JPS63308024A - Production of flame-retardant epoxy polymer - Google Patents
Production of flame-retardant epoxy polymerInfo
- Publication number
- JPS63308024A JPS63308024A JP14329887A JP14329887A JPS63308024A JP S63308024 A JPS63308024 A JP S63308024A JP 14329887 A JP14329887 A JP 14329887A JP 14329887 A JP14329887 A JP 14329887A JP S63308024 A JPS63308024 A JP S63308024A
- Authority
- JP
- Japan
- Prior art keywords
- bromine
- resin
- brominated
- reaction
- formula
- 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.)
- Granted
Links
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 8
- 239000003063 flame retardant Substances 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920000642 polymer Polymers 0.000 title abstract 6
- 239000004593 Epoxy Substances 0.000 title 1
- 229920003986 novolac Polymers 0.000 claims abstract description 38
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 24
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 239000003822 epoxy resin Substances 0.000 claims description 23
- 229920000647 polyepoxide Polymers 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 241000238557 Decapoda Species 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 150000003944 halohydrins Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-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 1
- 230000009471 action Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 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 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- -1 potassium hydroxide Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、耐熱、ｍ燃性に優れた難燃性エポキシ樹脂の
製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a flame-retardant epoxy resin having excellent heat resistance and flame resistance.
後記一般式（Ｉｆ）で表わされるノボラック型樹脂を臭
素の作用により置換臭素化することは、すでに知られて
いる。又、その際、副反応として生成する臭化水素を系
内で酸化剤を使用して臭素に変換して、ノボラック型樹
脂と反応させ、経済的に有利ならしめることも、すでに
知られている。It is already known that a novolak type resin represented by the general formula (If) described below is subjected to substitutional bromination by the action of bromine. In addition, it is already known that hydrogen bromide produced as a side reaction can be converted into bromine using an oxidizing agent within the system and reacted with the novolac type resin, making it economically advantageous. .
（特開昭４９−５４３０１．特開昭５８−２２５〔発明
が解決しようとする問題点〕
しかし、酸化剤を使用して、系内の臭化水素を臭素に変
換し、ノボラック型樹脂と反応させ臭素化ノボラック型
樹脂を得たとしても、更にアルカリ存在下、エピハロヒ
ドリンと反応させ臭素化ノボラック型エポキシ樹脂を製
造すると、樹脂の粘度が上昇してしまう欠点を有してい
る。この粘度の上昇は、最近の電子材料の進歩に伴う厳
しい品質要求に対して、ぜひとも解決しなければならな
い問題である。すなわち、粘度上昇による流れ特性の変
化は１品質の安定化、工程管理上、極めて本発明者らは
、臭素化ノボラック型エポキシ樹脂を製造するに当って
臭素とノボラック型樹脂との反応に際して副生ずる臭化
水素を系内で過酸化水素によって酸化し、臭素に変換さ
せてノボラック型樹脂と更に反応させる経済的に有利な
方法で臭素化ノボラック型樹脂を製造し、ついで、還元
剤による処理をした後、アルカリ存在下、エピハロヒド
リンと反応させることにより粘度の上昇を抑えることを
見い出し１本発明を完成させるに至った。(JP-A-49-54301; JP-A-58-225 [Problems to be solved by the invention]) However, using an oxidizing agent, hydrogen bromide in the system is converted to bromine, which reacts with the novolac type resin. Even if a brominated novolak-type resin is obtained, if a brominated novolak-type epoxy resin is produced by further reacting with epihalohydrin in the presence of an alkali, the viscosity of the resin increases.This increase in viscosity This is a problem that must be solved in response to the strict quality requirements accompanying the recent advances in electronic materials.In other words, changes in flow characteristics due to increased viscosity are extremely important in terms of quality stabilization and process control. In the production of brominated novolak-type epoxy resin, they oxidized hydrogen bromide, which is a by-product during the reaction between bromine and novolac-type resin, with hydrogen peroxide in the system, converting it to bromine, and converting it into novolac-type resin. We have discovered that the increase in viscosity can be suppressed by producing a brominated novolac type resin by an economically advantageous method of further reaction, and then treating it with a reducing agent and then reacting it with epihalohydrin in the presence of an alkali.1 The present invention was completed.
即ち、本発明は
一般式（１）
Ｃ式中、Ｒは水素またはメチル基を示し、ｎは平均値０
〜１０を示す。Ｘ及びｙは夫々０〜２の整数を示す。但
しＸとｙは同時にＯとなることはない。）
で表わされる臭素化ノボラック型樹脂とエピハロヒドリ
ンをアルカリ存在下反応させて難燃性エポキシ樹脂を製
造゛する方法において。That is, the present invention is based on the general formula (1) C, where R represents hydrogen or a methyl group, and n is an average value of 0.
~10 is shown. X and y each represent an integer of 0 to 2. However, X and y cannot become O at the same time. ) In a method for producing a flame-retardant epoxy resin by reacting a brominated novolac type resin represented by the following formula with epihalohydrin in the presence of an alkali.
一般式（ＩＩ）
Ｃ式中、Ｒは水素又は、メチル基を示し、ｎは平均値０
〜１０を示す。）
で表わされるノボラック型樹脂を有機溶媒中で臭素と過
酸化水素存在下反応させ１反応後、還元剤により処理し
て得られた臭素化ノボラック型樹脂を、アルカリ存在下
エピハロヒドリンと反応させることを特徴とする難燃性
エポキシ樹脂の製造法に関する。General formula (II) C In the formula, R represents hydrogen or a methyl group, and n is an average value of 0
~10 is shown. ) is reacted with bromine in an organic solvent in the presence of hydrogen peroxide, and after one reaction, the resulting brominated novolac resin is treated with a reducing agent, and the resulting brominated novolak resin is reacted with epihalohydrin in the presence of an alkali. This article relates to a method for producing a flame-retardant epoxy resin.
本発明で得られる難燃性エポ午シ樹脂は、一般（式中
Ｒ＊ ｎ ＋ 、ｘｒ Ｐは前記と同じ意味を表わす
。）
で表わされる臭素化ノボラック型エポキシ樹脂である。The flame-retardant epoxy resin obtained in the present invention can be used in general (in the formula
R* n + and xr P have the same meanings as above. ) is a brominated novolac type epoxy resin.
本発明によれば、一般式（Ｉｆ）で表わされるノボラッ
ク型樹脂を臭素化するに際し、臭素のみで臭素化して得
られる一般式（１）で表わされる臭素化ノボラック型樹
脂を使って、アルカリ存在下、エピハロヒドリンとの反
応により製造される一般式（Ｉ［ｌ）の臭素化ノボラッ
ク型エポキシ樹脂の粘度と同等の値を有する臭素化ノボ
ラック型エポキシ樹脂が得られる。According to the present invention, when brominating the novolac type resin represented by the general formula (If), the brominated novolak type resin represented by the general formula (1) obtained by bromination with bromine alone is used to prevent the presence of an alkali. Below, a brominated novolak epoxy resin having a viscosity equivalent to that of the brominated novolac epoxy resin of the general formula (I[l) produced by reaction with epihalohydrin is obtained.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
一般式〔Ｉ［）で表わされるノボラック型樹脂をメタノ
ール、四塩化炭素等の臭素と反応しない溶媒に溶かし、
臭素の沸点以下の温度、好ましくは１０〜５０℃で臭素
と反応させる。A novolak type resin represented by the general formula [I[] is dissolved in a solvent that does not react with bromine, such as methanol or carbon tetrachloride,
The reaction with bromine is carried out at a temperature below the boiling point of bromine, preferably from 10 to 50°C.
この際、使用する臭素量は、ノボラック型樹脂の目的の
臭素化度に応じた化学量論による置換反応に必要な量又
は僅□かに過剰量でよい。次に系内に副生ずる臭化水素
を臭素に変換するのに過酸化水素水を添加する。過酸化
水素は、臭素の当量もしくは僅かだ少ない量を使用する
のが好ましい。In this case, the amount of bromine used may be the amount required for the stoichiometric substitution reaction depending on the desired degree of bromination of the novolac type resin, or the amount slightly excessive. Next, hydrogen peroxide solution is added to convert hydrogen bromide produced as a by-product in the system into bromine. Preferably, hydrogen peroxide is used in an amount equivalent to or slightly less than bromine.
又、過酸化水素水の添加時期は、必ずしも所定量の臭素
を全量添加した後である必要はなく、臭素の添加と交互
に行なってもよいし、また、これを同時に行なってもよ
い。Further, the timing of adding the hydrogen peroxide solution does not necessarily need to be after the entire predetermined amount of bromine has been added, and may be performed alternately with the addition of bromine, or may be performed simultaneously.
かくして臭素化されたノボラック型樹脂溶液は。Thus, the brominated novolac type resin solution is.
僅かな未反応の臭化水素を含有しているから、あらかじ
め苛性ンーダ等で中和しておくことが望ましい。ついで
還元剤を添加して還元処理を行う。Since it contains a small amount of unreacted hydrogen bromide, it is desirable to neutralize it with caustic soda or the like in advance. Then, a reducing agent is added to perform a reduction treatment.
還元剤としては、特に限定されないが、ハイドロサルフ
ァイド、ジ岨すン酸、尿素、チオ尿素、トリフェニルホ
スフィン、アスコルビン酸が有効で。Effective reducing agents include, but are not limited to, hydrosulfide, dibasic acid, urea, thiourea, triphenylphosphine, and ascorbic acid.
特に、ハイドロサルファイド、ジ亜リン酸が有効である
。Hydrosulfide and diphosphorous acid are particularly effective.
還元剤の使用量は特に限定されないが、使用した過酸化
水素に対して２重量％〜３０重量％使用するのが好まし
く、特に５〜２５重量％使用するのが好ましい。The amount of the reducing agent used is not particularly limited, but it is preferably used in an amount of 2% to 30% by weight, particularly preferably 5 to 25% by weight, based on the hydrogen peroxide used.
還元処理は、室温乃至溶媒の沸点付近で実施すればよく
１例えば還元剤を、使用した過酸化水素に対して２重量
％〜３０重量％添加した後、ＳＯ℃〜６０℃の温度で約
３０分間〜２時間処理することにより実施することがで
きる。The reduction treatment may be carried out at room temperature or near the boiling point of the solvent. For example, after adding a reducing agent in an amount of 2% to 30% by weight based on the hydrogen peroxide used, the reduction treatment is carried out at a temperature of SO°C to 60°C for approximately 30% by weight. This can be carried out by treating for minutes to 2 hours.
かくして、還元処理を施された臭素化ノボラック型樹脂
溶液は、そのまま、あるいは必要により樹脂を回収後、
エビハロヒドリンと公知の方法によりエポキシ化され、
容易に臭素化ノボラック型エポキシ樹脂（難燃性エポキ
シ樹脂）を得ることができる。In this way, the reduced brominated novolac type resin solution can be used as it is or after recovering the resin if necessary.
Epoxidized with shrimp halohydrin by a known method,
A brominated novolac type epoxy resin (flame-retardant epoxy resin) can be easily obtained.
臭素化ノボラック型樹脂を、臭素化ノボラック型樹脂の
水酸基当量に対して過剰モル量のエビハロヒドリンとを
テトラメチルアンモニウムクロリド、テトラメチルアン
モニウムプロミド、トリエチルアンモニウムクロリドな
どの第４級アンモニウム塩または水酸化ナトリウム、水
酸化カリウムなどのアルカリ金属水酸化物などの存在下
で反応させ、第４級アンモニウム塩などを用いた場合は
開環付加反応の段階で反応がとまるので次いで上記アル
カリ金属水酸化物を加えて閉環反応させる。The brominated novolac type resin is mixed with shrimp halohydrin in an excess molar amount relative to the hydroxyl equivalent of the brominated novolac type resin, and a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, triethylammonium chloride, or sodium hydroxide. The reaction is carried out in the presence of an alkali metal hydroxide such as potassium hydroxide, and when a quaternary ammonium salt is used, the reaction stops at the stage of the ring-opening addition reaction, so the alkali metal hydroxide is then added. to perform a ring-closing reaction.
また最初からアルカリ金属水酸化物を加えて反応する場
合は、開環付加反応および閉環反応を一気に行わせる。In addition, when the alkali metal hydroxide is added from the beginning and the reaction is carried out, the ring-opening addition reaction and the ring-closing reaction are carried out at once.
エピハロヒドリンの使用割合は臭素化ノボラック樹脂の
水酸基当量ＩＫ対して通常１〜５０モル、好ましくは５
〜１５モルの範囲である。エビハロヒドリントシてハ、
エピクロルヒドリン、エビブロムヒドリン等が使用でき
る。The proportion of epihalohydrin used is usually 1 to 50 mol, preferably 5 mol to the hydroxyl equivalent IK of the brominated novolak resin.
~15 moles. Ebi halohydrinoshiteha,
Epichlorohydrin, ebibromohydrin, etc. can be used.
アルカリ金属水酸化物の使用量は臭素化ノボラック型樹
脂の水酸基当量１に対して通常０・８〜１・５モル、好
ましくは０．９〜１．３モルの範囲であり、第４級アン
モニウム塩を使用する場合その使用量は臭素化ノボラッ
ク型樹脂の水酸基当量１に対して通常０・００１〜１モ
ル、好ましくはｏ、ｏ ｏ ｓ〜０．５モルの範囲であ
る。The amount of alkali metal hydroxide used is usually in the range of 0.8 to 1.5 mol, preferably 0.9 to 1.3 mol, per 1 hydroxyl equivalent of the brominated novolac type resin, and quaternary ammonium When a salt is used, the amount used is usually 0.001 to 1 mol, preferably 0.001 to 0.5 mol, per 1 hydroxyl equivalent of the brominated novolak resin.
反応温度は通常３０〜１３０℃好ましくは４０〜８０℃
である。The reaction temperature is usually 30-130℃, preferably 40-80℃
It is.
また反応で生成した水を反応系外圧除去しながら反応を
進行させることもできる。The reaction can also be allowed to proceed while removing the external pressure of the reaction system to remove the water produced in the reaction.
反応終了後副生じた塩を、水洗、濾過等により除去し過
剰のエビハロヒドリンを留去することに化する方法に較
べて、高価な臭素の消費量を減少させ、しかも、得られ
るエポキシ樹脂は従来の樹脂と同等の安定した品質のも
のであるという利点を有している。Compared to the method of removing by-product salts after the completion of the reaction by washing with water, filtration, etc. and distilling off excess shrimp halohydrin, the amount of expensive bromine consumed is reduced, and the resulting epoxy resin is It has the advantage of being of stable quality equivalent to other resins.
以下に実施例を挙げて説明する。 Examples will be described below.
実施例１
フェノール・ノボラック樹脂（水酸基当量１０６９／８
’Ｌ、）５５９及びメタノール１ｏｏｙを温度計、攪拌
機付４つロフラスコに仕込み、窒素ガスを吹込みながら
溶解する。これに臭素４８２（０・５モル）を反応温度
２５℃〜３（ＩＣで滴下する。臭素滴下終了後、５５％
過酸化水素水２４．５９（０，２５モル）を反応温度２
５℃〜３０℃で滴下し、１ｗ下後後１応液をそのままの
温度で３０分間攪拌を続けた。その後、３０％苛性ンー
ダ水溶液を徐々に添加し、中和後、還元剤としてハイド
ロサルファイド１２を添加し、５０℃に加温して１時間
攪拌した。Example 1 Phenol/novolac resin (hydroxyl equivalent: 1069/8
559 L, ) and 1 ooy of methanol were placed in a four-bottle flask equipped with a thermometer and a stirrer, and dissolved while blowing in nitrogen gas. Bromine 482 (0.5 mol) is added dropwise to this at a reaction temperature of 25°C to 3 (IC). After the completion of the bromine addition, 55%
Hydrogen peroxide solution 24.59 (0.25 mol) at reaction temperature 2
It was added dropwise at 5°C to 30°C, and after lowering the temperature by 1w, the first reaction solution was continued to be stirred at the same temperature for 30 minutes. Thereafter, a 30% aqueous caustic solution was gradually added, and after neutralization, hydrosulfide 12 was added as a reducing agent, heated to 50° C., and stirred for 1 hour.
この反応液を激しく攪拌している水５を中に滴下し５粒
状の臭素化フェノール・ノボラック樹脂を得た。こうし
て得られた粒状臭素化フェノール・ノボラック樹脂をエ
ピクロルヒドリン２７８２（５モル）に溶解し、還流装
置のついた反応器に仕込み、減圧下（１００ｍＨｙ）で
共沸脱水により系内の水分を除去した。共沸脱水後％
４８チ苛性ソーダ水溶液４２２を６時間で滴下した。こ
の間。Water 5 was added dropwise to this reaction solution while vigorously stirring to obtain 5 grains of brominated phenol novolac resin. The granular brominated phenol novolac resin thus obtained was dissolved in epichlorohydrin 2782 (5 mol), charged into a reactor equipped with a reflux device, and water in the system was removed by azeotropic dehydration under reduced pressure (100 mHy). % after azeotropic dehydration
422 hours of a 48% caustic soda aqueous solution was added dropwise over 6 hours. During this time.
苛性ンーダ水溶液に含まれる水及び反応により生成する
水を減圧下（１５０１１１１Ｈｐ 〜２５０ ｔｍ Ｈ
ｙ ）で共沸脱水しながら反応温度を７５℃〜８０℃に
保った。苛性ソーダ水溶液滴下終了後、そのままの温度
で、さらに１時間攪拌した。The water contained in the caustic powder aqueous solution and the water produced by the reaction were purified under reduced pressure (1501111Hp ~ 250 tm H
The reaction temperature was maintained at 75°C to 80°C while performing azeotropic dehydration at step y). After completing the dropwise addition of the caustic soda aqueous solution, the mixture was stirred for an additional hour at the same temperature.
過剰のエピクロルヒドリンを追い出し、臭素化フェノー
ル拳ノボラック・エポキシ樹脂１１０ｆｔ−得た。得ら
れたエポキシ樹脂の溶融粘度（工Ｃ工粘度、１５０℃）
は１１．５ボイスであった。Excess epichlorohydrin was removed to obtain 110 ft of brominated phenolic novolak epoxy resin. Melt viscosity of the obtained epoxy resin (technical viscosity, 150°C)
had 11.5 voices.
実施例２
還元剤として３０％ジＩ ＩＪン酸水溶液３２を用いた
以外は、実施例１と同様に反応して、エポキシ樹脂１１
１２を得た。溶融粘度を表−１に示した。Example 2 Epoxy resin 11 was reacted in the same manner as in Example 1 except that 30% diIJ acid aqueous solution 32 was used as the reducing agent.
I got 12. The melt viscosity is shown in Table-1.
実施例５
還元剤として、アスコルビン酸１２を用いた以外は、実
施例１と同様に反応して、エポキシ樹脂１０８２を得た
。溶融粘度を表−ＩＫ示した。Example 5 Epoxy resin 1082 was obtained by reacting in the same manner as in Example 1, except that ascorbic acid 12 was used as the reducing agent. The melt viscosity is shown in Table IK.
実施例４
還元剤として、トリフェニル・ホスフィン１２を用いた
以外は、実施例１と同様に反応して、エポキシ樹脂１０
７２を得た。溶融粘度を表−１に示した。Example 4 Epoxy resin 10 was reacted in the same manner as in Example 1 except that triphenyl phosphine 12 was used as the reducing agent.
I got 72. The melt viscosity is shown in Table-1.
比較例１
還元剤を使用しない以外は、実施例１と同様に反応して
、エポキシ樹脂１００２を得た。溶融粘度を表−１に示
した。Comparative Example 1 Epoxy resin 1002 was obtained by reacting in the same manner as in Example 1 except that no reducing agent was used. The melt viscosity is shown in Table-1.
比較例２
フェノール・ノボラック樹脂（水酸基当量１ｏ６ｙ／ｅ
ｑ、）ｓｓｙ及びメタノール１００９を温度計、攪拌機
付４つロフラスコに仕込み、窒素ガスを吹込みながら溶
解する。Comparative Example 2 Phenol/novolak resin (hydroxyl equivalent 1o6y/e
q, )ssy and methanol 1009 are placed in a four-bottle flask equipped with a thermometer and a stirrer, and dissolved while blowing nitrogen gas.
これに、臭素Ｅ１８Ｆ（０，５５モル）を反応温度２５
℃〜３０℃で滴下する。臭素滴下終了後、そのままの温
度で３０分間攪拌を続けた。その後。To this, bromine E18F (0.55 mol) was added at a reaction temperature of 25
Add dropwise at ~30°C. After the bromine dropwise addition was completed, stirring was continued for 30 minutes at the same temperature. after that.
３０チ苛性ソーダ水溶液を徐々に添加し、副生じた臭化
水素を中和した。中和後、この反応液を激しく攪拌して
いる水５を中に滴下し１粒状の臭素化フェノール・ノボ
ラック樹脂を得た。こうして得られた粒状臭素化フェノ
ール・ノボラック樹脂を実施例１と同様の操作によりエ
ポキシ化して。A 30% aqueous solution of caustic soda was gradually added to neutralize by-produced hydrogen bromide. After neutralization, water 5 was added dropwise to the reaction solution while vigorously stirring it to obtain a single grain of brominated phenol novolac resin. The granular brominated phenol novolac resin thus obtained was epoxidized in the same manner as in Example 1.
エポキシ樹脂１１０２を得た。得られたエポキシ樹脂の
溶融粘度を表−１に示した。Epoxy resin 1102 was obtained. Table 1 shows the melt viscosity of the obtained epoxy resin.
表 −１
還 元 剤 過酸化水素 溶融粘度（ボイズ）実
施例１ ハイドロ・サルファイド 使用
１１．０実施例２ ジ亜リン酸 使用
１１・２実施例５ アスコルビン酸 使用 １２
．。Table-1 Reducing agent Hydrogen peroxide Melt viscosity (voids) Example 1 Hydro sulfide used
11.0 Example 2 Use of diphosphorous acid
11.2 Example 5 Ascorbic acid use 12
．． .
実ｍ例４ ）ＩＪ刀−ル営ホスフィン 使用
ＩＬ９比較例１ 無 信
用 １４．５比較例２ 無
無 １１・３※１ 工Ｃ工粘度（１５
０℃）
実施例５
実施例１〜４及び比較例１〜２１Ｃおいてフェノールノ
ボラック樹脂の代りにクレゾールノボラック樹脂を用い
て、その他は同様にして実験を行なったところ、還元剤
処理することにより、フェノールノボラック樹脂の場合
と同様にクレゾールノボラック樹脂の場合も、得られる
エポキシ樹脂の。Actual Example 4) IJ Toru Phosphine Used IL9 Comparative Example 1 None Trusted 14.5 Comparative Example 2 None
None 11・3*1 Engineering C viscosity (15
0°C) Example 5 Experiments were conducted in the same manner as in Examples 1 to 4 and Comparative Examples 1 to 21C, except that cresol novolac resin was used instead of phenol novolac resin. By treating with a reducing agent, In the case of cresol novolac resins as well as in the case of phenolic novolak resins, the resulting epoxy resins.
粘度の上昇を抑制することが出来た。It was possible to suppress the increase in viscosity.
本発明の方法によれば、過酸化水素水を使用することに
より、高価な臭素の消費量を減少させ。According to the method of the present invention, the consumption of expensive bromine is reduced by using hydrogen peroxide solution.
しかも、エポキシ樹脂の粘度を上昇させることなく、安
定な品質の樹脂を得ることが出来る。Furthermore, a resin of stable quality can be obtained without increasing the viscosity of the epoxy resin.
Claims (1)
〜１０を示す。ｘ及びｙは夫々０〜２の整数を示す。但
しｘとｙは同時に０となることはない。） で表わされる臭素化ノボラック型樹脂とエピハロヒドリ
ンをアルカリ存在下反応させて難燃性エポキシ樹脂を製
造する方法において、 一般式〔II〕 ▲数式、化学式、表等があります▼−−−−−−〔II〕 （式中、Ｒは水素又は、メチル基を示し、ｎは平均値０
〜１０を示す。） で表わされるノボラック型樹脂を有機溶媒中で臭素と過
酸化水素存在下反応させ、反応後、還元剤により処理し
て得られた臭素化ノボラック型樹脂を、アルカリ存在下
エピハロヒドリンと反応させることを特徴とする難燃性
エポキシ樹脂の製造法。[Claims] General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼------[I] (In the formula, R represents hydrogen or a methyl group, and n is the average value 0
~10 is shown. x and y each represent an integer of 0 to 2. However, x and y will never be 0 at the same time. ) In the method of producing a flame-retardant epoxy resin by reacting a brominated novolac type resin represented by the formula with epihalohydrin in the presence of an alkali, the general formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼−−−−−− [II] (In the formula, R represents hydrogen or a methyl group, and n is an average value of 0
~10 is shown. ) is reacted with bromine in an organic solvent in the presence of hydrogen peroxide, and after the reaction, the resulting brominated novolak resin is treated with a reducing agent, and the resulting brominated novolak resin is reacted with epihalohydrin in the presence of an alkali. A unique method for producing flame-retardant epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14329887A JPH0730162B2 (en) | 1987-06-10 | 1987-06-10 | Manufacturing method of flame retardant epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14329887A JPH0730162B2 (en) | 1987-06-10 | 1987-06-10 | Manufacturing method of flame retardant epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63308024A true JPS63308024A (en) | 1988-12-15 |
| JPH0730162B2 JPH0730162B2 (en) | 1995-04-05 |
Family
ID=15335494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14329887A Expired - Fee Related JPH0730162B2 (en) | 1987-06-10 | 1987-06-10 | Manufacturing method of flame retardant epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0730162B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286322A (en) * | 2017-06-02 | 2017-10-24 | 开美化学科技(南通)有限公司 | The preparation method of novolac epoxy resin bromide |
-
1987
- 1987-06-10 JP JP14329887A patent/JPH0730162B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286322A (en) * | 2017-06-02 | 2017-10-24 | 开美化学科技(南通)有限公司 | The preparation method of novolac epoxy resin bromide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0730162B2 (en) | 1995-04-05 |
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