JPH0420008B2 - - Google Patents
Info
- Publication number
- JPH0420008B2 JPH0420008B2 JP58139828A JP13982883A JPH0420008B2 JP H0420008 B2 JPH0420008 B2 JP H0420008B2 JP 58139828 A JP58139828 A JP 58139828A JP 13982883 A JP13982883 A JP 13982883A JP H0420008 B2 JPH0420008 B2 JP H0420008B2
- Authority
- JP
- Japan
- Prior art keywords
- epichlorohydrin
- amount
- hydrolyzable chlorine
- aprotic polar
- polar solvent
- 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
Links
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 19
- 239000003822 epoxy resin Substances 0.000 claims description 13
- 229920000647 polyepoxide Polymers 0.000 claims description 13
- 150000002989 phenols Chemical class 0.000 claims description 12
- 239000002798 polar solvent Substances 0.000 claims description 12
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 17
- 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 14
- 238000006243 chemical reaction Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 229920003986 novolac Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- -1 alkali metal salts Chemical class 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
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003586 protic polar solvent Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- ASHGTJPOSUFTGB-UHFFFAOYSA-N methyl resorcinol Natural products COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Landscapes
- Epoxy Compounds (AREA)
- Epoxy Resins (AREA)
- Organic Insulating Materials (AREA)
Description
本発明は、特に電気および電子産業用に好適に
用いられるエポキシ樹脂の製造法に関する。
電気および電子材料として使用されるエポキシ
樹脂では、加水分解性塩素の含有量の少ないこと
が不可欠であり、このことは業界で広く認知され
ている。すなわち、加水分解性塩素は、電気絶縁
性の低下、リード線の腐蝕等の悪影響を及ぼす。
特に、半導体を使用する集積回路の封入用原料と
してのエポキシ樹脂では、加水分解性塩素の含有
量の少ないことが必須である。例えば、集積度64
キロビツト以上の集積回路では、加水分解性塩素
の含有量が600ppm以下であることが要求される。
加水分解性塩素を低減するために、さまざまな
製造方法が提案されている。例えば、特公昭53−
36000号には、ビスフエノールAとエピクロルヒ
ドリンとを溶解した溶液に水酸化ナトリウム水溶
液を徐々に供給しビスフエノールAのグリシジル
エーテルを製造する方法において、減圧・低温の
条件で水をエピクロルヒドリンと共沸させて除去
し、留出するエピクロルヒドリンを反応系中に循
環する方法が記載されている。該特許の実施例で
は加水分解性塩素は1200〜4500ppmであり充分な
改良効果は得られていない。特開昭54−90400号、
特開昭54−13596号および米国特許3121727号に
は、多価フエノールのグリシジルエーテルを製造
する方法において、多価フエノールとエピハロヒ
ドリンとの溶液にアルコールを添加する方法が記
載されている。該特許等の実施例では、特開昭54
−90400号の場合、ビスフエノールAとエピクロ
ルヒドリンとから得られるビスフエノールAのグ
リシジルエーテルの加水分解性塩素は約1000ppm
であり全塩素含有量は1500〜3500ppmであり、特
開昭54−13596の場合、フエノールノボラツクと
エピクロルヒドリンとから得られるフエノールノ
ボラツクのグリシジルエーテルの加水分解性塩素
は1500ppmであるなど充分な改良効果は得られて
いない。また該特許等では反応系内からの水分除
去はしなくてもよいと記載されているが、エピク
ロルヒドリンは水と共存するだけでも分解するこ
とは公知であり、工業上不利益である。
本発明者等は加水分解性塩素の含有量の少ない
エポキシ樹脂を得るべく鋭意研究した結果、エポ
キシ化反応の際特定の溶媒を用いることによりか
かる目的が達成されることを見いだし本発明に至
つた。
すなわち、本発明は、一価又は多価のフエノー
ル類とエピクロルヒドリンとをアルカリ金属水酸
化物および非プロトン性極性溶媒の存在下で反応
させることを特徴とするエポキシ樹脂製造法であ
る。本発明により、加水分解性塩素の含有量の少
ないエポキシ樹脂の製造が可能となつた。
本発明に使用される一価又は多価フエノール類
は、ハロゲン、アルキル基、アリル基、アルケニ
ル基、アリール基或いはアラルキル基で置換され
た或いは無置換のフエノール単位より成る一価又
は多価フエノール類であり、具体的にはフエノー
ル、オルトクレゾール、メタクレゾール、パラク
レゾール、ジフエノールメタン(ビスフエノール
F)、ジフエノールエタン、ジフエノールプロパ
ン(ビスフエノールA)、四臭化ビスフエノール
A、1,1―ビス―(4―ヒドロキシフエニル)
―1―フエニルエタン、1,1―ビス(4―ヒド
ロキシフエニル)―1,1―ジメチルメタン、フ
エノールノボラツク、臭素化フエノールノボラツ
ク、クレゾールノボラツク、臭素化クレゾールノ
ボラツク、レゾルシンノボラツク、臭素化レゾル
シンノボラツク、レゾルシン、ヒドロキノン、メ
チルレゾルシン、四塩化ビスフエノールAなどが
挙げられるが、これらに限定されるものではな
い。
本発明に使用されるアルカリ金属水酸化物は、
具体的には水酸化ナトリウム、水酸化カリウムな
どであるが、これらに限定されるものではない。
アルカリ金属水酸化物の使用量は、フエノール型
水酸基1モルに対し当モル程度が好ましい。アル
カリ金属水酸化物の使用量が少ないと、副生する
ゲル量が少なく製造上有利であるが、加水分解性
塩素が残存する。アルカリ金属水酸化物の使用量
が多いとゲル量が増加するので製造上不利益とな
る。
本発明に使用される非プロトン性極性溶媒は、
具体的にはジメチルスルホキシド、ジメチルスル
ホン、ジメチルホルムアミド、ジメチルアセトア
ミド、テトラメチル尿素、ヘキサメチルホスホル
アミドなどであるがこれらに限定されるものでは
ない。これらの非プロトン性極性溶媒の使用量
は、エピクロルヒドリン100重量部当り5〜50重
量部が好ましい。使用量が5重量部未満では、本
発明の効果があまり顕著ではない。使用量が多い
と分子間反応が進行しエポキシ当量(エポキシ基
1モル当りの分子量)が増加し、フエノール類の
グリシジルエーテルの品質が低下する。このこと
を考えると、50重量部以下が好ましい。
本発明で使用されるエピクロルヒドリンの使用
量はフエノール型水酸基1モルに対し2・5モル
〜20モルが好ましく、より好ましくは、4モル〜
10モルである。このことは、エピクロルヒドリン
の使用量が少ないと、分子間反応により高分子量
物の生成によりエポキシ樹脂の溶融粘度上昇等の
品質低下が起り、さらにゲル生成量が増加するな
ど工業的に不利益となるためであり、またエピク
ロルヒドリンの使用量が多いと反応混合物の容積
が増加するので、生産性が低下する等の工業的な
不利益が生じるためである。
本発明において、フエノール類のエポキシ化反
応は溶媒として非プロトン性極性溶媒を使用する
点を除き公知の方法により行うことができるが例
えば次のようにして行うことができる。まず、一
価又は多価フエノール類とエピクロルヒドリンを
先に記述の割合で混合する。固体のフエノール類
もエピクロルヒドリンに溶解して均一の溶液とな
る。ここにさらに非プロトン性極性溶媒を加えて
混合する。撹拌混合しながら次にアルカリ金属水
酸化物を加えて反応を行う。この反応は、常圧又
は減圧下で温度は常圧下は約100〜110℃、減圧下
では圧力にもよるが約50℃〜80℃に保持しつつ内
容液を共沸させる。揮発分は凝縮せしめて凝縮液
は油―水分離し、油分は反応系に戻すとの方法で
脱水を行う。アルカリ金属水酸化物の添加は、均
一に反応させるため2〜7時間かけて少量づつ分
割添加又は連続添加させる。一時的に入れると局
部的に反応が進みゲルが生成して好ましくない。
反応終了後はまず、蒸留により未反応のエピクロ
ルヒドリンを除去し次にメチル・イソブチルケト
ンなどのケトン類又はトルエンの様な芳香族炭化
水素溶媒で溶解し、不溶のアルカリ金属の塩を
別する。さらに水洗して非プロトン極性溶媒を除
去し、蒸溜により溶媒を除去してエポキシ樹脂を
得る。フエノール類のグリシジルエーテルを得
る。
本発明で云うエポキシ当量とは、エポキシ基1
モル当りの分子量で定義される。また加水分解性
塩素とは、エポキシ樹脂をジオキサンに溶解し、
水酸化カリウムのアルコール溶液を加え還流状態
で30分間加熱したときに脱離する塩素イオンを硝
酸銀溶液で逆滴定で定量し、該化合物中の塩素原
子の重量百分率で表わしたものである。以下に、
本発明を実施例をもつて詳細に説明するか、これ
らに限定されるものではない。
実施例1〜5および比較例1〜2
温度計、アルカリ金属水酸化物水溶液を連続添
加するための滴下ロート、撹拌翼、および反応系
中から蒸発する水分、エピクロルヒドリンを冷却
液化し有機層と水層をその比重差で分離して有機
層は反応系内にもどし水層は除去する冷却管付分
離管を有する容量1のバツフル付セパラブルフ
ラスコを用い、第1表に示す種類、量のフエノー
ル類とエピクロルヒドリンを反応させた。該反応
は、第1表に示す量の水酸化ナトリウム水溶液を
5時間で連続的に添加しながら、第1表に示す種
類、量の非プロトン性極性溶媒の存在下で行つ
た。
反応終了後は、未反応のエピクロルヒドリンを
減圧蒸留により除去し、このとき得られた副生塩
と非プロトン性極性溶媒を含むフエノール類のグ
リシジルエーテルをメチルイソブチルケトンに溶
解し、副生塩と非プロトン性極性溶媒を水洗によ
り除去した。さらに、減圧蒸留によりメチルイソ
ブチルケトンを除去してエポキシ樹脂を得た。こ
のようにして得られたエポキシ樹脂の加水分解性
塩素量およびエポキシ当量を第1表に示す。
非プロトン性極性溶媒を使用した実施例1にお
ける加水分解性塩素量は330ppmであるのに対し、
非プロトン性極性溶媒を使用しない比較例1にお
ける加水解性塩素量は、650ppmとなつており、
非プロトン性極性溶媒使用による加水分解性塩素
低減効果は顕著である。
The present invention relates to a method for producing an epoxy resin that is particularly suitable for use in the electrical and electronic industries. In epoxy resins used as electrical and electronic materials, a low content of hydrolyzable chlorine is essential, and this is widely recognized in the industry. That is, hydrolyzable chlorine has adverse effects such as a decrease in electrical insulation and corrosion of lead wires.
In particular, in epoxy resins used as raw materials for encapsulating integrated circuits using semiconductors, it is essential that the content of hydrolyzable chlorine be low. For example, density 64
For integrated circuits larger than kilobits, the content of hydrolyzable chlorine is required to be less than 600 ppm. Various manufacturing methods have been proposed to reduce hydrolyzable chlorine. For example, the
No. 36000 describes a method for producing glycidyl ether of bisphenol A by gradually supplying an aqueous sodium hydroxide solution to a solution of bisphenol A and epichlorohydrin, in which water is azeotroped with epichlorohydrin under reduced pressure and low temperature conditions. A method is described in which the epichlorohydrin removed by distillation is recycled into the reaction system. In the examples of this patent, the hydrolyzable chlorine content is 1200 to 4500 ppm, and a sufficient improvement effect is not obtained. Japanese Patent Publication No. 54-90400,
JP-A-54-13596 and US Pat. No. 3,121,727 describe a method for producing glycidyl ether of polyhydric phenol, in which alcohol is added to a solution of polyhydric phenol and epihalohydrin. In the example of the patent, etc.,
-90400, the hydrolyzable chlorine of glycidyl ether of bisphenol A obtained from bisphenol A and epichlorohydrin is approximately 1000 ppm.
The total chlorine content is 1500 to 3500 ppm, and in the case of JP-A-13596, the hydrolyzable chlorine of the glycidyl ether of phenol novolac obtained from phenol novolac and epichlorohydrin is 1500 ppm, which is a sufficient improvement. No effect has been obtained. Further, although the patent and the like state that it is not necessary to remove water from the reaction system, it is known that epichlorohydrin decomposes even when it coexists with water, which is industrially disadvantageous. As a result of intensive research to obtain an epoxy resin with a low content of hydrolyzable chlorine, the present inventors discovered that this objective could be achieved by using a specific solvent during the epoxidation reaction, leading to the present invention. . That is, the present invention is an epoxy resin production method characterized by reacting monovalent or polyvalent phenols with epichlorohydrin in the presence of an alkali metal hydroxide and an aprotic polar solvent. The present invention has made it possible to produce an epoxy resin with a low content of hydrolyzable chlorine. The monovalent or polyvalent phenols used in the present invention are monovalent or polyvalent phenols consisting of phenol units substituted or unsubstituted with halogen, alkyl group, allyl group, alkenyl group, aryl group, or aralkyl group. Specifically, phenol, orthocresol, metacresol, para-cresol, diphenolmethane (bisphenol F), diphenolethane, diphenolpropane (bisphenol A), bisphenol tetrabromide A, 1,1 -Bis-(4-hydroxyphenyl)
-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1,1-dimethylmethane, phenol novolak, brominated phenol novolak, cresol novolak, brominated cresol novolak, resorcinol novolak, bromine Examples include, but are not limited to, resorcinol novolak, resorcinol, hydroquinone, methylresorcinol, bisphenol A tetrachloride, and the like. The alkali metal hydroxide used in the present invention is
Specific examples include sodium hydroxide, potassium hydroxide, etc., but are not limited to these.
The amount of the alkali metal hydroxide used is preferably about the same mole per mole of phenolic hydroxyl group. When the amount of alkali metal hydroxide used is small, the amount of gel produced as a by-product is small, which is advantageous in production, but hydrolyzable chlorine remains. If the amount of alkali metal hydroxide used is large, the amount of gel increases, which is disadvantageous in production. The aprotic polar solvent used in the present invention is
Specific examples include dimethyl sulfoxide, dimethyl sulfone, dimethyl formamide, dimethyl acetamide, tetramethyl urea, hexamethyl phosphoramide, etc., but are not limited to these. The amount of these aprotic polar solvents used is preferably 5 to 50 parts by weight per 100 parts by weight of epichlorohydrin. If the amount used is less than 5 parts by weight, the effects of the present invention will not be so significant. If the amount used is too large, intermolecular reactions will proceed, the epoxy equivalent (molecular weight per mole of epoxy group) will increase, and the quality of the glycidyl ether of phenols will deteriorate. Considering this, it is preferably 50 parts by weight or less. The amount of epichlorohydrin used in the present invention is preferably 2.5 mol to 20 mol, more preferably 4 mol to 20 mol, per 1 mol of phenolic hydroxyl group.
It is 10 moles. This means that if the amount of epichlorohydrin used is small, the quality of the epoxy resin will deteriorate due to the formation of high molecular weight products due to the intermolecular reaction, such as an increase in the melt viscosity of the epoxy resin, and furthermore, the amount of gel formed will increase, which is industrially disadvantageous. This is because, if the amount of epichlorohydrin used is large, the volume of the reaction mixture increases, resulting in industrial disadvantages such as decreased productivity. In the present invention, the epoxidation reaction of phenols can be carried out by a known method, except that an aprotic polar solvent is used as a solvent, and for example, it can be carried out as follows. First, monovalent or polyvalent phenols and epichlorohydrin are mixed in the proportions described above. Solid phenols are also dissolved in epichlorohydrin to form a homogeneous solution. Further, an aprotic polar solvent is added and mixed. While stirring and mixing, the alkali metal hydroxide is then added to carry out the reaction. In this reaction, the content liquid is azeotropically distilled under normal pressure or reduced pressure while maintaining the temperature at about 100 to 110°C under normal pressure and about 50 to 80°C under reduced pressure, depending on the pressure. Dehydration is performed by condensing the volatile components, separating the condensate from oil and water, and returning the oil to the reaction system. The alkali metal hydroxide is added in small portions or continuously over 2 to 7 hours in order to react uniformly. If it is added temporarily, the reaction will progress locally and a gel will form, which is not preferable.
After the reaction is completed, unreacted epichlorohydrin is first removed by distillation, then dissolved in a ketone such as methyl isobutyl ketone or an aromatic hydrocarbon solvent such as toluene, and insoluble alkali metal salts are separated. Further, the aprotic polar solvent is removed by washing with water, and the solvent is removed by distillation to obtain an epoxy resin. Glycidyl ethers of phenols are obtained. In the present invention, the epoxy equivalent means epoxy group 1
Defined by molecular weight per mole. In addition, hydrolyzable chlorine is produced by dissolving epoxy resin in dioxane.
The chlorine ions released when an alcoholic solution of potassium hydroxide was added and heated under reflux for 30 minutes were determined by back titration with a silver nitrate solution, and expressed as the weight percentage of chlorine atoms in the compound. less than,
The invention will be explained in more detail by way of examples, without restricting it thereto. Examples 1 to 5 and Comparative Examples 1 to 2 A thermometer, a dropping funnel for continuously adding an aqueous alkali metal hydroxide solution, a stirring blade, and water evaporating from the reaction system and epichlorohydrin are cooled and liquefied to form an organic layer and water. Using a separable flask with a baffle and a capacity of 1, which has a separating tube with a cooling tube that separates the layers based on their specific gravity differences, returns the organic layer to the reaction system, and removes the aqueous layer, the types and amounts of phenols shown in Table 1 are added. was reacted with epichlorohydrin. The reaction was carried out in the presence of an aprotic polar solvent of the type and amount shown in Table 1 while continuously adding an aqueous sodium hydroxide solution in the amount shown in Table 1 over a period of 5 hours. After the reaction is complete, unreacted epichlorohydrin is removed by vacuum distillation, and the resulting by-product salt and glycidyl ether of phenols containing an aprotic polar solvent are dissolved in methyl isobutyl ketone to separate the by-product salt and non-protic solvent. The protic polar solvent was removed by washing with water. Furthermore, methyl isobutyl ketone was removed by vacuum distillation to obtain an epoxy resin. Table 1 shows the amount of hydrolyzable chlorine and epoxy equivalent of the epoxy resin thus obtained. While the amount of hydrolyzable chlorine in Example 1 using an aprotic polar solvent was 330 ppm,
The amount of hydrolyzable chlorine in Comparative Example 1, which does not use an aprotic polar solvent, is 650 ppm.
The effect of reducing hydrolyzable chlorine by using an aprotic polar solvent is remarkable.
【表】
☆☆ エピクロルヒドリンのモル数
☆☆☆ 水酸化ナトリウムのモル数
[Table] ☆☆ Number of moles of epichlorohydrin ☆☆☆ Number of moles of sodium hydroxide
Claims (1)
ドリンとをアルカリ金属水酸化物および非プロト
ン性極性溶媒の存在下で反応させることを特徴と
するエポキシ樹脂製造法。1. A method for producing an epoxy resin, which comprises reacting monovalent or polyvalent phenols with epichlorohydrin in the presence of an alkali metal hydroxide and an aprotic polar solvent.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58139828A JPS6031517A (en) | 1983-07-29 | 1983-07-29 | Production of epoxy resin |
JP5014787A JP2555853B2 (en) | 1983-07-29 | 1993-02-01 | Epoxy resin manufacturing method |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58139828A JPS6031517A (en) | 1983-07-29 | 1983-07-29 | Production of epoxy resin |
JP5014787A JP2555853B2 (en) | 1983-07-29 | 1993-02-01 | Epoxy resin manufacturing method |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP5014787A Division JP2555853B2 (en) | 1983-07-29 | 1993-02-01 | Epoxy resin manufacturing method |
Publications (2)
Publication Number | Publication Date |
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JPS6031517A JPS6031517A (en) | 1985-02-18 |
JPH0420008B2 true JPH0420008B2 (en) | 1992-03-31 |
Family
ID=26350804
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP58139828A Granted JPS6031517A (en) | 1983-07-29 | 1983-07-29 | Production of epoxy resin |
JP5014787A Expired - Lifetime JP2555853B2 (en) | 1983-07-29 | 1993-02-01 | Epoxy resin manufacturing method |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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JP5014787A Expired - Lifetime JP2555853B2 (en) | 1983-07-29 | 1993-02-01 | Epoxy resin manufacturing method |
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JP (2) | JPS6031517A (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6230145A (en) * | 1985-08-01 | 1987-02-09 | Matsushita Electric Works Ltd | Epoxy resin composition for electronic material |
DE3689111D1 (en) * | 1985-12-13 | 1993-11-04 | Ciba Geigy | IMPROVED METHOD FOR PRODUCING GLYCIDYL COMPOUNDS. |
JPH0759616B2 (en) * | 1987-04-10 | 1995-06-28 | 住友化学工業株式会社 | Method for producing epoxy resin |
US4778863A (en) * | 1987-08-13 | 1988-10-18 | The Dow Chemical Company | Preparation of epoxy resins having low undesirable halogen content |
JP2565960B2 (en) * | 1987-12-23 | 1996-12-18 | 旭チバ株式会社 | Method for producing epoxy compound |
JP2565959B2 (en) * | 1987-12-24 | 1996-12-18 | 旭チバ株式会社 | Method for producing glycidyl ethers |
JP2532119B2 (en) * | 1987-12-24 | 1996-09-11 | 旭チバ株式会社 | Method for producing multifunctional epoxy resin |
JPH0791360B2 (en) * | 1987-12-26 | 1995-10-04 | 住友化学工業株式会社 | Process for producing glycidyl ether of polyphenol |
CA2157148A1 (en) | 1994-09-08 | 1996-03-09 | Masatsugu Akiba | Epoxy resin composition and resin-encapsulated semiconductor device |
ES2364790T3 (en) | 2008-05-15 | 2011-09-14 | Evonik Degussa Gmbh | ELECTRONIC WRAPPING |
KR101660237B1 (en) * | 2014-07-18 | 2016-09-27 | 국도화학 주식회사 | Preparation methode of Biobased Epoxy Resin and It's Composition for Cured System |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5783520A (en) * | 1980-11-12 | 1982-05-25 | Sumitomo Chem Co Ltd | Preparation of epoxy resin |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5218180A (en) * | 1975-08-01 | 1977-02-10 | Mitsubishi Electric Corp | Constant voltage diode |
DD153882A1 (en) | 1980-09-09 | 1982-02-10 | Rainer Ehrig | PROCESS FOR THE PREPARATION OF EPOXY RESINS |
-
1983
- 1983-07-29 JP JP58139828A patent/JPS6031517A/en active Granted
-
1993
- 1993-02-01 JP JP5014787A patent/JP2555853B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5783520A (en) * | 1980-11-12 | 1982-05-25 | Sumitomo Chem Co Ltd | Preparation of epoxy resin |
Also Published As
Publication number | Publication date |
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JPH0673039A (en) | 1994-03-15 |
JPS6031517A (en) | 1985-02-18 |
JP2555853B2 (en) | 1996-11-20 |
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