量を更に
過剰にしても、過剰に使用しているエピクロルヒ
ドリンの分解、副反応が促進されるばかりで閉環
効率のアツプはあまり望めない。 In this case, epichlorohydrin is used in excess with respect to the phenolic hydroxyl group, and sodium hydroxide is usually used in an amount of 0.9 to 10% per equivalent of the phenolic hydroxyl group.
1.1 equivalents are used. However, in the crude epoxy compound obtained in this way, not only when the amount of sodium hydroxide used is less than the phenolic hydroxyl group, but even when it is in excess, a trace amount of chlorohydrin ether group is present in the ring-closing compound. Even if the amount of sodium hydroxide used is further increased, the decomposition of the excessively used epichlorohydrin and side reactions will only be accelerated, and no increase in ring-closing efficiency can be expected.
特に電気関係の用途などでは、この残存してい
る加水分解性塩素が電気的な性能の低下の原因と
なるため、再閉環工程が必要となる。 Particularly in electrical applications, the remaining hydrolyzable chlorine causes a decrease in electrical performance, so a re-ring closure step is required.
再閉環工程は、一般に過剰のエピクロルヒドリ
ンを留去した後、トルエン、キシレンなどの芳香
族系溶媒あるいはメチルイソブチルケトン、メチ
ルエチルケトンなどのケトン系溶媒で希釈して、
濃度１〜20％の水酸化ナトリウム水溶液を、残存
している加水分解性塩素に対し、1.1〜10倍当量
添加し、60〜90℃で行われる。しかし、この方法
では加水分解性塩素を0.1％以下、特に0.05％以
下まで低減するには、前述の条件のうち、かなり
厳しい条件をとつても困難であり、その場合には
逆にエポキシ基の水和等の好ましくない副反応が
生じるおそれがある。この場合、上記の疎水性溶
剤に代えてアセトン、メチルアルコール、エチル
アルコール、プロピルアルコールなどの水溶性溶
媒を多量に用いれば、比較的ゆるやかな条件でも
加水分解性塩素を0.1％以下にすることはできる
が、水溶性溶媒は水と分離しにくいので、廃水中
にこれらの有機溶媒が混入し、このため廃水処理
が大変で製造コストは高いものとなる。 In the re-ring closure process, the excess epichlorohydrin is generally distilled off and then diluted with an aromatic solvent such as toluene or xylene or a ketone solvent such as methyl isobutyl ketone or methyl ethyl ketone.
An aqueous sodium hydroxide solution having a concentration of 1 to 20% is added in an equivalent amount of 1.1 to 10 times the remaining hydrolyzable chlorine, and the reaction is carried out at 60 to 90°C. However, with this method, it is difficult to reduce hydrolyzable chlorine to 0.1% or less, especially 0.05% or less, even under the extremely severe conditions mentioned above, and in that case, conversely, the epoxy group Undesirable side reactions such as hydration may occur. In this case, if you use a large amount of a water-soluble solvent such as acetone, methyl alcohol, ethyl alcohol, or propyl alcohol instead of the above-mentioned hydrophobic solvent, it is possible to reduce the hydrolyzable chlorine to 0.1% or less even under relatively mild conditions. However, since water-soluble solvents are difficult to separate from water, these organic solvents are mixed into wastewater, making wastewater treatment difficult and production costs high.
本発明者らは、かなり再閉環工程について鋭意
研究した結果、粗製エポキシ化合物をもし未反応
エピハロヒドリンが存在する場合にはこれを除去
した後、第４級アンモニウム塩又は第４級アンモ
ニウム塩基を閉環触媒として使用することによ
り、疎水性溶剤系でも水酸化アルカリ金属水溶液
にておだやかな条件で、加水分解性塩素を容易に
0.05％以下に低減することができることに成功
し、本発明を完成するに至つた。 As a result of extensive research into the ring-closing process, the present inventors have discovered that after removing unreacted epihalohydrin from the crude epoxy compound, if any, it is present, a quaternary ammonium salt or a quaternary ammonium base is added as a ring-closing catalyst. By using it as a hydrolytic solvent, it is possible to easily hydrolyze chlorine under mild conditions in aqueous alkali metal hydroxide solutions even in hydrophobic solvent systems.
We succeeded in reducing the amount to 0.05% or less, and completed the present invention.
即ち、本発明は、「多価フエノールとエピハロ
ヒドリンから製造された粗製エポキシ化合物を未
反応エピハロヒドリンが存在する場合にはこれを
蒸留などにより除去した後、第４級アンモニウム
塩又は第４級アンモニウム塩基の存在する水酸化
アルカリ金属水溶液と疎水性溶剤との混合系中で
処理し、残存ハロヒドリンエーテル基をグリシジ
ルエーテル基化することを特徴とする粗製エポキ
シ化合物の後処理方法」に関する。 That is, the present invention provides the following method: ``After removing unreacted epihalohydrin by distillation or the like from a crude epoxy compound produced from a polyhydric phenol and epihalohydrin, a quaternary ammonium salt or a quaternary ammonium base is prepared. This invention relates to a method for post-treatment of crude epoxy compounds, which comprises treating in a mixed system of an existing aqueous alkali metal hydroxide solution and a hydrophobic solvent to convert residual halohydrin ether groups into glycidyl ether groups.
多価フエノールとエピハロヒドリンから粗製エ
ポキシ化合物を製造する方法は、特に制限はない
が、水酸化アルカリ金属水溶液の存在下で行なう
方法が代表的であり、多価フエノールとしては、
例えばビスフエノールＡ、ビスフエノールＦ、レ
ゾルシノール、ハイドロキノン、フエノールまた
はクレゾールのようなアルキルフエノールとホル
ムアルデヒドのようなアルデヒドとの縮合によつ
て得られるノボラツク樹脂などが、エピハロヒド
リンとしては例えば、エピクロルヒドリン、エピ
ブロモヒドリンが挙げられる。 There are no particular restrictions on the method for producing a crude epoxy compound from polyhydric phenol and epihalohydrin, but a typical method is to carry out in the presence of an aqueous alkali metal hydroxide solution.
Examples of epihalohydrins include novolak resins obtained by condensing an alkylphenol such as bisphenol A, bisphenol F, resorcinol, hydroquinone, phenol, or cresol with an aldehyde such as formaldehyde; One example is phosphorus.
本発明では、このような粗製エポキシ化合物
を、もし未反応エピハロヒドリンが存在する場合
には蒸留などによりこれを除去した後、疎水性溶
剤例えばトルエン、キシレン、ベンゼンなどの芳
香族系溶剤、メチルエチルケトン、メチルイソブ
チルケトンなどのケトン系溶剤で希釈し、必要な
らばここで水洗を行なつて不純物を除去した後、
第４級アンモニウム塩又は第４級アンモニウム塩
基をエポキシ化合物（固形分）を基準にして0.01
〜３重量％添加し、更に水酸化アルカリ金属好ま
しくは水酸化ナトリウム水溶液（濃度は通常１〜
10％）を残存している加水分解性塩素１原子に対
してNaOH1.1〜２分子となるような割合で添加
し、60〜90℃で１〜５時間撹拌する。その後、水
層を分離除去し、場合によつて水及びNaH2PO4
のような弱酸を加えて中和洗浄した後、疎水性溶
剤を留去すれば、容易に精製されたエポキシ化合
物を得る。 In the present invention, such a crude epoxy compound is treated with a hydrophobic solvent such as an aromatic solvent such as toluene, xylene, benzene, methyl ethyl ketone, methyl ethyl ketone, methyl ethyl ketone, etc. After diluting with a ketone solvent such as isobutyl ketone and washing with water if necessary to remove impurities,
0.01 quaternary ammonium salt or quaternary ammonium base based on epoxy compound (solid content)
~3% by weight, and further alkali metal hydroxide, preferably an aqueous sodium hydroxide solution (concentration is usually 1~3% by weight).
10%) is added at a ratio of 1.1 to 2 molecules of NaOH per remaining 1 atom of hydrolyzable chlorine, and stirred at 60 to 90°C for 1 to 5 hours. The aqueous layer is then separated and removed, optionally containing water and NaH 2 PO 4
After neutralizing and washing by adding a weak acid such as, the hydrophobic solvent is distilled off to easily obtain a purified epoxy compound.
本発明において使用される第４級アンモニウム
塩及び第４級アンモニウム塩基の代表的なものと
しては、テトラアルキルアンモニウハライドまた
はヒドロキサイドがあげられるが、その例として
はベンジルトリエチルアンモニウムクロライド、
ベンジルトリブチルアンモニウムクロライド、テ
トラブチルアンモニウムブロマイド、トリオクチ
ルメチルアンモニウムクロライド、テトラメチル
アンモニウムクロライド、テトラメチルアンモニ
ウムヒドロキサイドなどがある。そのほか、Ｎ―
アルキルピリジニウムハライドまたはヒドロキサ
イドあるいはＮ―アルキルピコリニウムハライド
またはヒドロキサイド例えば、Ｎ―ラウリルピリ
ジニウムクロライド、Ｎ―ベンジルピコリニウム
クロライドなども使用することができる。 Typical quaternary ammonium salts and quaternary ammonium bases used in the present invention include tetraalkylammonium halide or hydroxide, examples of which include benzyltriethylammonium chloride,
Examples include benzyltributylammonium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride, tetramethylammonium chloride, and tetramethylammonium hydroxide. In addition, N-
Alkylpyridinium halides or hydroxides or N-alkylpicolinium halides or hydroxides such as N-laurylpyridinium chloride, N-benzylpicolinium chloride, etc. can also be used.
本発明の方法は、簡単で効率がよく廃水処理も
容易であり、しかも、得られるエポキシ化合物中
の加水分解性塩素は大巾に減少している。 The method of the present invention is simple, efficient, and easy to treat wastewater, and the amount of hydrolyzable chlorine in the resulting epoxy compound is greatly reduced.
次いで実施例により本発明を説明する。尚、文
中の「部」は「重量部」を意味するものとする。 Next, the present invention will be explained by examples. Note that "parts" in the text mean "parts by weight."
〔実施例 １〕
ビスフエノールA456ｇ（２モル）をエピクロ
ルヒドリン1850ｇ（20モル）に溶解し、105℃ま
で昇温した後、48％NaOH水溶液320ｇ（3.84ｇ
当量）を５時間かけて滴下した。その間、110±
５℃で水を共沸蒸留して系外に除去し、分離した
エピクロルヒドリンは系内にもどした。滴下終了
後、過剰のエピクロルヒドリンを蒸留除去し、最
終的に150℃／10mmHgで30分間保持した。[Example 1] 456 g (2 mol) of bisphenol A was dissolved in 1850 g (20 mol) of epichlorohydrin, and after heating to 105°C, 320 g (3.84 g) of 48% NaOH aqueous solution was dissolved.
equivalent amount) was added dropwise over 5 hours. Meanwhile, 110±
Water was removed from the system by azeotropic distillation at 5°C, and the separated epichlorohydrin was returned to the system. After the dropwise addition was completed, excess epichlorohydrin was removed by distillation, and the temperature was finally maintained at 150° C./10 mmHg for 30 minutes.
次にこの粗生成物をトルエン800ｇに溶解し、
水600ｇを加えて洗浄した後、不揮発分中の加水
分解性塩素含有率を測定すると、0.88％であつ
た。 Next, dissolve this crude product in 800g of toluene,
After washing with 600 g of water, the hydrolyzable chlorine content in the nonvolatile matter was measured and found to be 0.88%.
このようにして得られた粗エポキシ化合物のト
ルエン溶液を２等分し、その一つにベンジルトリ
エチルアンモニウムクロライド1.7ｇ（理論樹脂
量の0.5％）を添加し、３％NaOH水溶液168ｇ
（加水分解性塩素に対し1.5倍当量）を加えて80℃
で２時間かけて再閉環を行つた。その後、水層を
棄却し、水300ｇを加えNaH2PO4で中和して最後
に減圧下にトルエンを除去し、濾過して以下の性
状値のエポキシ化合物を得た。 The toluene solution of the crude epoxy compound thus obtained was divided into two equal parts, 1.7 g of benzyltriethylammonium chloride (0.5% of the theoretical resin amount) was added to one half, and 168 g of a 3% NaOH aqueous solution was added.
(1.5 times equivalent to hydrolyzable chlorine) and 80℃
The ring was re-closed over a period of 2 hours. Thereafter, the aqueous layer was discarded, 300 g of water was added, and the mixture was neutralized with NaH 2 PO 4 .Finally, toluene was removed under reduced pressure and filtered to obtain an epoxy compound having the following properties.
エポキシ当量 187
加水分解性塩素 0.03％
粘 度（25℃） 10700cps
〔比較例 １〕
実施例１で得られた粗エポキシ化合物のトルエ
ン溶液の２等分した残りの一つに、５％NaOH水
溶液236ｇ（加水分解性塩素に対し3.5倍当量）を
加えて、87℃で３時間かけて再閉環を行つた。そ
の後水層を棄却し、水300ｇを加えNaH2PO4で中
和して、最後に減圧下にトルエンを除去し、濾過
して以下の性状値のエポキシ化合物を得た。Epoxy equivalent: 187 Hydrolyzable chlorine: 0.03% Viscosity (25°C): 10,700 cps [Comparative Example 1] The toluene solution of the crude epoxy compound obtained in Example 1 was divided into two halves, and 236 g of a 5% NaOH aqueous solution was added to the remaining one. (3.5 times equivalent to hydrolyzable chlorine) was added to carry out re-ring closure at 87°C for 3 hours. Thereafter, the aqueous layer was discarded, 300 g of water was added, and the mixture was neutralized with NaH 2 PO 4 .Finally, toluene was removed under reduced pressure and filtered to obtain an epoxy compound having the following properties.
エポキシ当量 189
加水分解性塩素 0.18％
粘 度（25℃） 11200cps
〔実施例 ２〕
実施例１において、トルエンのかわりにメチル
イソブチルケトンを使用した以外は全く同じ方法
で、粗エポキシ化合物のメチルイソブチルケトン
溶液を調製し（加水分解性塩素固型分比0.90
％）、実施例１と全く同じ方法で再閉環処理し
（NaOHは加水分解性塩素に対し1.5倍当量）、以
下の性状値のエポキシ化合物を得た。Epoxy equivalent: 189 Hydrolyzable chlorine: 0.18% Viscosity (25°C): 11,200 cps [Example 2] The crude epoxy compound methyl isobutyl ketone was prepared in exactly the same manner as in Example 1, except that methyl isobutyl ketone was used instead of toluene. Prepare a solution (hydrolyzable chlorine solid content ratio 0.90
%) and was subjected to re-ring closure treatment in exactly the same manner as in Example 1 (NaOH was 1.5 times equivalent to hydrolyzable chlorine) to obtain an epoxy compound with the following properties.
エポキシ当量 187
加水分解性塩素 0.03％
粘 度（25℃） 10400cps
〔比較例 ２〕
実施例１において、過剰のエピクロルヒドリン
を蒸留除去する前に水240ｇを加えて、析出して
いるNaClを溶解除去し、その後、過剰のエピク
ロルヒドリンを蒸留除去し、最終的に150℃／10
mmHgで30分間保持した。Epoxy equivalent: 187 Hydrolyzable chlorine: 0.03% Viscosity (25°C): 10400 cps [Comparative example 2] In Example 1, before removing excess epichlorohydrin by distillation, 240 g of water was added to dissolve and remove precipitated NaCl. , then the excess epichlorohydrin was removed by distillation, and the final temperature was 150℃/10
Hold at mmHg for 30 minutes.
このようにして得られた粗エポキシ化合物の加
水分解性塩素を測定すると、0.85％であつた。 When the hydrolyzable chlorine content of the crude epoxy compound thus obtained was measured, it was 0.85%.
次にこの粗エポキシ化合物にメタノール34ｇ
（粗エポキシ化合物の５％）を加えた後、３％
NaOH水溶液141ｇ（加水分解性塩素に対し1.3倍
当量）で、70℃で４時間かけて再閉環を行つた。
その後トルエン40ｇを加えて水層を棄却し、更に
水洗、中和して、以下の性状値のエポキシ化合物
を得た。 Next, add 34g of methanol to this crude epoxy compound.
(5% of crude epoxy compound), then 3%
Re-ring closure was carried out using 141 g of NaOH aqueous solution (1.3 times equivalent to hydrolyzable chlorine) at 70° C. for 4 hours.
Thereafter, 40 g of toluene was added, the aqueous layer was discarded, and the mixture was further washed with water and neutralized to obtain an epoxy compound having the following properties.
エポキシ当量 189
加水分解性塩素 0.38％
粘 度（25℃） 11400cps
〔実施例 ３〕
軟化点72℃、水酸基当量104のフエノールノボ
ラツク樹脂624ｇ（６当量）を、エピクロルヒド
リン2220ｇ（24モル）に溶解し、105℃まで昇温
した後、48％NaOH水溶液474ｇ（5.7当量）を５
時間かけて滴下した。その間110±５℃で水を共
沸蒸留して系外に除去し、分離したエピクロルヒ
ドリンは系内にもどした。滴下終了後、過剰のエ
ピクロルヒドリンを蒸留除去し、最終的に150
℃／10mmHgで30分間保持した。Epoxy equivalent: 189 Hydrolyzable chlorine: 0.38% Viscosity (25°C): 11,400 cps [Example 3] 624 g (6 equivalents) of a phenol novolac resin with a softening point of 72°C and a hydroxyl equivalent of 104 was dissolved in 2,220 g (24 moles) of epichlorohydrin. , after raising the temperature to 105℃, 474g (5.7 equivalents) of 48% NaOH aqueous solution was added to
It dripped over time. During this time, water was removed from the system by azeotropic distillation at 110±5°C, and the separated epichlorohydrin was returned to the system. After the dropping, excess epichlorohydrin is distilled off and the final concentration is 150%.
The temperature was maintained at ℃/10 mmHg for 30 minutes.
次にこの粗生成物をメチルイソブチルケトン
1155ｇに溶解し、水900ｇを加えて洗浄した後、
不揮発分中の加水分解性塩素を測定すると、1.86
％であつた。 This crude product was then converted into methyl isobutyl ketone.
After dissolving in 1155g and washing with 900g of water,
Hydrolyzable chlorine in non-volatile matter was measured to be 1.86
It was %.
このようにして得られた粗エポキシ化合物のメ
チルイソブチルケトン溶液を３等分し、その一つ
にテトラメチルアンモニウムクロライド1.6ｇ
（理論樹脂量の0.5％）を添加し、５％NaOH水溶
液174ｇ（加水分解性塩素に対して1.3倍当量）を
加えて80℃で４時間かけて再閉環を行つた。その
後水層を棄却し水300ｇを加えNaH2PO4で中和し
て、最後に減圧下メチルイソブチルケトンを除去
し、濾過して以下の性状値のエポキシ化合物を得
た。 The methyl isobutyl ketone solution of the crude epoxy compound thus obtained was divided into three equal parts, and one of them was given 1.6 g of tetramethylammonium chloride.
(0.5% of the theoretical resin amount) was added, and 174 g of a 5% NaOH aqueous solution (1.3 times equivalent to hydrolyzable chlorine) was added to perform recirculation at 80° C. over 4 hours. Thereafter, the aqueous layer was discarded, 300 g of water was added, and the mixture was neutralized with NaH 2 PO 4 .Finally, methyl isobutyl ketone was removed under reduced pressure and filtered to obtain an epoxy compound having the following properties.
エポキシ当量 190
加水分解性塩素 0.04％
〔比較例 ３〕
実施例３で得られた粗エポキシ化合物のメチル
イソブチルケトン溶液の３等分したうちの一つに
５％NaOH水溶液201ｇ（加水分解性塩素に対し
て1.5倍当量）を加えて、80℃で４時間撹拌した
後、実施例３を同じ処理をして、以下の性状値の
エポキシ化合物を得た。Epoxy equivalent weight 190 Hydrolyzable chlorine 0.04% [Comparative example 3] 201 g of a 5% NaOH aqueous solution (hydrolyzable chlorine After stirring at 80° C. for 4 hours, the same treatment as in Example 3 was carried out to obtain an epoxy compound having the following properties.
エポキシ当量 191
加水分解性塩素 0.21％
〔実施例 ４〕
実施例３で得られた粗エポキシ化合物のメチル
イソブチルケトン溶液の３等分した残りの一つに
テトラメチルアンモニウムヒドロキサイド1.3ｇ
（理論樹脂量の0.4％）を水溶液の形で添加し、そ
の後は実施例３と全く同じ処理をして以下の性状
値のエポキシ化合物を得た。Epoxy equivalent: 191 Hydrolyzable chlorine: 0.21% [Example 4] The methyl isobutyl ketone solution of the crude epoxy compound obtained in Example 3 was divided into three equal parts, and 1.3 g of tetramethylammonium hydroxide was added to the remaining one.
(0.4% of the theoretical resin amount) was added in the form of an aqueous solution, and then the same treatment as in Example 3 was carried out to obtain an epoxy compound having the following properties.
エポキシ当量 190 加水分解性塩素 0.03％Epoxy equivalent weight 190 Hydrolyzable chlorine 0.03%
Claims (1)
された粗製エポキシ化合物を、未反応エピハロヒ
ドリンが存在する場合にはこれを除去した後、第
４級アンモニウム塩又は第４級アンモニウム塩基
の存在する水酸化アルカリ金属水溶液と疎水性溶
剤との混合系中で処理し、残存ハロヒドリンエー
テル基をグリシジルエーテル基化することを特徴
とする粗製エポキシ化合物の後処理方法。1. After removing unreacted epihalohydrin, if any, from a crude epoxy compound produced from polyhydric phenol and epihalohydrin, it is treated with an aqueous alkali metal hydroxide solution containing a quaternary ammonium salt or a quaternary ammonium base. 1. A method for post-treatment of a crude epoxy compound, which comprises treating a crude epoxy compound in a mixed system with a hydrophobic solvent to convert residual halohydrin ether groups into glycidyl ether groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10514080A JPS5731922A (en) | 1980-08-01 | 1980-08-01 | Aftertreatment of crude epoxy compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10514080A JPS5731922A (en) | 1980-08-01 | 1980-08-01 | Aftertreatment of crude epoxy compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5731922A JPS5731922A (en) | 1982-02-20 |
| JPS6231728B2 true JPS6231728B2 (en) | 1987-07-10 |
Family
ID=14399439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10514080A Granted JPS5731922A (en) | 1980-08-01 | 1980-08-01 | Aftertreatment of crude epoxy compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5731922A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4675777B2 (en) * | 2003-02-03 | 2011-04-27 | 新日鐵化学株式会社 | Epoxy resin, production method thereof, epoxy resin composition and cured product using the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1387668A (en) * | 1971-03-26 | 1975-03-19 | Ciba Geigy Ag | Methylolglycidyl ethers and process for their manufacture |
| JPS5490400A (en) * | 1977-12-20 | 1979-07-18 | Shell Int Research | Preparation of polyglycidyl ethers |
| JPS55141479A (en) * | 1979-04-19 | 1980-11-05 | Shell Int Research | Manufacture of polyglycidylether of polyhydric phenol |
-
1980
- 1980-08-01 JP JP10514080A patent/JPS5731922A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1387668A (en) * | 1971-03-26 | 1975-03-19 | Ciba Geigy Ag | Methylolglycidyl ethers and process for their manufacture |
| JPS5490400A (en) * | 1977-12-20 | 1979-07-18 | Shell Int Research | Preparation of polyglycidyl ethers |
| JPS55141479A (en) * | 1979-04-19 | 1980-11-05 | Shell Int Research | Manufacture of polyglycidylether of polyhydric phenol |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5731922A (en) | 1982-02-20 |
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