JP3795679B2 - Method for producing bromine compound - Google Patents

Description

【００６４】
ここで、不飽和化合物を溶媒に溶解した溶液の添加量（Ｌ／分）と臭素または臭素溶液の添加量（Ｌ／分）との合計量は、厳密にいえば反応器外に導出した反応溶液の導出量（Ｌ／分）と異なるが、通常臭素の添加量（Ｌ／分）は不飽和化合物を臭素に対して溶液の添加量（Ｌ／分）に比べてかなり少量であり、反応による体積変化はほぼ無視できる。また、反応器外に飛散する溶媒の量もごく少量であるため、不飽和化合物を臭素に対して溶媒に溶解した溶液の添加量（Ｌ／分）と臭素または臭素溶液の添加量（Ｌ／分）との合計量は、該反応器外に導出した反応溶液の導出量（Ｌ／分）と近似することになる。
【００６５】
また、該反応溶液の一部を該反応器に循環することは、さらに反応器をコンパクトにすることができ、反応効率に優れるため、有利に採用される。循環の方法は特に限定されず、反応器に反応溶液の導出口とは別に他の循環専用の配管を取り付けてもよく、また、導出した反応溶液の一部を反応器に循環することもできる。循環した反応溶液は、そのまま反応器に添加しても、不飽和結合化合物の溶液、臭素または臭素溶液、両者を混合した溶液に混合して、その得られた混合液を反応器に戻してもよい。
【００６６】
本発明の連続方式においては、短時間での臭素化反応が可能であり、生産性が向上するため、前記循環方法は好ましい。臭素化の反応そのものは、数十秒でほぼ完結するので、上述した滞留時間の範囲内で充分である。
【００６７】
本発明の臭素化反応における反応温度は、前述した臭素化の反応熱が、臭素または溶媒の気化熱で除去される温度であればよく、また、かかる臭素化反応は常圧下に限定されず、加圧下または減圧下でも行うことができる。反応温度は、前記したように０℃〜６０℃の範囲が好ましい。また、使用される溶媒の沸点が臭素の沸点より低い場合は、加圧することにより反応温度を高くすることができ、使用される溶媒の沸点が臭素の沸点より高い場合は、減圧することにより反応温度を低くすることができる。
【００６８】
本発明の連続方式を実施するに当たり、反応器は不飽和化合物、臭素および溶媒を均一にかつ効果的に接触させ、反応熱の実質量を溶媒または臭素の気化により反応器外へ排出するために撹拌器を備えたものが望ましく、また気化した溶媒または臭素は還流するためにコンデンサーを上部に備えたものが有利に使用される。
【００６９】
本発明者らの研究によれば、この連続方式を実施するに当たり、反応器において不飽和化合物、臭素および溶媒が互いに均一に接触して、臭素化反応と反応熱の溶媒または臭素の気化による除去を一層効果的に行わしめるために、不飽和化合物と臭素とを、望ましくは溶媒の少なくとも一部と一緒に、反応器へ供給する直前に短時間で均一に混合して供給することが有効であることが見出された。
【００７０】
この反応器へ供給する直前の不飽和化合物と臭素との混合（溶媒はさらに混合されていてもよい）は短時間にかつ均一に行われるべきであり、そのためにフローミキサーを使用して混合液流として反応器へ供給されるのが望ましい。フローミキサー中での混合は、不飽和化合物および臭素であるが、さらに溶媒の一部または全部が一緒に混合される。
【００７１】
フローミキサー中における混合液流は、混合が均一かつ短時間で達成されることが望ましく、１５〜５００ｃｍ／秒の流速、好ましくは５０〜４００ｃｍ／秒の流速であることが有利である。またフローミキサー中における混合液流の滞留時間は０.０１〜１８０秒、好ましくは０.０５〜１２０秒、より好ましくは０.１〜６０秒が適当である。特に０.１〜２０秒が推奨される。
【００７２】
このフローミキサーは液体混合流を短時間に効果的に均一に混合することができるものであればよく、特に好ましいのはスタテックミキサーである。このスタテックミキサーとしては４〜２０のエレメント、好ましくは５〜１５のエレメントを有するものが有利に利用される。
【００７３】
スタテックミキサーは、混合器または熱交換機として、通常よく知られた化学工学上の装置である。スタテックミキサーは、米国ケニックス社より市販されている混合器であって、駆動部を有しない管型の混合器であって、その内部にエレメントと称する長方形の板を左右逆方向に直角にねじった構造の物体が内蔵されており、そのねじれ方向を、左右交互にそれぞれの断面が直角に交わるよう配列されたものである。
【００７４】
本発明の連続方式において、不飽和化合物、臭素および溶媒を反応器へ連続的に供給する場合、これらの供給をフローミキサー、特にスタテックミキサーを使用して実施することは、臭素化反応を極めて短い時間で完結させ、副反応を抑制し、かつ高純度の臭素化合物を得るために極めて有効な手段である。
【００７５】
フローミキサー内で混合された混合溶液は直ちに反応器へ供給される。フローミキサー内で混合された溶液は、臭素化反応の一部が開始されるが、ミキサー内での滞留時間は短く制御されているから、ミキサーを通過した混合溶液は直ちに反応器へ放出される。反応器内では、溶液が充分に混合されるようにさらに撹拌される。撹拌は、撹拌機を使用して行うのが好ましいが、溶液の一部を反応器内から循環させる方法であってもよい。
【００７６】
かかる反応器の容量は、ミキサー容量の３０倍以上、５０倍以上の容量を有するものが好ましい。また、かかる反応器の大きさの上限は特に限定されないが、ミキサー容量の２００,０００倍以下であれば充分であり、２００,０００倍を超える反応器の使用は経済的に好ましくない。かかる容量の大きい反応器は、ミキサー内において反応した際に生じる反応熱を、かかる反応器内で放熱させることにより、溶媒および臭素の沸騰による飛散を抑制する働きがあり、また、撹拌混合を促進させることにより臭素化反応を完結する働きがある。
【００７７】
この際、臭素化の反応熱は、溶媒または臭素の気化熱で除去する方法を採用することができ、また、反応器にコンデンサーを付設して、気化した蒸気を冷却し液化させ再び反応溶液に戻す方法、すなわち還流させる方法が運転操作し易くより好ましく用いられる。この方法は、還流による撹拌効果によって、不飽和化合物および臭素が均一に溶液中に分散され、副反応が起こり難くなり、高純度の臭素化合物が得られ易くなり、また、反応温度を一定に保ちながら、溶媒や臭素の飛散が生じずに、臭素化反応が安定して進行するため好ましく用いられる。
【００７８】
臭素化合物の分離・回収；
前記した臭素化反応によって得られた反応混合物から目的の臭素化合物は、それ自体公知の方法で分離し回収することができる。しかし反応混合物中には、未反応の臭素が残留しており、そのため残留臭素は還元剤で処理し、一旦臭素を臭化水素酸とし、次いでアルカリ性の中和剤を添加する方法が通常採用されている。
【００７９】
しかし、この方法は、還元処理および中和処理の２つの工程が少なくとも必要であり、操作が煩雑でありかつ処理が長時間になる。しかもこの処理方法により回収された臭素化合物の純度および品質は充分に満足しうるものではない。
【００８０】
そこで本発明者らは、反応混合物から臭素化合物を簡単な手段で短時間で分離し回収しうる方法について改良を進めたところ、反応混合物中の残存臭素に対して特定量以上の還元剤およびアルカリ性中和剤を、同時に反応混合する方法により、簡単にかつ短時間で処理できることを見出した。
【００８１】
すなわち、反応終了後の反応混合液に、その中に残存する臭素１モル当たり、２モル以上の還元剤および２モル以上のアルカリ性中和剤を同時に添加し混合する方法が見出された。この方法を以下“処理方法”を称する。
【００８２】
この処理方法に使用される還元剤としては、通常の還元反応に用いられる還元剤であり、具体的には、亜硫酸水素ナトリウム、亜二チオン酸ナトリウム、亜硫酸ナトリウム、シュウ酸、硫化水素、亜硝酸ナトリウム、亜硝酸カリウム、硫酸ヒドロキシルアミン、スズ、酸化第１スズおよびヒドラジン等が挙げられ、亜硫酸水素ナトリウム、亜二チオン酸ナトリウム、亜硫酸ナトリウム、シュウ酸および亜硝酸ナトリウムが好ましく用いられる。これらの還元剤は水溶液としても使用することができる。また、これらの還元剤は単独もしくは二種以上混合して使用される。
【００８３】
また、アルカリ性の中和剤としては、例えば、アルカリ金属水酸化物、アルカリ金属炭酸塩、アルカリ土類金属水酸化物およびアルカリ土類金属炭酸塩等が挙げられ、具体的には、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、水酸化カルシウムおよび炭酸カルシウム等が好ましく、特に水酸化ナトリウムが好ましく用いられる。これらのアルカリ性の中和剤は水溶液として使用することが好ましい。また、これらのアルカリ性の中和剤は単独もしくは二種以上混合して使用される。
【００８４】
本発明の処理方法において、反応混合物中の残存臭素１モルに対して、２モル以上、好ましくは２〜３０モル、より好ましくは２.２〜１５モル、さらに好ましくは２.５〜１０モルの還元剤が、反応混合物中に添加される。添加する還元剤が２モルより少なくなると、臭素が混合物中に残留することとなり、低純度の茶色に着色した臭素化合物が得られ好ましくない。また、反応混合物中の残存臭素１モルに対して、２モル以上、好ましくは２〜５０モル、より好ましくは２.２〜３０モル、さらに好ましくは２.５〜２０モルのアルカリ性の中和剤が、反応混合物中に添加される。添加する中和剤が２モルより少なくなると、臭化水素が水溶液に残留し、この強酸水溶液はそのまま廃棄できず、また、混合物中に一部臭化水素が残存し、これが金属を腐食し易く、さらに、この臭化水素は、刺激臭が強く作業環境上においても好ましくない。
【００８５】
上記還元剤およびアルカリ性の中和剤は、かかる臭素化合物および臭素を含む反応混合物中に同時に添加する。かかる還元剤および中和剤は、別々にあるいは事前に混合したものを添加してもよいが、還元剤がアルカリによって副反応を起こすおそれがないため別々に添加することが好ましい。また、ここで、同時に添加するとは、厳密に全く両者を同時に添加することを意味するものではなく、一方の剤を添加し、この剤を添加終了後、少なくとも１０分以内、好ましくは５分以内に他方の剤が添加を終了することを意味している。添加方法としては、還元剤を添加し、すぐに続けて中和剤を添加する方法が好ましく採用される。
【００８６】
処理方法において、還元剤およびアルカリ性の中和剤を添加した反応混合物は、還元、中和反応がスムーズに進行するように混合される。混合する方法としては、種々の混合器を用いることができ、例えば撹拌翼を回転することにより撹拌を行う方式（槽の中心軸と撹拌軸とを一致させるもの、撹拌軸を傾斜させるもの、槽の側壁に撹拌軸を設けるもの等）、槽を揺動させることにより撹拌を行う方式、ポンプにより槽内の液を循環させる方式等を用いた撹拌槽やスタテックミキサー等のインラインミキサーが採用され、なかでも撹拌槽が好ましく使用される。
【００８７】
また、かかる還元および中和反応を行う際の反応混合物と水相との重量比は、２０：８０〜８０：２０が好ましく、３０：７０〜７０：３０がより好ましく、４０：６０〜６０：４０が特に好ましい。この範囲内では、還元、中和反応が効率よく進行し、短時間で臭素が除去される。従って、還元、中和反応を行う際に、上記範囲内となるように水あるいは溶媒を反応混合物に添加することが好ましい。
【００８８】
かかる反応混合物中の臭素の還元、中和反応に要する時間は２分以上が好ましく、２〜９０分がより好ましく、５〜６０分がさらに好ましく、１０〜４５分が特に好ましい。
かくして、本発明においては、水による洗浄回数は、還元、中和反応が終了した後の１工程のみである。従って、還元、中和反応において、工程操作が少なくなり、故に工程管理が容易となる。
【００８９】
前記した方法で処理された反応混合物から、目的の臭素化合物は、それ自体知られた方法、例えば貧溶媒による沈殿などの手段により回収される。
前記した臭素化反応によって得られた反応混合物からの目的臭素化合物の分離回収は、以下に説明するように、スタテックミキサーを使用して還元処理、次いで中和処理することによっても実施することができる。
【００９０】
すなわち、この方法は、目的臭素化合物および残存の臭素を含む反応混合液と還元剤を含む水溶液とを混合して、臭素を還元し処理する方法において、該臭素化合物および臭素を含む溶液と該還元剤を含む水溶液とを、その混合溶液の流速が５ｃｍ／秒以上の速度となるようにエレメント数４〜２０のスタテックミキサー内に導入し、該スタテックミキサー内での滞留時間を３００秒以内として混合させ、その後該スタテックミキサーから導出した混合溶液をスタテックミキサーの容量の２０倍以上の容量を有する撹拌槽に投入し、次いで中和処理する反応混合物の処理方法である。
【００９１】
この処理方法に使用される還元剤は、前記に例示したものが使用され、その還元剤の量は、残存臭素１モルに対して、2モル以上が好ましく、２〜１００モルがより好ましく、２〜５０モルがさらに好ましく、２〜２０モルが特に好ましい。２モルより少なくなると還元反応が不充分となり、臭素が残存し易くなる。
【００９２】
臭素に対する還元反応は、反応混合物と還元剤を含む水溶液との混合を効率よく行わねばならない。従って、通常の撹拌装置を使用すると、その撹拌効率が充分でなく、還元反応を完結させるには何度かに分けて繰り返し行うことが必要となる。そこで、混合器としてスタテックミキサーを用いることにより、効率よく混合が行われ、簡便な装置で、短時間に臭素を処理することができる。
【００９３】
スタテックミキサーを使用する際の条件としては、その管内でのエレメントの数により実質的な混合の程度が判別でき、通常はエレメントの数が２のべき乗として分割し、混合が行われると考えられ、混合効率は、管内への液成分の流速、粘性、レイノルズ数等の因子が考えられるが、特に重要なのは流速である。この処理方法においては、反応混合物と還元剤を含む水溶液との混合溶液のスタテックミキサーの導入口における流速が５ｃｍ／秒以上、好ましくは１０ｃｍ／秒以上の速度となるようにスタテックミキサーに導入する。流速が５ｃｍ／秒より小さくなると、混合の効率が不充分となり、還元反応が充分に行われない。また、流速が５００ｃｍ／秒を超えてスタテックミキサーに導入しても、実質的に混合効率は大差なくこれ以上の流速は必要ない。ここで、流速は、スタテックミキサーへ導入する反応混合物の添加速度をＡ（ｍＬ／秒）、還元剤を含む水溶液の添加速度をＢ（ｍＬ／秒）とし、またスタテックミキサーの断面積をＣ（ｃｍ²）とした場合に、（Ａ＋Ｂ）／Ｃ（ｃｍ／秒）の計算式で算出される。
【００９４】
反応混合物や還元剤を含む水溶液をスタテックミキサーに導入する手法としては、特に限定されず、滴下ロートを用いて導入してもよく、また、所望の流速を与え易くするために、ポンプにより定時間内に定容量を供給することも好ましく用いられる。
【００９５】
また、スタテックミキサーのエレメント数は４〜２０の範囲であり、３以下のエレメント数では混合が充分でなく、得られる臭素化合物の純度は低くなり、また、混合効率から２１以上のエレメント数は必要でない。
【００９６】
スタテックミキサー内に導入した反応混合物と還元剤を含む水溶液との混合溶液のスタテックミキサー内における滞留時間は、３００秒以内であり、０.００１〜３００秒が好ましく、０.００５〜１８０秒がより好ましく、０.０１〜１２０秒がさらに好ましく、０.０５〜６０秒がさらに好ましく、０.１〜１０秒が特に好ましい。滞留時間が長すぎると、後の有機溶媒相と水相との分液が困難となり好ましくない。ここで、滞留時間は、前記スタテックミキサーへ導入する反応混合物の添加速度をＡ（ｍＬ／秒）、還元剤を含む水溶液の添加速度をＢ（ｍＬ／秒）とし、またスタテックミキサーの内容積をＸ（ｃｍ³）とした場合に、Ｘ／（Ａ＋Ｂ）（秒）の計算式で算出される。
【００９７】
前記処理方法においては、さらに、該スタテックミキサー内で混合した反応混合物ならびに還元剤を含む水溶液を、スタテックミキサーから導出し、この混合溶液をスタテックミキサーの容量の２０倍以上の容量を有する撹拌槽に投入する。
【００９８】
その際、反応混合物と還元剤を含む水溶液をスタテックミキサー内で混合することにより、還元反応の一部は進行するが、さらに還元反応を行い、また、スタテックミキサー内での反応熱を放熱するために、かかる混合溶液を別の撹拌槽に導入する必要がある。ここで撹拌槽とは、スタティックミキサー内で混合された溶液を継続的に混合溶液の状態で保持するようなものであればよく、撹拌の方式は限定されないが、例えば、撹拌翼を回転することにより撹拌を行う方式（槽の中心軸と撹拌軸とを一致させるもの、撹拌軸を傾斜させるもの、槽の側壁に撹拌軸を設けるもの等）、槽を揺動させることにより撹拌を行う方式、ポンプにより槽内の液を循環させる方式等が用いられる。
【００９９】
かかる撹拌槽の容量は、スタテックミキサー容量の２０倍以上であり、３０倍以上の容量を有するものが好ましい。また、かかる撹拌槽の大きさの上限は特に限定されないが、スタテックミキサー容量の２００,０００倍以下の撹拌槽であれば充分であり、２００,０００倍を超える撹拌槽の使用は経済的に好ましくない。かかる容量の大きい撹拌槽は、撹拌混合することにより還元反応を完結する働きがあり、また、スタテックミキサー内において反応した際に生じる反応熱を、かかる撹拌槽内で放熱させる働きがある。また、かかる撹拌槽からスタテックミキサーの導入口への配管を設置し、撹拌槽中の溶液をスタテックミキサー内に再度導入してもよい。
【０１００】
かかる撹拌槽中の溶液の撹拌時間は2分以上が好ましく、２〜９０分がより好ましく、３〜６０分がさらに好ましく、５〜４５分が特に好ましい。かかる時間の撹拌混合により還元反応が完結する。
【０１０１】
かかる還元反応が完了した後は、臭素は臭化水素となり、その大半は還元剤を含む水溶液に溶解し、比較的ｐＨの低い酸性水となる。かかる状態で、目的の臭素化合物を回収しても構わないが、反応装置は通常金属製であるために酸による腐食、穴あき等の安全上の問題を生起することが多く、このために臭化水素を中和することが好ましく、アルカリ性の中和剤が好ましく用いられる。
【０１０２】
かかるアルカリ性の中和剤としては、前記したものと同様に例えば、アルカリ金属水酸化物、アルカリ金属炭酸塩、アルカリ土類金属水酸化物およびアルカリ土類金属炭酸塩等が挙げられ、具体的には、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、水酸化カルシウムおよび炭酸カルシウム等が好ましく、特に水酸化ナトリウムが好ましく用いられる。これらのアルカリ性の中和剤は水溶液として使用することが好ましい。また、これらのアルカリ性の中和剤は単独もしくは二種以上混合して使用される。
【０１０３】
また、この場合反応混合物中の残存臭素１モルに対して、2モル以上、好ましくは２〜１００モル、より好ましくは２〜５０モル、さらに好ましくは２〜２０モルのアルカリ性の中和剤が、かかる還元反応が終了した溶液と混合される。この際かかる溶液のｐＨが７.５以上であることが好ましく、ｐＨが8以上であることがより好ましい。添加する中和剤が２モルより少なくなると、臭化水素が水溶液に残留し、この強酸水溶液はそのまま廃棄できず、また、臭素化合物中に一部臭化水素が残存し、これが金属を腐食し易く、さらに、この臭素化合物は、刺激臭が強く作業環境上においても好ましくない。
【０１０４】
かかる中和反応に要する時間は2分以上が好ましく、２〜９０分がより好ましく、５〜６０分がさらに好ましく、１０〜４５分が特に好ましい。
本発明の方法により得られた臭素化合物は、当業者にはよく知られた適当な方法、例えば貧溶媒による沈殿等により回収される。
【０１０５】
かくして本発明方法によれば、前記一般式（１）で表される不飽和化合物の臭素化反応により、その不飽和化合物の不飽和基が臭素原子によって飽和された下記一般式（２）で表される臭素化合物が高純度のものとして得られる。
Ｒ³−Ｏ−Ａｒ¹−Ｙ−Ａｒ²−Ｏ−Ｒ⁴ （２）
（式中、Ａｒ¹、Ａｒ²およびＹは前記一般式（１）における定義と同じものを意味する。Ｒ³およびＲ⁴は、それぞれ前記一般式（１）におけるＲ¹およびＲ²における不飽和基が臭素原子によって飽和した基を意味する。）
【０１０６】
本発明により得られた臭素化合物は、その純度が８０重量％以上、好ましくは８５重量％以上であり、特に好適なものは９０重量％以上である。かかる高純度の臭素化合物は、熱可塑性樹脂の難燃剤と極めて優れている。
【０１０７】
本発明方法において得られた臭素化合物は、純度に優れているばかりでなく、難燃剤として使用した場合、悪影響を与える不純物の含有量が少ない点において優れた品質を有している。
【０１０８】
すなわち、得られた臭素化合物中には、下記一般式（４）

（式中、Ａｒ¹、Ａｒ²およびＹは、前記一般式（１）における定義と同じものを意味する。Ｒ⁶およびＲ⁷は同一もしくは異なり、炭素数２〜１１の炭化水素基を示す。ｐおよびｑは、それぞれ０〜１０の整数であり、（ｐ＋ｑ）は１以上、好ましくは２〜１０の整数を示し、ｓおよびｔはそれぞれ０〜５の整数を示し、（ｓ＋ｔ）は1以上、好ましくは１〜５の整数を示す。）
で表されるヒドロキシ臭素化合物は少量含有されている。
【０１０９】
本発明の臭素化合物において、前記式（４）で示されるヒドロキシ臭素化合物の含有量が前記式（１）で示される臭素化合物１モルに対して０.０２モル以下であり、０.０００１〜０.０２モルが好ましく、０.０００１〜０.０１５モルがより好ましく、０.０００１〜０.０１モルがさらに好ましい。かかる式（４）で示される化合物の含有量が式（１）で示される臭素化合物1モルに対して０.０２モルを越えると、本発明の臭素化合物の熱安定性が低下するため好ましくない。
【０１１０】
かかる式（４）で示される化合物は、前述した不飽和結合化合物と臭素とを反応し、式（１）で示される臭素化合物を合成する際、不飽和化合物の溶液、臭素または臭素溶液およびアルコール化合物から実質的になる反応溶液中に存在する水分と臭素との反応によって生成する中間体が、不飽和結合化合物と反応して生成する副生成物である。
【０１１１】
殊に本発明方法における臭素化反応を、前記一般式（３）で表されるアルコールの添加により実施した場合、得られた臭素化合物は、高純度であるばかりでなく、その熱安定性に悪影響を与えない下記一般式（５）で表されるアルコキシ臭素化合物を少割合有している。
【０１１２】

（式中、Ａｒ¹、Ａｒ²およびＹは、前記一般式（１）における定義と同じものを意味する。Ｒ⁶およびＲ⁷は同一もしくは異なり、炭素数２〜１１の炭化水素基を示す。ｐ、ｑ、sおよびtは、前記一般式（４）における定義と同じものを意味する。Ｒ⁸およびＲ⁹はそれぞれ炭素数１〜６の脂肪族基を示す。）
【０１１３】
かかる式（５）で示される化合物は、前述したように式（３）で示されるアルコールと臭素との反応によって生成する中間体が、不飽和化合物の脂肪族不飽和基と反応することにより生成する副生成物であり、この副生成物は該臭素化合物の熱安定性に悪影響を与えない。かかる式（５）で示されるアルコキシ臭素化合物の含有量は、式（１）で示される臭素化合物1モルに対して、０.０１〜０.２モルが好ましく、０.０１〜０.１５モルがより好ましく、０.０１〜０.１モルがさらに好ましく、０.０１〜０.０５モルが特に好ましい。かかる式（５）で示されるアルコキシ臭素化合物の含有量が、式（１）で示される臭素化合物１モルに対して０.２モル以下であれば、該臭素化合物を難燃剤として樹脂に配合した樹脂組成物の難燃性に悪影響を与えることがなく好ましい。
【０１１４】
【実施例】
以下に、実施例を挙げて、本発明を詳述する。
以下に示す実施例１〜３９は、本発明の実施例を示すものではなく、参考実施例であり、実施例４０〜５６は本発明の実施例を示すものである。さらに調製例１〜４および実施例５７〜７１は、本発明の実施例を示すものではなく、参考実施例である。なお、実施例中一般式（１）で表される脂肪族不飽和結合を有する化合物を“原料”と略称することがある。また、純度、臭素含有率、比重の測定は、次の方法に従った。
（１）臭素化合物の純度、水由来の不純物、水酸基含有化合物に由来する不純物；
臭素化合物の純度、水由来の不純物、水酸基含有化合物に由来する不純物の測定は、高速液体クロマトグラフィー（島津製作所（株）製ＳＣＬ−６Ｂ）により、２８０ｎｍの吸収を検出する方法で行った。臭素化合物の純度は、このクロマトグラフィーより得られた各成分のピーク面積の和を１００とし、これに対する臭素化合物のピーク面積比を求めた。また、水由来の不純物および水酸基含有化合物に由来する不純物の測定は、このクロマトグラフィーより得られた臭素化合物のピーク面積を求め、これに対する水由来の不純物の各成分のピーク面積の和および水酸基含有化合物に由来する不純物の各成分のピーク面積の和を求め、それぞれの臭素化合物１モルに対する含有量（モル）を算出した。
【０１１５】
（２）臭素含有率の分析
試料を、密閉容器中で、発煙硝酸と加熱し、分解せしめ、発生する臭化水素酸を、硝酸銀にて滴定する方法（カリウス法）を用いて定量分析した。
【０１１６】
（３）比重
ガラス製比重瓶を用い、２０℃にて測定した。
【０１１７】
（４）水分量の分析
電量滴定式水分測定装置（三菱化学（株）製ＣＡ−０６型）を用い、カールフィッシャー法により求めた。
【０１１８】
（５）傾斜角（７０℃、４時間加熱後）
試料０.５ｇをガラス製シャーレ（岩城硝子（株）製パイレックスガラス；底部の中心線平均粗さ０.１μｍ）の中心部にいれ、熱風循環式乾燥機を用いて７０℃で４時間加熱した後、シャーレを取り出し、室温になるまで冷却した。このシャーレを水平な面において、一端が水平な面と接した状態で反対側を持ち上げて傾け、シャーレ内の固体試料が滑りを生じたとき、側面からみた水平な面に対するシャーレの傾斜角を分度器により測定した（図１参照）。この傾斜角は、加熱処理に伴う固体の凝集度合を意味し、かかる傾斜角が７０°より大きいと、その試料は熱安定性が不充分で、ブロッキング現象を起こし易いことを意味する。
【０１１９】
なお、以下の実施例および比較例中原料Ｎｏ．（１）〜（６）はそれぞれ下記化合物を意味する。

【０１２０】
実施例１
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた１Ｌのガラス製反応容器に、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン１３５ｇ（０.２１６ｍｏｌ）および合成ゼオライトで脱水した塩化メチレン２３０ｇを入れ溶解させた（この溶液の比重は１.４７であり、これから算出した濃度は０.８７ｍｏｌ／Ｌであった）。この溶液を撹拌し、３９〜４１℃の温度で塩化メチレンを還流させながら、臭素７２.７ｇ（０.４５５ｍｏｌ）を８分で滴下漏斗より滴下した（原料１モルに対して、臭素の添加速度は、４.４ｍｍｏｌ／秒）。滴下終了後、反応溶液を３９〜４１℃の温度で塩化メチレンを還流させながら３０分間撹拌し続け、臭素の付加反応を終了した。
【０１２１】
次に、反応溶液中の過剰の臭素を１５重量％重亜硫酸ソーダ水溶液５０ｇで還元した後、生成した臭化水素を２５重量％の水酸化ナトリウム水溶液を用いて中和した。その後、この溶液から塩化メチレン層を分液し、かかる塩化メチレン層から塩化メチレンを約９０％蒸発、除去し、これにメタノールを５００ｍＬ加え反応生成物を沈殿させ、この沈殿物をろ過して塊状固体を取り出した。この塊状固体を乳鉢で粉砕し、８０℃、３時間、５ｍｍＨｇで減圧乾燥し生成物１９８.５ｇを得た（収率９７.２％）。
【０１２２】
得られた生成物を¹Ｈ−ＮＭＲで分析したところ４.５１〜４.５３ｐｐｍに−ＣＨＢｒ−由来のシグナルが、３.９４〜４.０９ｐｐｍに−ＣＨ₂Ｂｒ由来のシグナルが認められた。またＦＴ−ＩＲ分析より、−Ｏ−ＣＨ₂−の吸収を認め、アリル基の吸収は認められないのを確認した。以上の分析結果より、生成物は、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物は、純度９６.８％、融点１１０℃、臭素含有率６７.５％（理論値６７.８％）であった。
【０１２３】
実施例２
実施例１で使用した１Ｌのガラス製反応容器に、２,２−ビス｛（３,５−ジブロモ−４−イソブテニルオキシ）フェニル｝プロパン１４０.８ｇ（０.２１６ｍｏｌ）および合成ゼオライトで脱水した塩化メチレン１６３ｇと１,４−ジオキサン７０ｇの混合溶媒を入れ溶解させた（溶液の比重１.３５）。この溶液を撹拌し、混合溶媒を還流させながら、臭素７９.５ｇ（０.４９７ｍｏｌ）を９分で滴下漏斗より滴下した（原料１モルに対して、臭素の添加速度は、１.０９ｍｍｏｌ／秒であった。）。滴下終了後、混合溶媒を還流させながら反応溶液を３０分間撹拌し続け、臭素の付加反応を終了した。
【０１２４】
得られた反応溶液を、実施例１と同様の操作を行い、白色固体の生成物２０３.３ｇを得た（収率９６.８％）。実施例１と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−２−メチルプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物は、純度９６.５％、臭素含有率６５.３％（理論値６５.８％）であった。
【０１２５】
実施例３
実施例２において、２,２−ビス｛（３,５−ジブロモ−４−イソブテニルオキシ）フェニル｝プロパンの代わりにビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝メタン１２８.７ｇ（０.２１６ｍｏｌ）を使用し（溶液の比重１.３４）、臭素７９.５ｇを９分で滴下する代わりに８.３分で滴下した以外は、実施例２と同様の方法で臭素化を行い、生成物１９１.４ｇを得た（収率９６.７％）。
【０１２６】
実施例１と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−プロピルオキシ）フェニル｝メタンであることが確認された。この臭素化合物は、純度９６.７％、臭素含有率６９.５％（理論値６９.８％）であった。
【０１２７】
実施例４
実施例１において、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン１３５ｇの代わりにビス｛（３,５−ジブロモ−４−イソブテニルオキシ）フェニル｝メタン１３４.８ｇ（０.２１６ｍｏｌ）を使用した（溶液の比重１.４７）以外は、実施例１と同様の方法で臭素化を行い生成物１９７.６ｇを得た（収率９６.９％）。
【０１２８】
実施例１と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−２−メチルプロピルオキシ）フェニル｝メタンであることが確認された。この臭素化合物は、純度９６.８％、臭素含有率６７.７％（理論値６７.８％）であった。
【０１２９】
実施例５
実施例１において、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン１３５ｇの代わりに（３,３’,５,５’−テトラブロモ−４,４’−ジアリルオキシ）ビフェニル１２５.７ｇ（０.２１６ｍｏｌ）を使用した（溶液の比重１.４７）以外は、実施例１と同様の方法で臭素化を行い、生成物１８６.６ｇを得た（収率９５.８％）。
【０１３０】
実施例１と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、｛３,３’,５,５’−テトラブロモ−４,４’−（２,３−ジブロモ−プロピルオキシ）｝ビフェニルであることが確認された。該化合物は、純度９５.７％、臭素含有率、７０.８％（理論値７０.９％）であった。
【０１３１】
実施例６
実施例１において、塩化メチレン２３０ｇを８６ｇに代え（溶液の比重１.４２）、臭素７２.７ｇを７５ｇ（０.４６９ｍｏｌ）に代えた以外は、実施例１と同様の方法で臭素化を行い生成物１９９.５ｇを得た（収率９７.７％）。
実施例１と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物は、純度９６.７％であった。
【０１３２】
実施例７
実施例１において、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン１３５ｇを２６８ｇに代えて（０.４３０ｍｏｌ）、塩化メチレン２３０ｇを４９３ｇに代えて（溶液の比重１.４２）、臭素７２.７ｇを８０ｇ（０.５００ｍｏｌ）に代えた以外は、実施例１と同様の方法で臭素化を行い生成物３９２.８ｇを得た（収率９６.９％）。
【０１３３】
実施例１と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物は、純度９６.８％であった。
【０１３４】
実施例８
実施例１において、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン１３５ｇを１６２ｇに代えて（０.２６０ｍｏｌ）、塩化メチレン２３０ｇを２３４ｇに代えて（溶液の比重１.４７）、臭素７２.７ｇを９５ｇ（０.５９４ｍｏｌ）に代えた以外は、実施例１と同様の方法で臭素化を行い生成物２３４.７ｇを得た（収率９５.８％）。
【０１３５】
実施例１と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物は、純度９６.６％であった。
【０１３６】
実施例９
実施例１において、２,２−ビス｛（３,５−ジブロモ−４−イソブテニルオキシ）フェニル｝プロパン１４０.８ｇの代わりにビス｛３,５−ジブロモ−４−イソブテニルオキシ）フェニル｝スルフォン１４８ｇ（０.２２０ｍｏｌ）を使用し、塩化メチレン２３０ｇを１２１ｇに代えて（溶液の比重１.４１）、臭素７２.７ｇを７２.０ｇ（０.４５１ｍｏｌ）に代えた以外は、実施例１と同様の方法で臭素化を行い生成物２０６.９ｇを得た（収率９４.８％）。
【０１３７】
実施例１と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−２−メチルプロピルオキシ）｝スルフォンであることが確認された。該化合物は、純度９５.３％、臭素含有率６４.１％（理論値６４.４％）であった。
【０１３８】
比較例１
実施例１において、臭素の滴下を１２０分かけて行い、冷却しながら反応温度２０℃で、塩化メチレンを還流させずに臭素化反応させる以外は（原料１モルに対して、臭素の添加速度は、０.２９ｍｍｏｌ／秒）、実施例１と同様の方法で行ったところ、得られた２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンの収率は９６.５％であったが、その純度は８９.７％と低かった。
【０１３９】
比較例２
実施例１において、臭素の滴下を１２０分かけて行い臭素化反応させる以外は（原料１モルに対して、臭素の添加速度は、０.２９ｍｍｏｌ／秒）、実施例１と同様の方法で行った。この際臭素の滴下開始時の溶液温度は２０℃であったが、臭素を滴下するに伴い、反応熱により徐々に溶液温度は上昇し、滴下終了時には溶液温度は３７℃となった。反応容器は冷却せず、また、塩化メチレンの還流は起こらなかった。得られた２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンの純度は６３.０％と低かった。
【０１４０】
なお、実施例１〜９および比較例１の結果を表１および表２に示した。ここで、溶媒（Ａ）および（Ｂ）は、下記組成を示す。
（Ａ）塩化メチレン
（Ｂ）塩化メチレン／１,４−ジオキサン＝７０／３０（重量比）
添加速度は、原料１モルに対する臭素の添加速度である。
【０１４１】
【表１】

【０１４２】
【表２】

【０１４３】
実施例１０
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた１Ｌのガラス製反応容器に、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン１３５ｇ（０.２１６ｍｏｌ）および合成ゼオライトで脱水処理した塩化メチレン２３０ｇを入れ溶解させた。また、この溶液中に、メタノール０.３６ｇ（０.０１１３ｍｏｌ）を加えた（脂肪族不飽和基１００コ当り水酸基の数２.６コ）。この溶液中の含水率は２００ｐｐｍであった（脂肪族不飽和基１００コ当り水分子の数０.９４コ）。次に、この溶液を約２℃に冷却し、撹拌しながら、臭素７２.７ｇ（０.４５５ｍｏｌ）を６０分かけて滴下漏斗より滴下した。滴下終了時には、反応溶液の温度は１６℃であった。滴下終了後、反応溶液を３０分間撹拌を続け、臭素の付加反応を終了した。
【０１４４】
次に、反応溶液中の過剰の臭素を１５重量％重亜硫酸ソーダ水溶液５０ｇで還元した後、生成した臭化水素を２５重量％の水酸化ナトリウム水溶液を用いて中和した。その後、この溶液から塩化メチレン層を分液し、かかる塩化メチレン層から塩化メチレンを９０％程度蒸発、除去し、これにメタノールを５００ｍＬ加え反応生成物を沈殿させ、この沈殿物をろ過して塊状固体を取り出した。この塊状固体を乳鉢で粉砕し、８０℃、３時間、５ｍｍＨｇで減圧乾燥し生成物１９８.５ｇを得た（収率９７.０％）。
【０１４５】
得られた生成物を¹Ｈ−ＮＭＲで分析したところ４.５１〜４.５３ｐｐｍに−ＣＨＢｒ−由来のシグナルが、３.９４〜４.０９ｐｐｍに−ＣＨ₂Ｂｒ由来のシグナルが認められた。またＦＴ−ＩＲ分析より、−Ｏ−ＣＨ₂−の吸収を認め、アリル基の吸収は認められないのを確認した。以上の分析結果より、生成物は、主として２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物は純度９５.１％であり、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパン１モルに対して、水に由来する不純物は０.００４モル、メタノールに由来する不純物は０.０１５モルであった。また、かかる臭素化合物の傾斜角は４４°であった。
【０１４６】
実施例１１
実施例１０において、メタノールの代わりにエタノール０.３６ｇ（０.００７８３ｍｏｌ、脂肪族不飽和基１００コ当り水酸基の数１.８コ）を用いる以外は、実施例１０と同様の方法を行い、主として２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンを得た。この臭素化合物は純度９５.３％、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパン１モルに対して、水に由来する不純物は０.００４モル、エタノールに由来する不純物は０.０１３モルであった。
【０１４７】
実施例１２
実施例１０において、メタノールの代わりにｉ−プロパノール２.３３ｇ（０.０３８８ｍｏｌ、脂肪族不飽和基１００コ当り水酸基の数９.０コ）を用い、反応溶液の初期温度を２５℃とする以外は、実施例１０と同様の方法を行った。臭素滴下終了時には、反応溶液の温度は３６℃であった。滴下終了後、反応溶液を３０分間撹拌を続け、臭素の付加反応を終了し、実施例１と同様に処理し、主として２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンを得た。この臭素化合物は純度９５.０％、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパン１モルに対して、水に由来する不純物は０.００３モル、ｉ−プロパノールに由来する不純物は０.０３７モルであった。
【０１４８】
実施例１３
実施例１２において、ｉ−プロパノールの代わりにｎ−ブタノール１.１３ｇ（０.０１５ｍｏｌ、脂肪族不飽和基１００コ当り水酸基の数３.５コ）を用いた以外は、実施例１２と同様の方法を行い、主として２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンを得た。この臭素化合物は純度９４.９％、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパン１モルに対して、水に由来する不純物は０.００３モル、ｎ−ブタノールに由来する不純物は０.０２１モルであった。
【０１４９】
実施例１４
実施例１０で使用したガラス製反応容器に、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン１３５ｇ（０.２１６ｍｏｌ）および塩化メチレン２３０ｇを入れ溶解させた。また、この溶液中に、エタノール０.７２ｇ（０.０１５７ｍｏｌ）を加えた（脂肪族不飽和基１００コ当り水酸基の数３.６コ）。この溶液中の含水率は５００ｐｐｍであった（脂肪族不飽和基１００コ当り水分子の数２.４コ）。次に、この溶液を約２℃に冷却し、撹拌しながら、臭素７２.７ｇ（０.４５５ｍｏｌ）を６０分かけて滴下漏斗より滴下した。滴下終了時には、反応溶液の温度は１６℃であった。滴下終了後、反応溶液を３０分間撹拌を続け、臭素の付加反応を終了した。
【０１５０】
次に、この反応溶液を実施例１０と同様の処理を行い、主として２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンを得た。この臭素化合物は純度９４.９％、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパン１モルに対して、水に由来する不純物は０.００５モル、エタノールに由来する不純物は０.０１６モルであった。また、かかる臭素化合物の傾斜角は４５°であった。
【０１５１】
実施例１５
実施例１０において、臭素の滴下時間を１２０分とし、滴下終了後、反応溶液を３０分間撹拌を続け、臭素化反応の間、反応溶液の温度を２０℃に保持するように冷却する以外は、実施例１０と同様の方法を行い、主として２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンを得た。この臭素化合物は純度９５.２％、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパン１モルに対して、水に由来する不純物は０.００３モル、メタノールに由来する不純物は０.０１５モルであった。
【０１５２】
実施例１６
実施例１０において、メタノールに代えてエタノール０.７２ｇ（０.０１６ｍｏｌ、脂肪族不飽和基１００コ当り水酸基の数３.６コ）を用い、塩化メチレン２３０ｇを６１５ｇとして（この溶液中の含水率は２００ｐｐｍ、脂肪族不飽和基１００コ当り水分子の数１.９コ）、反応温度を３９〜４１℃に設定し、溶媒を還流させながら、臭素８０.０ｇ（０.５０１ｍｏｌ）を約５分間で滴下した。臭素滴下終了後、反応溶液を６０分間撹拌を続け、臭素の付加反応を終了した。この反応溶液は、実施例１０と同様の処理を行い、主として２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンを得た。この臭素化合物は純度９６.１％、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパン１モルに対して、水に由来する不純物は０.００３モル、メタノールに由来する不純物は０.０１６モルであった。また、かかる臭素化合物の傾斜角は４１°であった。
【０１５３】
実施例１７
実施例１０で使用したガラス製反応容器に、２,２−ビス｛（３,５−ジブロモ−４−イソブテニルオキシ）フェニル｝プロパン１３５ｇ（０.２０７ｍｏｌ）および合成ゼオライトで脱水処理した塩化メチレン２３０ｇを入れ溶解させた。また、この溶液中に、メタノール０.３６ｇ（０.０１１３ｍｏｌ）を加えた（脂肪族不飽和基１００コ当り水酸基の数２.７コ）。この溶液中の含水率は２００ｐｐｍであった（脂肪族不飽和基１００コ当り水分子の数０.９８コ）。次に、この溶液を約２℃に冷却し、撹拌しながら、臭素７２.０ｇ（０.４１９ｍｏｌ）を６０分かけて滴下漏斗より滴下した。滴下終了時には、反応溶液の温度は１６℃であった。滴下終了後、反応溶液を３０分間撹拌を続け、臭素の付加反応を終了した。
【０１５４】
次に、この反応溶液を実施例１０と同様の処理を行い、主として２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−２−メチルプロピルオキシ）フェニル｝プロパンを得た。この臭素化合物は純度９４.９％、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−２−メチルプロピルオキシ）フェニル｝プロパン１モルに対して、水に由来する不純物は０.００３モル、メタノールに由来する不純物は０.０１９モルであった。
【０１５５】
実施例１８
実施例１０で使用したガラス製反応容器に、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝スルフォン１３５ｇ（０.２０９ｍｏｌ）および塩化メチレン２３０ｇを入れ溶解させた。また、この溶液中に、エタノール１.５４ｇ（０.０３３５ｍｏｌ）を加えた（脂肪族不飽和基１００コ当り水酸基の数８.０コ）。この溶液中の含水率は５００ｐｐｍであった（脂肪族不飽和基１００コ当り水分子の数２.４コ）。次に、この溶液を約２℃に冷却し、撹拌しながら、臭素８０.０ｇ（０.５０１ｍｏｌ）を６０分かけて滴下漏斗より滴下した。滴下終了時には、反応溶液の温度は１６℃であった。滴下終了後、反応溶液を３０分間撹拌を続け、臭素の付加反応を終了した。
【０１５６】
次に、この反応溶液を実施例１０と同様の処理を行い、主として２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝スルフォンを得た。この臭素化合物は純度９３.７％、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝スルフォン１モルに対して、水に由来する不純物は０.００５モル、エタノールに由来する不純物は０.０４０モルであった。
【０１５７】
実施例１９
実施例１０で使用したガラス製反応容器に、ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝メタン１３５ｇ（０.２２７ｍｏｌ）および合成ゼオライトで脱水処理したクロロホルム２３０ｇを入れ溶解させた。また、この溶液中に、ｎ−プロパノール２.３３ｇ（０.０３８８ｍｏｌ）を加えた（脂肪族不飽和基１００コ当り水酸基の数８.５コ）。この溶液中の含水率は２００ｐｐｍであった（脂肪族不飽和基１００コ当り水分子の数０.９０コ）。次に、この溶液を２５℃に設定し、撹拌しながら、臭素８０.０ｇ（０.５０１ｍｏｌ）を１００分かけて滴下漏斗より滴下した。滴下終了時には、反応溶液の温度は３５℃であった。滴下終了後、反応溶液を３０分間撹拌を続け、臭素の付加反応を終了した。
【０１５８】
次に、この反応溶液を実施例１０と同様の処理を行い、主として２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝メタンを得た。この臭素化合物は純度９４.５％、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝メタン１モルに対して、水に由来する不純物は０.００３モル、ｎ−プロピルアルコールに由来する不純物は０.０３６モルであった。
【０１５９】
実施例２０
実施例１０で使用したガラス製反応容器に、（３,３’,５,５’−テトラブロモ−４,４’−ジアリルオキシ）ビフェニル１３５ｇ（０.２３２ｍｏｌ）および合成ゼオライトで脱水処理した１,４−ジオキサン６１５ｇを入れ溶解させた。また、この溶液中に、エタノール１.５４ｇ（０.０３３５ｍｏｌ）を加えた（脂肪族不飽和基１００コ当り水酸基の数７.２コ）。この溶液中の含水率は４００ｐｐｍであった（脂肪族不飽和基１００コ当り水分子の数３.６コ）。次に、この溶液を２５℃に設定し、撹拌しながら、臭素８０.０ｇ（０.５０１ｍｏｌ）を１００分かけて滴下漏斗より滴下した。滴下終了時には、反応溶液の温度は３５℃であった。滴下終了後、反応溶液を３０分間撹拌を続け、臭素の付加反応を終了した。
【０１６０】
次に、この反応溶液を実施例１０と同様の処理を行い、主として｛３,３’,５,５’−テトラブロモ−４,４’−（２,３−ジブロモプロピルオキシ）｝ビフェニルを得た。この臭素化合物は純度９４.０％、｛３,３’,５,５’−テトラブロモ−４,４’−（２,３−ジブロモプロピルオキシ）｝ビフェニル１モルに対して、水に由来する不純物は０.００５モル、エタノールに由来する不純物は０.０３２モルであった。
【０１６１】
なお、実施例１０〜２０の結果を表３および表４に示した。
表３および表４中、水酸基を有する化合物の濃度は、脂肪族不飽和結合を有する化合物の不飽和基１００コ当りの水酸基の数（コ）を示し、水の濃度は、脂肪族不飽和結合を有する化合物の不飽和基１００コ当りの水分子の数（コ）を示す。また、水由来の不純物（モル）および水酸基を有する化合物由来の不純物（モル）は、得られた臭素化合物１モルに対する量を表す。
【０１６２】
【表３】

【０１６３】
【表４】

【０１６４】
実施例２１
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた１Ｌのガラス製反応容器に、臭素７２.６ｇ（０.４５４ｍｏｌ）を入れた。また、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン１３５ｇ（０.２１６ｍｏｌ）を塩化メチレン２３０ｇに溶解した溶液を準備した（この溶液中の含水率は２００ｐｐｍであり、脂肪族不飽和基１００コ当り水分子０.９４コである）。次に、反応容器内を撹拌しながら、１５〜２０℃の温度で、かかる２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパンの塩化メチレン溶液３６５ｇを６０分で滴下漏斗より臭素に滴下した。滴下終了後、反応溶液を１５〜２０℃の温度で３０分間撹拌し続け、臭素の付加反応を終了した。
【０１６５】
次に、反応溶液中の過剰の臭素を１５重量％重亜硫酸ソーダ水溶液１００ｇで還元した後、生成した臭化水素を２５重量％の水酸化ナトリウム水溶液を用いて中和した。その後、この溶液から塩化メチレン層を分液し、かかる塩化メチレン層から塩化メチレンを９０％程度蒸発、除去し、これにメタノールを５００ｍＬ加え反応生成物を沈殿させ、この沈殿物をろ過して塊状固体を取り出した。この塊状固体を乳鉢で粉砕し、８０℃、３時間、５ｍｍＨｇで減圧乾燥し生成物を得た。
【０１６６】
得られた生成物を¹Ｈ−ＮＭＲで分析したところ４.５１〜４.５３ｐｐｍに−ＣＨＢｒ−由来のシグナルが、３.９４〜４.０９ｐｐｍに−ＣＨ₂Ｂｒ由来のシグナルが認められた。またＦＴ−ＩＲ分析より、−Ｏ−ＣＨ₂−の吸収を認め、アリル基の吸収は認められないのを確認した。以上の分析結果より、生成物は、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物は、純度９６.５％、臭素含有率６７.５％（理論値６７.８％）であった。
【０１６７】
実施例２２
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた１Ｌのガラス製反応容器に、臭素７２.６ｇ（０.４５４ｍｏｌ）および塩化メチレン５８.１ｇを入れた。次に、反応容器内を撹拌しながら、１５〜２０℃の温度で、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン１３５ｇ（０.２１６ｍｏｌ）ｇを６０分で滴下漏斗より臭素溶液に滴下した。滴下終了後、反応溶液を１５〜２０℃の温度で３０分間撹拌し続け、臭素の付加反応を終了した。
【０１６８】
得られた反応溶液を、実施例２１と同様の操作を行い、白色固体の生成物を得た。実施例２１と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物は、純度９６.３％、臭素含有率６７.５％（理論値６７.８％）であった。
【０１６９】
実施例２３
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた１Ｌのガラス製反応容器に、臭素７２.６ｇ（０.４５４ｍｏｌ）および塩化メチレン５８.１ｇを入れた。また、２,２−ビス｛（３,５−ジブロモ−４−イソブテニルオキシ）フェニル｝プロパン１４０.８ｇ（０.２１６ｍｏｌ）を塩化メチレン２３０ｇに溶解した溶液を準備した。次に、反応容器内を撹拌しながら、１５〜２０℃の温度で、かかる２,２−ビス｛（３,５−ジブロモ−４−イソブテニルオキシ）フェニル｝プロパンの塩化メチレン溶液３７０.８ｇを１２０分で滴下漏斗より臭素溶液に滴下した。滴下終了後、反応溶液を１５〜２０℃の温度で３０分間撹拌し続け、臭素の付加反応を終了した。
【０１７０】
得られた反応溶液を、実施例２１と同様の操作を行い、白色固体の生成物を得た。実施例２１と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−２−メチルプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物は、純度９６.５％、臭素含有率６５.３％（理論値６５.８％であった。）
【０１７１】
実施例２４
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた１Ｌのガラス製反応容器に、臭素７２.６ｇ（０.４５４ｍｏｌ）および塩化メチレン５８.１ｇを入れた。また、ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝メタン１２８.７ｇ（０.２１６ｍｏｌ）を塩化メチレン１６１ｇと１,４−ジオキサン６９ｇとの混合溶媒に溶解した溶液を準備した。次に、反応容器内を撹拌しながら、１５〜２０℃の温度で、かかるビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝メタンの溶液３５８.７ｇを６０分で滴下漏斗より臭素溶液に滴下した。滴下終了後、反応溶液を１５〜２０℃の温度で３０分間撹拌し続け、臭素の付加反応を終了した。
【０１７２】
得られた反応溶液を、実施例２１と同様の操作を行い、白色固体の生成物を得た。実施例２１と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−プロピルオキシ）フェニル｝メタンであることが確認された。この臭素化合物は、純度９６.０％、臭素含有率６９.５％（理論値６９.８％）であった。
【０１７３】
実施例２５
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた１Ｌのガラス製反応容器に、臭素７.２６ｇ（０.０４５ｍｏｌ）および塩化メチレン２１７.７ｇを入れた。また、ビス｛（３,５−ジブロモ−４−イソブテニルオキシ）フェニル｝メタン１３.５ｇ（０.０２１６ｍｏｌ）を塩化メチレン２３ｇに溶解した溶液を準備した。次に、反応容器内を撹拌しながら、１５〜２０℃の温度で、かかるビス｛（３,５−ジブロモ−４−イソブテニルオキシ）フェニル｝メタンの塩化メチレン溶液３６.５ｇを６０分で滴下漏斗より臭素溶液に滴下した。滴下終了後、反応溶液を１５〜２０℃の温度で３０分間撹拌し続け、臭素の付加反応を終了した。
【０１７４】
得られた反応溶液を、実施例２１と同様の操作を行い、白色固体の生成物を得た。実施例２１と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−２−メチルプロピルオキシ）フェニル｝メタンであることが確認された。この臭素化合物は、純度９６.２％、臭素含有率６７.７％（理論値６７.８％）であった。
【０１７５】
実施例２６
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた１Ｌのガラス製反応容器に、臭素７２.６ｇ（０.４５４ｍｏｌ）および塩化メチレン３００ｇを入れた。また、（３,３’,５,５’−テトラブロモ−４,４’−ジアリルオキシ）ビフェニル１２５.７ｇ（０.２１６ｍｏｌ）を塩化メチレン２３０ｇに溶解した溶液を準備した。次に、反応容器内を撹拌しながら、１５〜２０℃の温度で、かかる（３,３’,５,５’−テトラブロモ−４,４’−ジアリルオキシ）ビフェニルの塩化メチレン溶液３５５.７ｇを６０分で滴下漏斗より臭素溶液に滴下した。滴下終了後、反応溶液を１５〜２０℃の温度で３０分間撹拌し続け、臭素の付加反応を終了した。
【０１７６】
得られた反応溶液を、実施例２１と同様の操作を行い、白色固体の生成物を得た。実施例２１と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、｛３,３’,５,５’−テトラブロモ−４,４’−（２,３−ジブロモ−プロピルオキシ）｝ビフェニルであることが確認された。この臭素化合物は、純度９５.７％、臭素含有率、７０.７％（理論値７０.９％）であった。
【０１７７】
実施例２７
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた１Ｌのガラス製反応容器に、臭素７２.６ｇ（０.４５４ｍｏｌ）および塩化メチレン１４.５ｇを入れた。また、ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝スルフォン１３９.５ｇ（０.２１６ｍｏｌ）を塩化メチレン２３０ｇに溶解した溶液を準備した。次に、反応容器内を撹拌しながら、１５〜２０℃の温度で、かかるビス｛３,５−ジブロモ−４−アリルオキシ）フェニル｝スルフォンの塩化メチレン溶液３６９.５ｇを６０分で滴下漏斗より臭素溶液に滴下した。滴下終了後、反応溶液を１５〜２０℃の温度で３０分間撹拌し続け、臭素の付加反応を終了した。
【０１７８】
得られた反応溶液を、実施例２１と同様の操作を行い、白色固体の生成物を得た。実施例２１と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝スルフォンであることが確認された。この臭素化合物は、純度９５.４％、臭素含有率６６.０％（理論値６６.２％）であった。
【０１７９】
実施例２８
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた１Ｌのガラス製反応容器に、臭素７２.６ｇ（０.４５４ｍｏｌ）および塩化メチレン５８.１ｇを入れた。また、ビス｛（３,５−ジブロモ−４−イソブテニルオキシ）フェニル｝スルフォン１４５.６ｇ（０.２１６ｍｏｌ）を塩化メチレン１６１ｇと１,４−ジオキサン６９ｇとの混合溶媒に溶解した溶液を準備した。次に、反応容器内を撹拌しながら、１５〜２０℃の温度で、かかるビス｛３,５−ジブロモ−４−イソブテニルオキシ）フェニル｝スルフォンの溶液３７５.６ｇを１２０分で滴下漏斗より臭素溶液に滴下した。滴下終了後、反応溶液を１５〜２０℃の温度で３０分間撹拌し続け、臭素の付加反応を終了した。
【０１８０】
得られた反応溶液を、実施例２１と同様の操作を行い、白色固体の生成物を得た。実施例２１と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−２−メチルプロピルオキシ）｝スルフォンであることが確認された。この臭素化合物は、純度９５.０％、臭素含有率６４.１％（理論値６４.４％）であった。なお、実施例２１〜２８の結果を表５および表６に示した。
【０１８１】
【表５】

【０１８２】
【表６】

【０１８３】
実施例２９
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた５００ｍＬのガラス製反応容器に、臭素７２.７ｇ（０.４５５ｍｏｌ）を入れた。また、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン１３５ｇ（０.２１６ｍｏｌ）を合成ゼオライトで脱水処理した塩化メチレン２３０ｇに溶解し、これにメタノール０.３６ｇ（０.０１１３ｍｏｌ、脂肪族不飽和基１００コ当り水酸基の数２.６コ）を加えた溶液を準備した。次に、反応容器内の臭素を２℃に冷却し、撹拌しながら、かかる２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパンの塩化メチレン溶液を６０分かけて滴下漏斗より臭素に滴下した。滴下終了時には、反応溶液の温度は１６℃であった。滴下終了後、反応溶液を３０分間撹拌し続け、臭素の付加反応を終了した。この反応溶液中の含水率は２００ｐｐｍであった（脂肪族不飽和基１００コ当り水分子の数１.１コ）。
【０１８４】
次に、反応溶液中の過剰の臭素を１５重量％重亜硫酸ソーダ水溶液５０ｇで還元した後、生成した臭化水素を２５重量％の水酸化ナトリウム水溶液を用いて中和した。その後、イオン交換水１００ｇを加え、撹拌後この溶液から塩化メチレン層を分液し、かかる塩化メチレン層から塩化メチレンを９０％程度蒸発、除去し、これにメタノールを５００ｍＬ加え反応生成物を沈殿させ、この沈殿物をろ過して塊状固体を取り出した。この塊状固体を乳鉢で粉砕し、８０℃、３時間、５ｍｍＨｇで減圧乾燥し生成物を得た。
【０１８５】
得られた生成物を¹Ｈ−ＮＭＲで分析したところ４.５１〜４.５３ｐｐｍに−ＣＨＢｒ−由来のシグナルが、３.９４〜４.０９ｐｐｍに−ＣＨ₂Ｂｒ由来のシグナルが認められた。またＦＴ−ＩＲ分析より、−Ｏ−ＣＨ₂−の吸収を認め、アリル基の吸収は認められないのを確認した。以上の分析結果より、生成物は、主として２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物は、純度９６.７％であり、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパン１モルに対して、水に由来する不純物は０.００２３モル、メタノールに由来する不純物は０.０１５５モルであった。また、かかる臭素化合物の傾斜角は４０°であった。
【０１８６】
実施例３０
実施例２９において、メタノールの代わりにエタノール０.３６ｇ（０.００７８３ｍｏｌ、脂肪族不飽和基１００コ当り水酸基の数１.８コ）を用いる以外は、実施例２９と同様の方法を行い、臭素の付加反応を行った。この反応溶液中の含水率は２１０ｐｐｍであった（脂肪族不飽和基１００コ当り水分子１.２コ）。
【０１８７】
この反応溶液を、実施例２９と同様の操作を行い、主として２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンを得た。この臭素化合物は、純度９６.１％であり、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパン１モルに対して、水に由来する不純物は０.００２５モル、エタノールに由来する不純物は０.０１２４モルであった。また、かかる臭素化合物の傾斜角は４１°であった。
【０１８８】
実施例３１
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた１Ｌのガラス製反応容器に、臭素７２.６ｇ（０.４５４ｍｏｌ）および塩化メチレン２３０ｇを入れた。また、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン１３５ｇ（０.２１６ｍｏｌ）を塩化メチレン２３０ｇに溶解し、これにエタノール０.３６ｇ（０.００７８３ｍｏｌ、脂肪族不飽和基１００コ当り水酸基の数１.８コ）を加えた溶液を準備した。次に、反応容器内の臭素溶液を２℃に冷却し、撹拌しながら、かかる２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパンの塩化メチレン溶液を６０分かけて滴下漏斗より臭素溶液に滴下した。滴下終了時には、反応溶液の温度は１６℃であった。滴下終了後、反応溶液を３０分間撹拌し続け、臭素の付加反応を終了した。この反応溶液中の含水率は４２０ｐｐｍであった（脂肪族不飽和基１００コ当り水分子の数３.６コ）。
【０１８９】
得られた反応溶液を、実施例２９と同様の操作を行い、白色固体の生成物を得た。実施例２９と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、主として２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物は、純度９５.９％であり、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパン１モルに対して、水に由来する不純物は０.００４１モル、エタノールに由来する不純物は０.０１２４モルであった。また、かかる臭素化合物の傾斜角は４４°であった。
【０１９０】
実施例３２
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた１Ｌのガラス製反応容器に、臭素７２.６ｇ（０.４５４ｍｏｌ）および塩化メチレン２３０ｇを入れた。また、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン１３５ｇ（０.２１６ｍｏｌ）を塩化メチレン２３０ｇに溶解し、これにエタノール０.３６ｇ（０.００７８３ｍｏｌ、脂肪族不飽和基１００コ当り水酸基の数１.８コ）を加えた溶液を準備した。次に、反応容器内を撹拌しながら、３９〜４１℃の温度で塩化メチレンを還流させながら、かかる２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパンの塩化メチレン溶液を１０分かけて滴下漏斗より臭素溶液に滴下した。滴下終了後、反応溶液を３９〜４１℃の温度で塩化メチレンを還流させながら３０分間撹拌し続け、臭素の付加反応を終了した。この反応溶液中の含水率は４２０ｐｐｍであった（脂肪族不飽和基１００コ当り水分子の数３.６コ）。
【０１９１】
得られた反応溶液を、実施例２９と同様の操作を行い、白色固体の生成物を得た。実施例２９と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、主として２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物は、純度９６.４％であり、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパン１モルに対して、水に由来する不純物は０.００２３モル、エタノールに由来する不純物は０.０１２３モルであった。
【０１９２】
実施例３３
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた５００ｍＬのガラス製反応容器に、臭素７２.６ｇ（０.４５４ｍｏｌ）、合成ゼオライトで脱水処理した塩化メチレン２３０ｇおよびエタノール０.３６ｇ（０.００７８３ｍｏｌ、脂肪族不飽和基１００コ当り水酸基の数１.８コ）を入れた。次に、反応容器内を撹拌しながら、３９〜４１℃の温度で塩化メチレンを還流させながら、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン１３５ｇ（０.２１６ｍｏｌ）を５分かけて臭素溶液に添加した。添加終了後、反応溶液を３９〜４１℃の温度で塩化メチレンを還流させながら３０分間撹拌し続け、臭素の付加反応を終了した。この反応溶液中の含水率は２１０ｐｐｍであった（脂肪族不飽和基１００コ当り水分子の数１.２コ）。
【０１９３】
得られた反応溶液を、実施例２９と同様の操作を行い、白色固体の生成物を得た。実施例２９と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、主として２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物は、純度９６.５％であり、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパン１モルに対して、水に由来する不純物は０.００２１モル、エタノールに由来する不純物は０.０１３５モルであった。
【０１９４】
実施例３４
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた１Ｌのガラス製反応容器に、臭素７２.７ｇ（０.４５５ｍｏｌ）を入れた。また、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン１３５ｇ（０.２１６ｍｏｌ）を合成ゼオライトで脱水処理した塩化メチレン２３０ｇに溶解し、これにｉ−プロパノール０.３６ｇ（０.００６０ｍｏｌ、脂肪族不飽和基１００コ当り水酸基の数１.４コ）を加えた溶液を準備した。次に、反応容器内の臭素を約２℃に冷却し、撹拌しながら、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパンの溶液を６０分かけて滴下漏斗より臭素に滴下した。滴下終了時には、反応溶液の温度は２０℃であった。滴下終了後、反応溶液を３０分間撹拌し続け、臭素の付加反応を終了した。この反応溶液中の含水率は２００ｐｐｍであった（脂肪族不飽和基１００コ当り水分子の数１.１コ）。
【０１９５】
得られた反応溶液を、実施例２９と同様の操作を行い、白色固体の生成物を得た。実施例２９と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、主として２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物は、純度９６.３％であり、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパン１モルに対して、水に由来する不純物は０.００１９モル、ｉ−プロパノールに由来する不純物は０.０１４６モルであった。また、かかる臭素化合物の傾斜角は４０°であった。
【０１９６】
実施例３５
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた１Ｌのガラス製反応容器に、臭素７２.７ｇ（０.４５５ｍｏｌ）を入れた。また、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン１３５ｇ（０.２１６ｍｏｌ）を合成ゼオライトで脱水処理したクロロホルム６１５ｇに溶解し、これにメタノール０.５４ｇ（０.０１６９ｍｏｌ、脂肪族不飽和基１００コ当り水酸基の数３.９コ）を加えた溶液を準備した。次に、反応容器内の臭素を２℃に冷却し、撹拌しながら、かかる２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパンのクロロホルム溶液を６０分かけて滴下漏斗より臭素に滴下した。滴下終了時には、反応溶液の温度は１６℃であった。滴下終了後、反応溶液を３０分間撹拌し続け、臭素の付加反応を終了した。この反応溶液中の含水率は１００ｐｐｍであった（脂肪族不飽和基１００コ当り水分子の数１.１コ）。
【０１９７】
次に、反応溶液中の過剰の臭素を１５重量％重亜硫酸ソーダ水溶液５０ｇで還元した後、生成した臭化水素を２５重量％の水酸化ナトリウム水溶液を用いて中和した。その後、イオン交換水２００ｇを加え、撹拌後この溶液からクロロホルム層を分液し、かかるクロロホルム層からクロロホルムを９０％程度蒸発、除去し、これにメタノールを５００ｍＬ加え反応生成物を沈殿させ、この沈殿物をろ過して塊状固体を取り出した。この塊状固体を乳鉢で粉砕し、８０℃、３時間、５ｍｍＨｇで減圧乾燥し生成物を得た。実施例２９と同様に、得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、主として２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物は、純度９５.８％であり、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパン１モルに対して、水に由来する不純物は０.００２２モル、メタノールに由来する不純物は０.０１５５モルであった。
【０１９８】
実施例３６
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた５００ｍＬのガラス製反応容器に、臭素６９.５ｇ（０.４３５ｍｏｌ）を入れた。また、２,２−ビス｛（３,５−ジブロモ−４−イソブテニルオキシ）フェニル｝プロパン１３５ｇ（０.２０７ｍｏｌ）を合成ゼオライトで脱水処理した塩化メチレン２３０ｇに溶解し、これにメタノール０.３６ｇ（０.０１１３ｍｏｌ、脂肪族不飽和基１００コ当り水酸基の数２.７コ）を加えた溶液を準備した。次に、反応容器内の臭素を約２℃に冷却し、撹拌しながら、２,２−ビス｛（３,５−ジブロモ−４−イソブテニルオキシ）フェニル｝プロパンの溶液を６０分かけて滴下漏斗より臭素に滴下した。滴下終了時には、反応溶液の温度は１６℃であった。滴下終了後、反応溶液を３０分間撹拌し続け、臭素の付加反応を終了した。この反応溶液中の含水率は１９０ｐｐｍであった（脂肪族不飽和基１００コ当り水分子の数１.１コ）。
【０１９９】
得られた反応溶液を、実施例２９と同様の操作を行い、白色固体の生成物を得た。実施例２９と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、主として２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−２−メチルプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物は、純度９５.８％であり、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−２−メチルプロピルオキシ）フェニル｝プロパン１モルに対して、水に由来する不純物は０.００２１モル、メタノールに由来する不純物は０.０２１２モルであった。
【０２００】
実施例３７
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた５００ｍＬのガラス製反応容器に、臭素７０.１ｇ（０.４３９ｍｏｌ）を入れた。また、ビス｛３,５−ジブロモ−４−アリルオキシ）フェニル｝スルフォン１３５ｇ（０.２０９ｍｏｌ）を合成ゼオライトで脱水処理した塩化メチレン２３０ｇに溶解し、これにメタノール０.３６ｇ（０.０１１３ｍｏｌ、脂肪族不飽和基１００コ当り水酸基の数２.７コ）を加えた溶液を準備した。次に、反応容器内の臭素を約２℃に冷却し、撹拌しながら、ビス｛３,５−ジブロモ−４−アリルオキシ）フェニル｝スルフォンの溶液を６０分かけて滴下漏斗より臭素に滴下した。滴下終了時には、反応溶液の温度は１６℃であった。滴下終了後、反応溶液を３０分間撹拌し続け、臭素の付加反応を終了した。この反応溶液中の含水率は１８０ｐｐｍであった（脂肪族不飽和基１００コ当り水分子の数１.０コ）。
【０２０１】
得られた反応溶液を、実施例２９と同様の操作を行い、白色固体の生成物を得た。実施例２９と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、主としてビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝スルフォンであることが確認された。この臭素化合物は、純度９４.２％であり、ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝スルフォン１モルに対して、水に由来する不純物は０.００２０モル、メタノールに由来する不純物は０.０３２８モルであった。
【０２０２】
実施例３８
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた５００ｍＬのガラス製反応容器に、臭素７６.２ｇ（０.４７７ｍｏｌ）を入れた。また、ビス｛３,５−ジブロモ−４−アリルオキシ）フェニル｝メタン１３５ｇ（０.２２７ｍｏｌ）を合成ゼオライトで脱水処理したクロロホルム６１５ｇに溶解し、これにｎ−ブタノール１.１３ｇ（０.０１５７ｍｏｌ、脂肪族不飽和基１００コ当り水酸基の数３.５コ）を加えた溶液を準備した。次に、反応容器内の臭素を約２℃に冷却し、撹拌しながら、ビス｛３,５−ジブロモ−４−アリルオキシ）フェニル｝メタンの溶液を６０分かけて滴下漏斗より臭素に滴下した。滴下終了時には、反応溶液の温度は１６℃であった。滴下終了後、反応溶液を３０分間撹拌し続け、臭素の付加反応を終了した。この反応溶液中の含水率は１００ｐｐｍであった（脂肪族不飽和基１００コ当り水分子の数１.０コ）。
【０２０３】
得られた反応溶液を、実施例３５と同様の操作を行い、白色固体の生成物を得た。実施例２９と同様に、得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、主としてビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝メタンであることが確認された。この臭素化合物は、純度９４.９％であり、ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝メタン１モルに対して、水に由来する不純物は０.００１４モル、ｎ−ブタノールに由来する不純物は０.０３５３モルであった。
【０２０４】
実施例３９
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた１Ｌのガラス製反応容器に、臭素７７.９ｇ（０.４８７ｍｏｌ）および合成ゼオライトで脱水処理した１,４−ジオキサン１２３ｇを入れた。また、（３,３’,５,５’−テトラブロモ−４,４’−ジアリルオキシ）ビフェニル１３５ｇ（０.２３２ｍｏｌ）を合成ゼオライトで脱水処理した１,４−ジオキサン６１５ｇに溶解し、これにｎ−ブタノール１.１３ｇ（０.０１５７ｍｏｌ、脂肪族不飽和基１００コ当り水酸基の数３.４コ）を加えた溶液を準備した。次に、反応容器内の臭素溶液を約２２℃に設定し、撹拌しながら、（３,３’,５,５’−テトラブロモ−４,４’−ジアリルオキシ）ビフェニルの溶液を１０分かけて滴下漏斗より臭素溶液に滴下した。滴下終了時には、反応溶液の温度は５０℃であった。滴下終了後、反応溶液を３０分間撹拌し続け、臭素の付加反応を終了した。この反応溶液中の含水率は１２０ｐｐｍであった（脂肪族不飽和基１００コ当り水分子の数１.４コ）。
【０２０５】
次に、反応溶液中の過剰の臭素を１５重量％重亜硫酸ソーダ水溶液５０ｇで還元した後、生成した臭化水素を２５重量％の水酸化ナトリウム水溶液を用いて中和した。その後、イオン交換水１００ｇを加え、撹拌後この溶液から１,４−ジオキサン層を分液し、かかる１,４−ジオキサン層から１,４−ジオキサンを９０％程度蒸発、除去し、これにメタノールを５００ｍＬ加え反応生成物を沈殿させ、この沈殿物をろ過して塊状固体を取り出した。この塊状固体を乳鉢で粉砕し、８０℃、３時間、５ｍｍＨｇで減圧乾燥し生成物を得た。実施例２９と同様に、得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、主として｛３,３’,５,５’−テトラブロモ−４,４’−（２,３−ジブロモ−プロピルオキシ）｝ビフェニルであることが確認された。この臭素化合物は、純度９４.６％であり、｛３,３’,５,５’−テトラブロモ−４,４’−（２,３−ジブロモ−プロピルオキシ）｝ビフェニル１モルに対して、水に由来する不純物は０.００１８モル、ｎ−ブタノールに由来する不純物は０.０２５４モルであった。
【０２０６】
なお、実施例２９〜３９の結果を表７および表８に示した。
表７および表８中、水酸基を有する化合物の濃度は、脂肪族不飽和結合を有する化合物の不飽和基１００コ当りの水酸基の数（コ）を示し、水の濃度は、脂肪族不飽和結合を有する化合物の不飽和基１００コ当りの水分子の数（コ）を示す。また、水由来の不純物（モル）および水酸基を有する化合物由来の不純物（モル）は、得られた臭素化合物１モルに対する量を表す。
【０２０７】
【表７】

【０２０８】
【表８】

【０２０９】
実施例４０
２,２−ビス｛（３,５−ジブロモー４−アリルオキシ）フェニル｝プロパン（原料Ｎｏ．（１））１０００ｇ（１.６０ｍｏｌ）を塩化メチレン１７０３ｇ（２０.０ｍｏｌ）に溶解した。この溶液の比重は１.４６であり、カールフィッシャー法で測定した結果１６０ｐｐｍの水を含有していた。
【０２１０】
図２に示される撹拌翼３、コンデンサー４、温度計５を備えたガラス製の反応容器に、かかる溶液を投入口１より５.３×１０^-3Ｌ／分の速度で、臭素を投入口２より０.５８×１０^-3Ｌ／分の速度で連続的に添加した（臭素／化合物（１）のモル比は２.４５）。反応容器中で混合された溶液は、臭素化の反応熱で発熱し、気化した蒸気は、充分に冷却されたコンデンサー４により反応容器に還流された。原料Ｎｏ．（１）の溶液および臭素の添加を開始してから約２０分後に、導出口８から反応溶液が導出し始め、その後連続的に導出し続けた（滞留時間２０.４分）。また、反応容器（１２０ｍｌ）内の反応溶液は、反応溶液が導出し始めた時から反応溶液の一部をポンプ６を用い０.０３Ｌ／分の速度で、反応容器内に循環した。
【０２１１】
該反応容器から導出してきた反応溶液は、二亜硫酸ソーダ水溶液（約１５重量％）で過剰の臭素を還元後、生成した臭化水素を水酸化ナトリウム水溶液で中和した。その後、この溶液にイオン交換水１０００ｇを加え撹拌し、塩化メチレン層を分液し、かかる塩化メチレン層から塩化メチレンを９０％程度蒸発、除去し、これにメタノールを加え反応生成物を沈殿させ、この沈殿物をろ過して塊状固体を取り出した。この塊状固体を乳鉢で粉砕し、８０℃、１０時間減圧乾燥し、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンを得た。この臭素化合物は、純度９４.２％、臭素含有率６７.３％（理論値６７.８％）であった。
【０２１２】
実施例４１
実施例４０において、塩化メチレン１７０３ｇを４４０５ｇ（５１.８ｍｏｌ）に代えて（溶液の比重１.４２、含水率１３０ｐｐｍ）、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパンの溶液の添加速度を、１０.５×１０^-3Ｌ／分とする以外は、実施例４０と同様の方法で反応を行った。得られた２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンは純度９４.２％であった。
【０２１３】
実施例４２
実施例４０において、溶媒を塩化メチレン１７０３ｇに代えて塩化メチレン９００ｇ（１０.６ｍｏｌ）とクロロホルム８０３ｇ（６.７ｍｏｌ）との混合溶媒を用いる（溶液の比重１.４８、含水率２６０ｐｐｍ）以外は、実施例４０と同様の方法で反応を行った。得られた２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンは純度９４.０％であった。
【０２１４】
実施例４３
実施例４０において、２,２−ビス｛（３,５−ジブロモー４−アリルオキシ）フェニル｝プロパンの溶液の添加速度を１３５.２×１０^-3Ｌ／分、臭素の添加速度を１４.８×１０^-3Ｌ／分する以外は、実施例４０と同様の方法で反応を行った。得られた２、２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンは純度９４.１％であった。
【０２１５】
実施例４４
２,２−ビス｛（３,５−ジブロモー４−イソブテニルオキシ）フェニル｝プロパン（原料Ｎｏ．（２））１０４３ｇ（１.６０ｍｏｌ）を塩化メチレン３４００ｇ（４０.０ｍｏｌ）に溶解した。この溶液の比重は１.４６であり、カールフィッシャー法で測定した結果１２０ｐｐｍの水を含有していた。
【０２１６】
図２に示される撹拌翼３、コンデンサー４、温度計５を備えたガラス製の反応容器に、かかる溶液を投入口１より１０.５×１０^-3Ｌ／分の速度で、臭素を投入口２より０.５９×１０^-3Ｌ／分の速度で連続的に添加した（臭素／化合物（２）のモル比は２.０７）。反応容器中で混合された溶液は、臭素化の反応熱で発熱し、気化した蒸気は、充分に冷却されたコンデンサー４により反応容器に還流された。原料Ｎｏ．（２）の溶液および臭素の添加を開始してから約１１分後に、導出口８から反応溶液が導出し始め、その後連続的に導出し続けた（滞留時間１０.８分）。また、反応容器（１２０ｍｌ）内の反応溶液は、反応溶液が導出し始めた時から反応溶液の一部をポンプ６を用い０.０３Ｌ／分の速度で、反応容器内に循環した。
【０２１７】
該反応容器から導出してきた反応溶液は、実施例４０と同様の方法で処理し、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−２−メチルプロピルオキシ）フェニル｝プロパンを得た。この臭素化合物は、純度９３.９％であった。
【０２１８】
実施例４５
ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝メタン（原料Ｎｏ．（３））４７６ｇ（０.８ｍｏｌ）を塩化メチレン１７００ｇ（２０.０ｍｏｌ）と１,４−ジオキサン１７００ｇ（１９.３ｍｏｌ）との混合溶媒に溶解した。この溶液の比重は１.２２であり、カールフィッシャー法で測定した結果３２０ｐｐｍの水を含有していた。
【０２１９】
図２に示される撹拌翼３、コンデンサー４、温度計５を備えたガラス製の反応容器に、かかる溶液を投入口１より１０.６×１０^-3Ｌ／分の速度で、臭素を投入口２より０.４３×１０^-3Ｌ／分の速度で連続的に添加した（臭素／化合物（３）のモル比は３.１３）。反応容器中で混合された溶液は、臭素化の反応熱で発熱し、気化した蒸気は、充分に冷却されたコンデンサー４により反応容器に還流された。原料Ｎｏ．（３）の溶液および臭素の添加を開始してから約１１分後に、導出口８から反応溶液が導出し始め、その後連続的に導出し続けた（滞留時間１０.９分）。また、反応容器（１２０ｍｌ）内の反応溶液は、反応溶液が導出し始めた時から反応溶液の一部をポンプ６を用い０.０３Ｌ／分の速度で、反応容器内に循環した。
【０２２０】
該反応容器から導出してきた反応溶液は、実施例４０と同様の方法で処理し、ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−プロピルオキシ）フェニル｝メタンを得た。この臭素化合物は、純度９３.３％であった。
【０２２１】
実施例４６
ビス｛（３,５−ジブロモ−４−イソブテニルオキシ）フェニル｝メタン（原料Ｎｏ．（４））５００ｇ（０.８ｍｏｌ）を塩化メチレン１７００ｇ（２０.０ｍｏｌ）に溶解した。この溶液の比重は１.４１であり、カールフィッシャー法で測定した結果１６０ｐｐｍの水を含有していた。
【０２２２】
図２に示される撹拌翼３、コンデンサー４、温度計５を備えたガラス製の反応容器に、かかる溶液を投入口１より１０.５×１０^-3Ｌ／分の速度で、臭素を投入口２より０.６２×１０^-3Ｌ／分の速度で連続的に添加した（臭素／化合物（４）のモル比は２.２３）。反応容器中で混合された溶液は、臭素化の反応熱で発熱し、気化した蒸気は、充分に冷却されたコンデンサー４により反応容器に還流された。原料Ｎｏ．（４）の溶液および臭素の添加を開始してから約１１分後に、導出口８から反応溶液が導出し始め、その後連続的に導出し続けた（滞留時間１０.８分）。また、反応容器（１２０ｍｌ）内の反応溶液は、反応溶液が導出し始めた時から反応溶液の一部をポンプ６を用い０.０３Ｌ／分の速度で、反応容器内に循環した。
【０２２３】
該反応容器から導出してきた反応溶液は、実施例４０と同様の方法で処理し、ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−２−メチルプロピルオキシ）フェニル｝メタンを得た。この臭素化合物は、純度９３.５％であった。
【０２２４】
実施例４７
ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝スルフォン（原料Ｎｏ．（７））５１７ｇ（０.８ｍｏｌ）を塩化メチレン１７００ｇ（２０.０ｍｏｌ）に溶解した。この溶液の比重は１.４２であり、カールフィッシャー法で測定した結果１８０ｐｐｍの水を含有していた。
【０２２５】
図２に示される撹拌翼３、コンデンサー４、温度計５を備えたガラス製の反応容器に、かかる溶液を投入口１より１０.５×１０^-3Ｌ／分の速度で、臭素を投入口２より０.５９×１０^-3Ｌ／分の速度で連続的に添加した（臭素／化合物（７）のモル比は２.１３）。反応容器中で混合された溶液は、臭素化の反応熱で発熱し、気化した蒸気は、充分に冷却されたコンデンサー４により反応容器に還流された。原料Ｎｏ．（７）の溶液および臭素の添加を開始してから約１１分後に、導出口８から反応溶液が導出し始め、その後連続的に導出し続けた（滞留時間１０.８分）。また、反応容器（１２０ｍｌ）内の反応溶液は、反応溶液が導出し始めた時から反応溶液の一部をポンプ６を用い０.０３Ｌ／分の速度で、反応容器内に循環した。
【０２２６】
該反応容器から導出してきた反応溶液は、実施例４０と同様の方法で処理し、ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−プロピルオキシ）フェニル｝スルフォンを得た。この臭素化合物は、純度９２.３％であった。
【０２２７】
実施例４８
（３,３’,５,５’−テトラブロモ−４,４’−ジアリルオキシ）ビフェニル（原料Ｎｏ．（５））４６６ｇ（０.８ｍｏｌ）を塩化メチレン１７００ｇ（２０.０ｍｏｌ）と１,４−ジオキサン１７００ｇ（１９.３ｍｏｌ）との混合溶媒に溶解した。この溶液の比重は１.２０であり、カールフィッシャー法で測定した結果３２０ｐｐｍの水を含有していた。
【０２２８】
図２に示される撹拌翼３、コンデンサー４、温度計５を備えたガラス製の反応容器に、かかる溶液を投入口１より１０.６×１０^-3Ｌ／分の速度で、臭素を投入口２より０.４３×１０^-3Ｌ／分の速度で連続的に添加した（臭素／化合物（５）のモル比は３.１６）。反応容器中で混合された溶液は、臭素化の反応熱で発熱し、気化した蒸気は、充分に冷却されたコンデンサー４により反応容器に還流された。原料Ｎｏ．（５）の溶液および臭素の添加を開始してから約１１分後に、導出口８から反応溶液が導出し始め、その後連続的に導出し続けた（滞留時間１０.９分）。また、反応容器（１２０ｍｌ）内の反応溶液は、反応溶液が導出し始めた時から反応溶液の一部をポンプ６を用い０.０３Ｌ／分の速度で、反応容器内に循環した。
【０２２９】
該反応容器から導出してきた反応溶液は、実施例４０と同様の方法で処理し、｛３,３’,５,５’−テトラブロモ−４,４’−（２,３−ジブロモ−プロピルオキシ）｝ビフェニルを得た。この臭素化合物は、純度９３.０％であった。
【０２３０】
実施例４９
実施例４０において、２,２−ビス｛（３,５−ジブロモー４−アリルオキシ）フェニル｝プロパンの溶液の添加速度を０.５７×１０^-3Ｌ／分として、臭素の添加速度を０.０６２×１０^-3Ｌ／分とする以外は、実施例１と同様の方法で反応を行った。得られた２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンは純度９４.１％であった。
【０２３１】
比較例３
２,２−ビス｛（３,５−ジブロモー４−アリルオキシ）フェニル｝プロパンの溶液の添加速度は５.３×１０^-3Ｌ／分の一定として、臭素の添加速度は最初の１０分間を０.２８×１０^-3Ｌ／分（臭素／化合物（１）のモル比は１.１８）とし、次の１０分間を０.８４×１０^-3Ｌ／分（臭素／化合物（１）のモル比は３.５５）として連続的に添加し、これを繰り返して行う以外は、実施例４０と同様の方法で４０分間反応させた。原料Ｎｏ．（１）の溶液および臭素の添加を開始してから約２０分後に、導出口８から反応溶液が導出し始め、その後連続的に導出し続けた（滞留時間２０.５分）。また、反応容器（１２０ｍｌ）内の反応溶液は、反応溶液が導出し始めた時から反応溶液の一部をポンプ６を用い０.０３Ｌ／分の速度で、反応容器内に循環した。
【０２３２】
該反応容器から導出してきた反応溶液は、実施例４０と同様に処理し、２,２−ビス｛（３,５−ジブロモー４−アリルオキシ）フェニル｝プロパンを得た。この臭素化合物の純度は、８５.０％であり、相互に付着しやすい保存安定性の悪い粉末であった。
【０２３３】
比較例４
実施例４０において、２,２−ビス｛（３,５−ジブロモー４−アリルオキシ）フェニル｝プロパンの溶液の添加速度を５.３×１０^-3Ｌ／分として、臭素の添加速度を０.４×１０^-3Ｌ／分とする（臭素／原料Ｎｏ．（１）のモル比は１.６９）以外は、実施例４０と同様の方法で反応を行い、実施例４０と同様に処理して２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンを得た。この臭素化合物の純度は、７１.０％であり、相互に付着しやすい保存安定性の悪い粉末であった。
【０２３４】
比較例５
２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン１０００ｇ（１.６０ｍｏｌ）を塩化メチレン１７０３ｇ（２０.０ｍｏｌ）に溶解した。かかる溶液１６９４ｇを撹拌翼、コンデンサー、温度計および滴下ロートを備えた３０００ｍｌのガラス製容器に入れ、撹拌下、臭素３９６ｇを２２０分かけて滴下ロートより徐々に滴下した。臭素の滴下開始時の溶液温度は２０℃であったが、臭素を滴下するに伴い、反応熱により徐々に溶液温度は上昇し、滴下終了時には溶液温度は３７℃となった。臭素を滴下している間は反応容器を冷却せず、また、塩化メチレンの還流は起こらなかった。臭素の滴下終了後、反応溶液を実施例４０と同様の処理を行い、２、２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンを得た。この臭素化合物の純度は、８２.１％と低く、その外観は着色が認められ、かつ、相互に付着しやすい保存安定性の悪いものであった。
【０２３５】
なお、実施例４０〜４９および比較例３〜４の結果を表９および表１０に示した。
表９および表１０中、溶媒（Ａ）〜（Ｃ）は、
（Ａ）塩化メチレン
（Ｂ）塩化メチレン／クロロホルム＝５３／４７（重量比）
（Ｃ）塩化メチレン／１,４−ジオキサン＝５０／５０（重量比）
を表し、水の濃度は、原料化合物の不飽和基のモル数に対するモル％である。
【０２３６】
【表９】

【０２３７】
【表１０】

【０２３８】
実施例５０
予め、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン１８.５ｋｇの塩化メチレン溶液５０ｋｇを調整した（溶液の比重は１.４７、含水率１５０ｐｐｍ）。
【０２３９】
内容積２０ｃｍ³のエレメント数１２からなるスタテックミキサー（断面積０.５ｃｍ²）に、調整した上記塩化メチレン溶液を添加速度１３３.９ｇ／秒（９１.１ｍＬ／秒）、臭素を添加速度２５.７ｇ／秒（８.３ｍＬ／秒）、すなわち混合溶液の流速が１９９ｃｍ／秒｛≒（９１.１＋８.３）／０.５｝となるように、スタテックミキサー内に連続的に導入し、混合させた後［このスタテックミキサー内での滞留時間は０.２０秒｛≒２０／（９１.１＋８.３）｝］、スタテックミキサーから導出した混合溶液をコンデンサーを備えた容量３０Ｌの撹拌槽に投入した。この撹拌槽において、反応熱が放熱され、また、気化した蒸気を還流することにより、臭素の飛散が抑制された。かかる撹拌槽で、引き続き混合溶液を撹拌し、撹拌槽内で約５分間滞留させた後に、撹拌槽のオーバーフロー口から流出させた。
【０２４０】
かかるオーバーフロー口から流出してくる反応溶液約１０ｍｌを採取し、過剰の臭素を１５重量％の重亜硫酸ソーダ水溶液５ｇで還元した後、２５重量％の苛性ソーダ水溶液を用いて中和した。得られた塩化メチレン層から塩化メチレンを大部分蒸発、除去した後、メタノール５０ｍＬを加え反応生成物を沈殿させ、この沈殿物をろ過して塊状固体を取り出した。この塊状固体を乳鉢で粉砕し、８０℃、３時間減圧乾燥し生成物１.７ｇを得た。
【０２４１】
得られた生成物を¹Ｈ−ＮＭＲで分析したところ４.５１〜４.５３ｐｐｍに−ＣＨＢｒ−由来のシグナルが、３.９４〜４.０９ｐｐｍに−ＣＨ₂Ｂｒ由来のシグナルが認められた。またＦＴ−ＩＲ分析より、−Ｏ−ＣＨ₂−の吸収を認め、アリル基の吸収は認められないのを確認した。以上の分析結果より、生成物は、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物は、純度９６.３％、融点１１４℃、臭素含有率６７.５％（理論値６７.８％）であった。
【０２４２】
実施例５１
実施例５０の内容積２０ｃｍ³のエレメント数１２からなるスタテックミキサー（断面積０.５ｃｍ²）の代わりに内容積１０ｃｍ³のエレメント数６からなるスタテックミキサー（断面積０.５ｃｍ²）を使用する以外は、実施例１と同様の反応を行った（スタテックミキサー内の滞留時間は０.１０秒）。この反応生成物は、実施例１と同様に分析したところ２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンであることが確認された。また、この臭素化合物は、純度９６.３％、融点１１４℃、臭素含有率６７.５％（理論値６７.８％）であった。
【０２４３】
実施例５２
予め、２,２−ビス｛（３,５−ジブロモ−４−イソブテニルオキシ）フェニル｝プロパン１４.８ｋｇの塩化メチレン溶液４０ｋｇを調整した（溶液の比重は１.４７、含水率１５０ｐｐｍ）。
【０２４４】
実施例５０で使用したものと同様のスタテックミキサーに、調整した上記塩化メチレン溶液を添加速度９８.９ｇ／秒（６７.３ｍＬ／秒）、臭素を添加速度２２.４ｇ／秒（７.２ｍＬ／秒）、すなわち混合溶液の流速が１４９ｃｍ／秒となるように、スタテックミキサー内に連続的に導入し、混合させた後（このスタテックミキサー内での滞留時間は０.２７秒）、スタテックミキサーから導出した混合溶液をコンデンサーを備えた容量２３Ｌの撹拌槽に投入した。この撹拌槽において、反応熱が放熱され、また、気化した蒸気を還流することにより、臭素の飛散が抑制された。かかる撹拌槽で、引き続き混合溶液を撹拌し、撹拌槽内で約５分間滞留させた後に、撹拌槽のオーバーフロー口から流出させた。
【０２４５】
この反応溶液は、実施例５０と同様の処理を行い、反応生成物１.６ｇを得た。実施例５０と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−２−メチルプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物は、純度９４.０％、臭素含有率６５.３％（理論値６５.８％）であった。
【０２４６】
実施例５３
予め、ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝メタン１４.８ｋｇの塩化メチレン溶液４０ｋｇを調整した（溶液の比重は１.４７、含水率２００ｐｐｍ）。
【０２４７】
実施例５０で使用したものと同様のスタテックミキサーに、調整した上記塩化メチレン溶液を添加速度７９.８ｇ／秒（５４.３ｍＬ／秒）、臭素を添加速度１６.６ｇ／秒（５.４ｍＬ／秒）、すなわち混合溶液の流速が１１９ｃｍ／秒となるように、スタテックミキサー内に連続的に導入し、混合させた後（このスタテックミキサー内での滞留時間は０.３４秒）、スタテックミキサーから導出した混合溶液をコンデンサーを備えた容量２８Ｌの撹拌槽に投入した。この撹拌槽において、反応熱が放熱され、また、気化した蒸気を還流することにより、臭素の飛散が抑制された。かかる撹拌槽で、引き続き混合溶液を撹拌し、撹拌槽内で約８分間滞留させた後に、撹拌槽のオーバーフロー口から流出させた。
【０２４８】
この反応溶液は、実施例５０と同様の処理を行い、反応生成物１.８ｇを得た。実施例５０と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−プロピルオキシ）フェニル｝メタンであることが確認された。この臭素化合物は、純度９１.８％、臭素含有率６９.１％（理論値６９.８％）であった。
【０２４９】
実施例５４
予め、ビス｛（３,５−ジブロモ−４−イソブテニルオキシ）フェニル｝メタン１４.８ｋｇの塩化メチレンと１,４−ジオキサンの混合溶媒溶液（塩化メチレン／１,４−ジオキサン＝７０／３０重量比）４０ｋｇを調整した（溶液の比重は１.３５、含水率２５０ｐｐｍ）。
【０２５０】
実施例５０で使用したものと同様のスタテックミキサーに、調整した上記混合溶媒溶液を添加速度１２６.８ｇ／秒（９３.９ｍＬ／秒）、臭素を添加速度２８.８ｇ／秒（９.３ｍＬ／秒）、すなわち混合溶液の流速が２０６ｃｍ／秒となるように、スタテックミキサー内に連続的に導入し、混合させた後（このスタテックミキサー内での滞留時間は０.１９秒）、スタテックミキサーから導出した混合溶液をコンデンサーを備えた容量３０Ｌの撹拌槽に投入した。この撹拌槽において、反応熱が放熱され、また、気化した蒸気を還流させることにより、臭素の飛散が抑制された。かかる撹拌槽で、引き続き混合溶液を撹拌し、撹拌槽内で約５分間滞留させた後に、撹拌槽のオーバーフロー口から流出させた。
【０２５１】
この反応溶液は、実施例５０と同様の処理を行い、反応生成物１.８ｇを得た。実施例５０と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−２−メチルプロピルオキシ）フェニル｝メタンであることが確認された。この臭素化合物は、純度９２.０％、臭素含有率６７.０％（理論値６７.７％）であった。
【０２５２】
実施例５５
予め、（３,３’,５,５’−テトラブロモ−４,４’−ジアリルオキシ）ビフェニル１１.１ｋｇの塩化メチレンと１,４−ジオキサンの混合溶媒溶液（塩化メチレン／１,４−ジオキサン＝７０／３０重量比）３０ｋｇを調整した（溶液の比重は１.３５、含水率２５０ｐｐｍ）。
【０２５３】
実施例５０で使用したものと同様のスタテックミキサーに、調整した上記混合溶媒溶液を添加速度１４０.０ｇ／秒（１０３.７ｍＬ／秒）、臭素を添加速度２８.８ｇ／秒（９.３ｍＬ／秒）、すなわち混合溶液の流速が２２６ｃｍ／秒となるように、スタテックミキサー内に連続的に導入し、混合させた後（このスタテックミキサー内での滞留時間は０.１８秒）、スタテックミキサーから導出した混合溶液をコンデンサーを備えた容量２０Ｌの撹拌槽に投入した。この撹拌槽において、反応熱が放熱され、また、気化した蒸気を還流させることにより、臭素の飛散が抑制された。かかる撹拌槽で、引き続き混合溶液を撹拌し、撹拌槽内で約３分間滞留させた後に、撹拌槽のオーバーフロー口から流出させた。
【０２５４】
この反応溶液は、実施例５０と同様の処理を行い、反応生成物１.５ｇを得た。実施例５０と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、｛３,３’,５,５’−テトラブロモ−４,４’−（２,３−ジブロモ−プロピルオキシ）｝ビフェニルであることが確認された。この臭素化合物は、純度９３.５％、臭素含有率７０.０％（理論値７０.９％）であった。
【０２５５】
実施例５６
予め、ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝スルフォン１４.８ｋｇの塩化メチレン溶液４０ｋｇを調整した（溶液の比重は１.４７、含水率６００ｐｐｍ）。
【０２５６】
実施例５１で使用したものと同様のスタテックミキサーに、調整した上記塩化メチレン溶液を添加速度９９.３ｇ／秒（６７.６ｍＬ／秒）、臭素を添加速度２８.８ｇ／秒（９.３ｍＬ／秒）、すなわち混合溶液の流速が１５４ｃｍ／秒となるように、スタテックミキサー内に連続的に導入し、混合させた後（このスタテックミキサー内での滞留時間は０.１３秒）、スタテックミキサーから導出した混合溶液をコンデンサーを備えた容量１５Ｌの撹拌槽に投入した。この撹拌槽において、反応熱が放熱され、また、気化した蒸気を還流させることにより、臭素の飛散が抑制された。かかる撹拌槽で、引き続き混合溶液を撹拌し、撹拌槽内で約３分間滞留させた後に、撹拌槽のオーバーフロー口から流出させた。
【０２５７】
この反応溶液は、実施例５０と同様の処理を行い、反応生成物１.５ｇを得た。実施例５０と同様に得られた生成物を¹Ｈ−ＮＭＲおよびＦＴ−ＩＲを用いて分析した結果、生成物は、｛３,３’,５,５’−テトラブロモ−４,４’−（２,３−ジブロモ−プロピルオキシ）｝スルフォンであることが確認された。この臭素化合物は、純度９１.０％、臭素含有率６３.９％（理論値６６.２％）であった。 なお、実施例５０〜５６の結果を表１１に示した。
【０２５８】
【表１１】

【０２５９】
調整例１
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた１０Ｌのガラス製反応容器に、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン２７００ｇ（４.３３ｍｏｌ）および合成ゼオライトで脱水した塩化メチレン４６００ｇを入れ溶解させた。この溶液を撹拌しながら、３９〜４１℃の温度で塩化メチレンを還流させながら、臭素１３９４ｇ（８.７２ｍｏｌ）を８分で滴下漏斗より滴下した。滴下終了後、反応溶液を３９〜４１℃の温度で塩化メチレンを還流させながら３０分間撹拌し続け、臭素の付加反応を終了した。この反応溶液からホールピペットで１０ｍＬを分取し、臭素化合物溶液中の残留臭素を測定した結果３.６８ｇ／Ｌであった。
【０２６０】
調整例２
撹拌装置、コンデンサー、温度計および滴下漏斗を備えた１０Ｌのガラス製反応容器に、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン２７００ｇ（４.３３ｍｏｌ）および合成ゼオライトで脱水したクロロベンゼン４６０ｇを入れ溶解させた。この溶液を撹拌しながら、１５℃の温度で、臭素１３９４ｇ（８.７２ｍｏｌ）を１２０分で滴下漏斗より滴下した。滴下終了後、反応溶液を１５℃の温度で３０分間撹拌し続け、臭素の付加反応を終了した。この反応溶液からホールピペットで１０ｍＬを分取し、臭素化合物溶液中の残留臭素を測定した結果３.６０ｇ／Ｌであった。
【０２６１】
調整例３
調整例１において、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン２７００ｇの代わりに、２,２−ビス｛（３,５−ジブロモ−４−イソブテニルオキシ）フェニル｝プロパン２８２０ｇ（４.３３ｍｏｌ）を用いた以外は、調整例１と同様に臭素化反応を行い、臭素化合物溶液中の残留臭素を測定した結果３.０５ｇ／Ｌであった。
【０２６２】
調整例４
調整例１において、２,２−ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝プロパン２７００ｇの代わりに、ビス｛（３,５−ジブロモ−４−アリルオキシ）フェニル｝メタン２５８０ｇ（４.３３ｍｏｌ）を用いた以外は、調整例１と同様に臭素化反応を行い、臭素化合物溶液中の残留臭素を測定した結果３.０５ｇ／Ｌであった。
【０２６３】
実施例５７
調整例１で得られた臭素化合物溶液３２８ｇに、１５.６重量％の亜硫酸水素ナトリウム水溶液１２.５ｇ（臭素１モルに対して亜硫酸水素ナトリウム３.７モル）を添加して、直ちに２５重量％の水酸化ナトリウム水溶液３.８ｇ（臭素１モルに対して水酸化ナトリウム４.７モル）を加え、さらに、塩化メチレン相と水相との重量比がほぼ１：１となるように水３００ｇを加えて、２０℃で３０分間撹拌を行った。撹拌終了後、塩化メチレン相と水相とを分離した。水相を除去し、塩化メチレン相に水１００ｍＬを加えて１５分間撹拌、洗浄した。水相のｐＨは７.２であり、また、両相とも臭素は検出されなかった。
【０２６４】
次に、この還元、中和処理した塩化メチレン相１００ｍＬを取り、かかる塩化メチレン相から塩化メチレンを９０％程度蒸発、除去し、これにメタノールを２５０ｍＬ加え反応生成物を沈殿させ、この沈殿物をろ過して塊状固体を取り出した。この塊状固体を乳鉢で粉砕し、８０℃、３時間、５ｍｍＨｇで減圧乾燥し生成物１１４.７ｇを得た。
【０２６５】
得られた生成物を¹Ｈ−ＮＭＲで分析したところ４.５１〜４.５３ｐｐｍに−ＣＨＢｒ−由来のシグナルが、３.９４〜４.０９ｐｐｍに−ＣＨ₂Ｂｒ由来のシグナルが認められた。またＦＴ−ＩＲ分析より、−Ｏ−ＣＨ₂−の吸収を認め、アリル基の吸収は認められないのを確認した。以上の分析結果より、生成物は、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンであることが確認された。この臭素化合物１ｇを水１０ｇに添加し、２０℃で２４時間撹拌した後、臭素化合物を濾過して、水相の臭素濃度を測定したところ臭素は検出されなかった。
【０２６６】
実施例５８
実施例５７において、１５.６重量％の亜硫酸水素ナトリウム水溶液１２.５ｇを２４.５ｇ（臭素１モルに対して亜硫酸水素ナトリウム７.３モル）に代え、２５重量％の水酸化ナトリウム水溶液３.８ｇを１３.１ｇ（臭素１モルに対して水酸化ナトリウム１６.３モル）に代える以外は、実施例５７と同様に還元、中和処理した。塩化メチレン相と水相とを分離して、水相を除去し、塩化メチレン相に水１００ｍＬを加えて１５分間撹拌、洗浄した。水相のｐＨは７.２であり、また、両相とも臭素は検出されなかった。
【０２６７】
次に、実施例５７と同様にして、塩化メチレン相から２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンを得た。この臭素化合物１ｇを水１０ｇに添加し、２０℃で２４時間撹拌した後、臭素化合物を濾過して、水相の臭素濃度を測定したところ臭素は検出されなかった。
【０２６８】
実施例５９
実施例５７において、１５.６重量％の亜硫酸水素ナトリウム水溶液１２.５ｇを１５.６重量％のシュウ酸水溶液９.７ｇ（臭素１モルに対してシュウ酸３.３モル）に代える以外は、実施例５７と同様に還元、中和処理した。塩化メチレン相と水相とを分離して、水相を除去し、塩化メチレン相に水１００ｍＬを加えて１５分間撹拌、洗浄した。水相のｐＨは７.２であり、また、両相とも臭素は検出されなかった。
【０２６９】
次に、実施例５７と同様にして、塩化メチレン相から２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンを得た。この臭素化合物１ｇを水１０ｇに添加し、２０℃で２４時間撹拌した後、臭素化合物を濾過して、水相の臭素濃度を測定したところ臭素は検出されなかった。
【０２７０】
実施例６０
実施例５７において、１５.６重量％の亜硫酸水素ナトリウム水溶液１２.５ｇを１５.６重量％の亜硝酸ナトリウム水溶液７.１ｇ（臭素１モルに対して亜硝酸ナトリウム３.２モル）に代える以外は、実施例５７と同様に還元、中和処理した。塩化メチレン相と水相とを分離して、水相を除去し、塩化メチレン相に水１００ｍＬを加えて１５分間撹拌、洗浄した。水相のｐＨは７.２であり、また、両相とも臭素は検出されなかった。
【０２７１】
次に、実施例５７と同様にして、塩化メチレン相から２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンを得た。この臭素化合物１ｇを水１０ｇに添加し、２０℃で２４時間撹拌した後、臭素化合物を濾過して、水相の臭素濃度を測定したところ臭素は検出されなかった。
【０２７２】
実施例６１
調整例２で得られた臭素化合物溶液３２８ｇに、１５.６重量％の亜硫酸水素ナトリウム水溶液１２.５ｇ（臭素１モルに対して亜硫酸水素ナトリウム３.０モル）を添加して、直ちに２５重量％の水酸化ナトリウム水溶液３.８ｇ（臭素１モルに対して水酸化ナトリウム３.９モル）を加え、さらに、クロロベンゼン相と水相との重量比がほぼ１：１となるように水３００ｇを加えて、２０℃で３０分間撹拌を行った。撹拌終了後、クロロベンゼン相と水相とを分離した。水相を除去し、クロロベンゼン相に水１００ｍＬを加えて１５分間撹拌、洗浄した。水相のｐＨは７.２であり、また、両相とも臭素は検出されなかった。
【０２７３】
次に、この還元、中和処理したクロロベンゼン相１００ｍＬを取り、かかるクロロベンゼン相からクロロベンゼンを９０％程度蒸発、除去し、これにメタノールを２５０ｍＬ加え反応生成物を沈殿させ、この沈殿物をろ過して塊状固体を取り出した。この塊状固体を乳鉢で粉砕し、８０℃、３時間、５ｍｍＨｇで減圧乾燥し、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝プロパンを得た。この臭素化合物１ｇを水１０ｇに添加し、２０℃で２４時間撹拌した後、臭素化合物を濾過して、水相の臭素濃度を測定したところ臭素は検出されなかった。
【０２７４】
実施例６２
調整例３で得られた臭素化合物溶液３２４ｇに、１５.６重量％の亜硫酸水素ナトリウム水溶液１３.０ｇ（臭素１モルに対して亜硫酸水素ナトリウム４.７モル）を添加して、直ちに２５重量％の水酸化ナトリウム水溶液４.０ｇ（臭素１モルに対して水酸化ナトリウム６.１モル）を加え、さらに、塩化メチレン相と水相との重量比がほぼ１：１となるように水３００ｇを加えて、２０℃で３０分間撹拌を行った。撹拌終了後、塩化メチレン相と水相とを分離した。水相を除去し、塩化メチレン相に水１００ｍＬを加えて１５分間撹拌、洗浄した。水相のｐＨは７.２であり、また、両相とも臭素は検出されなかった。
【０２７５】
次に、この還元、中和処理した塩化メチレン相１００ｍＬを取り、かかる塩化メチレン相から塩化メチレンを９０％程度蒸発、除去し、これにメタノールを２５０ｍＬ加え反応生成物を沈殿させ、この沈殿物をろ過して塊状固体を取り出した。この塊状固体を乳鉢で粉砕し、８０℃、３時間、５ｍｍＨｇで減圧乾燥し、２,２−ビス｛３,５−ジブロモ−４−（２,３−ジブロモ−２−メチルプロピルオキシ）フェニル｝プロパンを得た。この臭素化合物１ｇを水１０ｇに添加し、２０℃で２４時間撹拌した後、臭素化合物を濾過して、水相の臭素濃度を測定したところ臭素は検出されなかった。
【０２７６】
実施例６３
調整例４で得られた臭素化合物溶液３２８ｇに、１５.６重量％の亜硫酸水素ナトリウム水溶液１２.５ｇ（臭素１モルに対して亜硫酸水素ナトリウム４.５モル）を添加して、直ちに２５重量％の水酸化ナトリウム水溶液３.９ｇ（臭素１モルに対して水酸化ナトリウム５.８モル）を加え、さらに、塩化メチレン相と水相との重量比がほぼ１：１となるように水３００ｇを加えて、２０℃で３０分間撹拌を行った。撹拌終了後、塩化メチレン相と水相とを分離した。水相を除去し、塩化メチレン相に水１００ｍＬを加えて１５分間撹拌、洗浄した。水相のｐＨは７.２であり、また、両相とも臭素は検出されなかった。
【０２７７】
次に、この還元、中和処理した塩化メチレン相１００ｍＬを取り、かかる塩化メチレン相から塩化メチレンを９０％程度蒸発、除去し、これにメタノールを２５０ｍＬ加え反応生成物を沈殿させ、この沈殿物をろ過して塊状固体を取り出した。この塊状固体を乳鉢で粉砕し、８０℃、３時間、５ｍｍＨｇで減圧乾燥し、ビス｛３,５−ジブロモ−４−（２,３−ジブロモプロピルオキシ）フェニル｝メタンを得た。この臭素化合物１ｇを水１０ｇに添加し、２０℃で２４時間撹拌した後、臭素化合物を濾過して、水相の臭素濃度を測定したところ臭素は検出されなかった。
【０２７８】
実施例６４
内容積２０ｃｍ³のエレメント数１２からなるスタテックミキサー（断面積０.５ｃｍ²）に、調整例１で調整した塩化メチレン溶液を添加速度１０.７ｇ／秒（７.２ｍＬ／秒）、１５.６重量％の亜硫酸水素ナトリウムの水溶液を添加速度０.４ｇ／秒（０.３８ｍＬ／秒）、すなわち混合溶液の流速が１５.３ｃｍ／秒となるようにスタテックミキサー内に連続的に導入し、混合させた後（このスタテックミキサー内での滞留時間は２.６秒であり、臭素１モルに対して亜硫酸水素ナトリウム３.７モルである）、容量３０Ｌの底部に底抜きバルブのある攪拌槽に投入した。この撹拌槽内で、引き続き混合溶液を撹拌し、撹拌槽内で約１０分間滞留させた後に、一部を底部より取り出した。塩化メチレン溶液相の臭素濃度を測定したところ臭素は検出されなかった。
【０２７９】
次に、撹拌槽の底部より取り出した還元処理した混合溶液１４Ｌを２.５重量％の水酸化ナトリウムの水溶液３０００ｇに激しく撹拌しながら加えた（臭素１モルに対して水酸化ナトリウム５.９モルである）。この撹拌を２０分間行った。撹拌終了後、塩化メチレン相と水相とを分離した。水相を除去し、塩化メチレン相に純水２０００ｇを加えて２０分間撹拌、洗浄した。還元および中和反応を終了させるに要した時間は約１時間であった。
【０２８０】
実施例６５
実施例６４の内容積２０ｃｍ³のエレメント数１２からなるスタテックミキサー（断面積０.５ｃｍ²）の代わりに内容積３０ｃｍ³のエレメント数１８からなるスタテックミキサー（断面積０.５ｃｍ²）を使用し、亜硫酸水素ナトリウムの水溶液の濃度を５.２重量％とし、その添加速度を０.８ｇ／秒（０.７５ｍＬ／秒）とする以外は実施例６４と全く同様の操作を行った（混合溶液の流速が１５.９ｃｍ／秒であり、スタテックミキサー内での滞留時間は３.８秒であり、臭素１モルに対して亜硫酸水素ナトリウム２.５モルである）。実施例６４と同様に還元反応後の塩化メチレン溶液相の臭素濃度を測定したところ臭素は検出されなかった。
【０２８１】
実施例６６
実施例６４の内容積２０ｃｍ³のエレメント数１２からなるスタテックミキサー（断面積０.５ｃｍ²）の代わりに内容積３０ｃｍ³のエレメント数１８からなるスタテックミキサー（断面積０.５ｃｍ²）を使用し、塩化メチレン溶液を添加速度２６.９ｇ／秒（１８.２ｍＬ／秒）とし、亜硫酸水素ナトリウムの水溶液の添加速度を１.０４ｇ／秒（０.９５ｍＬ／秒）とする以外は実施例１と全く同様の操作を行った（混合溶液の流速が３８.３ｃｍ／秒であり、スタテックミキサー内での滞留時間は１.５秒であり、臭素１モルに対して亜硫酸水素ナトリウム３.７モルである）。実施例６４と同様に還元反応後の塩化メチレン溶液相の臭素濃度を測定したところ臭素は検出されなかった。
【０２８２】
実施例６７
実施例６４において、亜硫酸水素ナトリウムの水溶液の添加速度を０.８ｇ／秒（０.７５ｍＬ／秒）に代える以外は実施例１と全く同様の操作を行った（混合溶液の流速が１６.０ｃｍ／秒であり、スタテックミキサー内での滞留時間は２.６秒であり、臭素１モルに対して亜硫酸水素ナトリウム７.４モルである）。実施例６４と同様に還元反応後の塩化メチレン溶液相の臭素濃度を測定したところ臭素は検出されなかった。
【０２８３】
実施例６８
実施例６４において、調整例１で調整した塩化メチレン溶液を調整例２で調整したクロロベンゼン溶液に代え、その添加速度を１０.９ｇ／秒（９.９ｍＬ／秒）とする以外は実施例１と全く同様の操作を行った（混合溶液の流速が２０.７ｃｍ／秒であり、スタテックミキサー内での滞留時間は１.９秒であり、臭素１モルに対して亜硫酸水素ナトリウム３.０モルである）。実施例１と同様に還元反応後のクロロベンゼン溶液相の臭素濃度を測定したところ臭素は検出されなかった。
【０２８４】
実施例６９
実施例６４において、調整例１で調整した塩化メチレン溶液を調整例４で調整した塩化メチレン溶液に代える以外は実施例６４と全く同様の操作を行った（混合溶液の流速が１５.２ｃｍ／秒であり、スタテックミキサー内での滞留時間は２.７秒であり、臭素１モルに対して亜硫酸水素ナトリウム３.７モルである）。実施例６４と同様に還元反応後の塩化メチレン溶液相の臭素濃度を測定したところ臭素は検出されなかった。
【０２８５】
実施例７０
実施例６４において、塩化メチレン溶液を添加速度５.４ｇ／秒（３.６ｍＬ／秒）とし、亜硫酸水素ナトリウムの水溶液の添加速度を０.２ｇ／秒（０.１９ｍＬ／秒）とする以外は実施例１と全く同様の操作を行った（混合溶液の流速が７.６ｃｍ／秒であり、スタテックミキサー内での滞留時間は５.３秒であり、臭素１モルに対して亜硫酸水素ナトリウム３.７モルである）。実施例６４と同様に還元反応後の塩化メチレン溶液相の臭素濃度を測定したところ臭素は検出されなかった。
【０２８６】
実施例７１
実施例６４において、亜硫酸水素ナトリウムの水溶液の代わりに１５.６重量％の亜二チオン酸ナトリウムの水溶液を使用し、その添加速度を０.４ｇ／秒（０.３８ｍＬ／秒）とする以外は実施例１と全く同様の操作を行った（混合溶液の流速が１５.２ｃｍ／秒であり、スタテックミキサー内での滞留時間は２.６秒であり、臭素１モルに対して亜二チオン酸ナトリウム２.５モルである）。実施例６４と同様に還元反応後の塩化メチレン溶液相の臭素濃度を測定したところ臭素は検出されなかった。
【図面の簡単な説明】
【図１】傾斜角（７０℃、４時間加熱後）の評価における傾斜角を示す図である。
【符号の説明】
１ ガラス面
２ 試料
３ 水平な面
【図２】本発明における臭素化反応を行う反応装置の一例を示すものである。
【図３】本発明における臭素化反応を行う反応装置の他の一例を示すものである。
【符号の説明】
１ 原料化合物溶液の投入口
２ 臭素または臭素溶液の投入口
３ 撹拌翼
４ コンデンサー
５ 温度計
６ ポンプ
７ 循環液の投入口
８ 反応溶液の導入口
９ 反応溶液[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a bromine compound by brominating a compound having an aliphatic unsaturated bond. More specifically, the present invention relates to a method for industrially advantageously producing a high purity bromine compound from a compound having an aliphatic unsaturated bond.
[0002]
[Prior art]
In general, a bromination reaction to an aliphatic unsaturated group is a reaction that is frequently employed in the field of organic chemistry when synthesizing a brominated derivative. It is essential to remove the heat of reaction from the inside, and for this purpose, an operation of cooling the reaction system and adding bromine over time in a mild state is generally employed.
[0003]
For example, Japanese Patent Publication No. 49-39655 describes a method for producing β, γ-dibromopropylbenzene, but when adding bromine, the reaction is carried out at a low temperature so that no side reaction occurs. Is described.
[0004]
Japanese Patent Laid-Open No. 55-111429 discloses an aromatic halogenated carbonization of diallyl ether obtained from 2,2-bis-{(4-hydroxy-3,5-dibromo) phenyl} propane and allyl chloride. Although it has been shown to carry out bromination in a hydrogen solvent, it has been described that such bromination is carried out at temperatures of 10-30 ° C., in particular 15-25 ° C., and in the examples about 20 A method of adding bromine under cooling at a temperature of 0 ° C. is specifically shown.
[0005]
JP-A-50-30853 relates to a method for recovering solids, and in the examples, the reaction between 2,2-bis ({(3,5-dibromo-4-allyloxy) phenyl} propane and bromine is 20 ° C. or less. Specifically, a method of dropping bromine at a temperature of 5 is described.
[0006]
In JP-A-7-173092, as a method for obtaining a 2,3-dibromopropyl compound, specifically, 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane and bromine are used. As for the reaction, a method is described in which bromine is added dropwise at a reaction temperature of 10 to 20 ° C. over 1 hour.
[0007]
Furthermore, in Japanese Patent Application Laid-Open No. 7-316087, as a specific example, a reaction temperature is set to 24 by using a cooling pipe in a methylene chloride solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane. A method is disclosed in which bromine is added dropwise over 1 hour while controlling at ˜27 ° C.
[0008]
On the other hand, for example, in Japanese Patent Publication No. 50-23893, as a specific example, in bromination of bis {(3,5-dibromo-4-allyloxy) phenyl} sulfone, such a compound is dissolved in methylene chloride, and bromine is added thereto. The process of reacting at the boiling point of methylene chloride is shown.
[0009]
Further, bromination of bis {(3,5-dibromo-4-allyloxy) phenyl} sulfone is also disclosed in JP-A-3-271267 and JP-A-4-234354. Describes a method in which bromine is dropped into a methylene chloride solution of such a compound at 39 ° C. or 40 ° C. over 1 hour, and the latter is a method in which bromine is dropped at 35 to 39 ° C. over 1.5 hours. Yes. In any of these methods, the reaction is performed in a container having a cooling pipe.
[0010]
All of the methods described in these patent publications are small-scale reactions at the laboratory level. In many cases, a flask is used as a reaction apparatus, and most of the reaction itself is cooled to remove reaction heat. The method to do is adopted. These publications disclose conditions and means at the laboratory level, but on an industrial scale to effectively remove a large amount of reaction heat and obtain a high yield and high purity bromide. No specific conditions or means are disclosed.
[0011]
In order to carry out bromination of a compound having an aliphatic unsaturated bond, particularly polybromination on an industrial scale, it is necessary to effectively remove a large amount of reaction heat, and means and equipment therefor. Development is required. In addition, when the reaction heat is not effectively removed, bromine must be supplied gradually, which increases the reaction time, leading to a decrease in yield and purity.
[0012]
[Problems to be solved by the invention]
In view of the present situation, the present inventor has conducted intensive research for the purpose of providing a method for producing a high-purity bromine compound by efficiently reacting a compound having an aliphatic unsaturated bond with bromine on an industrial scale. As a result, when bromination is carried out by reacting a compound having an aliphatic unsaturated bond with bromine in the presence of a solvent inert to the reaction, the substantial amount of heat of the bromination reaction is determined by the heat of vaporization of the solvent or bromine. It was found that by removing from the reaction system by the above, a bromine compound having high yield and high purity can be produced without causing side reactions, and the present invention has been achieved.
[0013]
[Means for Solving the Problems]
That is, according to the present invention, in a method for producing a bromine compound represented by the following general formula (2) by reacting a compound having an aliphatic unsaturated bond represented by the following general formula (1) with bromine. , The compound represented by the general formula (1), bromine, and a solvent inert to the reaction are continuously fed into the reactor separately or as a mixture of any combination, in which case the general formula (1) ) Is supplied in an amount of 1 to 5 molecules of bromine per unsaturated group in the compound, and the substantial amount of heat of reaction is vaporized in the solvent or bromine in the reactor. Reaction while removing by heat, taking out the reaction mixture from the reactor, and then recovering the bromine compound represented by the general formula (2) from the reaction mixture A continuous process for producing a bromine compound is provided.
R ¹ -O-Ar ¹ -Y-Ar ² -O-R ² (1)
(Wherein Ar ¹ And Ar ² May be the same or different and each represents an aromatic hydrocarbon group having 5 to 16 carbon atoms or a saturated alicyclic hydrocarbon group having 5 to 12 carbon atoms, and these hydrocarbon groups have at least one halogen atom Y represents a saturated hydrocarbon group having 1 to 6 carbon atoms, a sulfone group, a sulfide group, a ketone group, an alkylene oxide group having 2 to 6 carbon atoms or a single bond; R ¹ And R ² May be the same or different and each represents a C 2-11 hydrocarbon group having at least one aliphatic unsaturated group, ¹ And R ² In any one of these, a part of the unsaturated group may be added with a halogen atom. )
R ³ -O-Ar ¹ -Y-Ar ² -O-R ⁴ (2)
(Wherein Ar ¹ , Ar ² And Y are the same as defined in the general formula (1). R ³ And R ⁴ Are R in the general formula (1), respectively. ¹ And R ² The group in which the unsaturated group in is saturated with a bromine atom. )
[0014]
Hereinafter, the method for producing a bromine compound according to the present invention will be described more specifically and in detail.
The compound having an aliphatic unsaturated bond used in the method of the present invention is represented by the general formula (1). In this general formula (1), Ar ¹ And Ar ² May be the same or different and is an aromatic hydrocarbon group having 5 to 16 carbon atoms, preferably 6 to 12 carbon atoms or a saturated alicyclic hydrocarbon group having 5 to 12 carbon atoms, preferably 6 to 10 carbon atoms. It is. Ar ¹ And Ar ² Are industrially advantageous if they are the same and are aromatic hydrocarbon groups. Ar ¹ And Ar ² Specific examples thereof include 1,4-dimethylphenylene group, 1,4-methylphenylene group, 1,4-dimethylphenylene group, 2,6-naphthylene group, and 2,7-naphthylene group. A phenylene group is preferred.
[0015]
These Ar ¹ And Ar ² The carbon atom forming the hydrocarbon may be substituted with a halogen atom, and for the purpose of producing a flame retardant, it is preferable that a halogen atom, particularly a bromine atom is substituted. Ar ¹ And Ar ² In each of the above, the number of substituted halogen atoms is Ar ¹ (Or Ar ² 1 to 6, preferably 2 to 4, are advantageous.
[0016]
In general formula (1), Y represents Ar. ¹ And Ar ² A saturated hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms; a sulfone group (—SO 2 —); a sulfide group (—S—); a ketone group (—CO—). ); An alkylene oxide group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms; or a single bond. Preferred Y is a methylene group, isopropylidene group, cyclohexylidene group, sulfide group, sulfone group, ketone group or single bond.
[0017]
In the general formula (1), R ¹ And R ² May be the same or different and represents a hydrocarbon group having 2 to 11 carbon atoms, preferably 2 to 5 carbon atoms, having at least one aliphatic unsaturated group, ¹ And R ² In any one of these, a part of the unsaturated group may be substituted with a halogen atom, preferably a bromine atom, and may be saturated. R ¹ And R ² Specific examples of these include vinyl group, allyl group and isobutenyl group.
[0018]
As the compound having an aliphatic unsaturated bond represented by the general formula (1) of the present invention, specifically, 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane, 2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane, bis {(3,5-dibromo-4-allyloxy) phenyl} methane, bis {(3,5-dibromo-4- Isobutenyloxy) phenyl} methane, (3,3 ′, 5,5′-tetrabromo-4,4′-diallyloxy) biphenyl, (3,3 ′, 5,5′-tetrabromo-4,4′- Examples include divinyloxy) biphenyl, bis {(3,5-dibromo-4-allyloxy) phenyl} sulfone, and bis {(3,5-dibromo-4-isobutenyloxy) phenyl} sulfone. , 2-bis {(3,5-di Lomo-4-allyloxy) phenyl} propane, 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane, bis {(3,5-dibromo-4-allyloxy) phenyl} methane Bis {(3,5-dibromo-4-isobutenyloxy) phenyl} methane, (3,3 ′, 5,5′-tetrabromo-4,4′-diallyloxy) biphenyl and (3,3 ′, 5,5′-tetrabromo-4,4′-divinyloxy) biphenyl is preferred, and 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane, 2,2-bis {(3, 5-dibromo-4-isobutenyloxy) phenyl} propane, bis {(3,5-dibromo-4-allyloxy) phenyl} methane and bis {(3,5-dibromo-4-isobutenyloxy) phenyl} More preferably Tan, in particular 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane is preferably used.
[0019]
In the method of the present invention, the reaction between a compound having an aliphatic unsaturated bond and bromine is carried out in the presence of a solvent, and the solvent must be inert without adversely affecting the reaction. Such a solvent is more preferable as it has higher solubility in a compound having an aliphatic unsaturated bond, but may be partially soluble. Moreover, it is preferable that the bromine compound produced | generated by bromination reaction of the compound which has this aliphatic unsaturated bond substantially melt | dissolves in this solvent.
[0020]
The solvent in the method of the present invention is not only used as a mere solvent for uniformly carrying out the reaction, but preferably has a function as a solvent for effectively removing heat of reaction out of the system. . Therefore, the solvent has an atmospheric pressure boiling point of 0 to 100 ° C., preferably 20 to 90 ° C., and particularly when the heat of reaction is substantially removed by the heat of vaporization of the solvent, the atmospheric pressure boiling point is 20 Those in the range of -80 ° C, particularly 20-60 ° C are desirable.
[0021]
Examples of such solvents include halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, 1,1-dichloroethane, bromoethane, butyl chloride, and chloropropane, and ether-based carbonization such as diethyl ether, ethyl isopropyl ether, tetrahydrofuran, and dioxane. Examples thereof include hydrogen compounds, aromatic hydrocarbon compounds such as benzene, carbon disulfide, and pentane. Bromine can also be used as a solvent.
[0022]
Of these solvents, halogenated hydrocarbons are preferable, and methylene chloride and chloroform are particularly preferably used as the solvent. These solvents are used alone or in combination. These halogenated hydrocarbons can also be used as a mixed solvent with dioxane.
[0023]
These solvents are used in an amount of 2-1000 molecules, preferably 2.5-800 molecules, per unsaturated group in the compound represented by the general formula (1). In the reaction of the present invention, it is preferable that a substantial amount of the reaction heat is removed from the reaction system by the heat of vaporization of the solvent. Therefore, the solvent is more preferably 3 to 700 molecules, and particularly preferably 4 to 600. The use in molecular proportions is advantageous.
[0024]
The method of the present invention is characterized in that the heat of reaction is discharged by the heat of vaporization of the solvent or bromine. Therefore, it is sufficient that the amount of solvent or bromine that can provide the heat of vaporization corresponding to the heat of reaction is present in the reaction system. However, since bromine is involved in the reaction, it is reasonable and advantageous to remove the heat of reaction, preferably with the heat of vaporization by the solvent.
[0025]
The amount of bromine used in the method of the present invention may be a sufficient molar ratio with respect to the compound having an aliphatic unsaturated bond in order to obtain a desired bromine compound, and the compound having such an aliphatic unsaturated bond. The amount of bromine is preferably in the range of 1 to 5 molecules per unsaturated group, and more preferably in the range of 1.1 to 3 molecules of bromine.
[0026]
In the method of the present invention, bromine itself or a bromine solution is used. As the solvent for use in the bromine solution, the same solvents as those described above are used, and the bromine concentration in that case is preferably in the range of 10 to 90% by weight.
[0027]
In the method of the present invention, as a specific means, an aliphatic unsaturated bond is formed by mixing a solution of a compound having an aliphatic unsaturated bond in a solvent inert to bromine with bromine or a bromine solution. The compound which has and bromine are made to react. In this bromination reaction, it is an essential condition that a substantial amount of reaction heat of bromination is removed by the heat of vaporization of the solvent or bromine. The substantial amount of reaction heat means 80% or more, preferably 85% or more of the theoretical calorific value generated by the desired bromination reaction.
[0028]
The reaction temperature in the bromination reaction of the present invention is not particularly limited, as long as the substantial amount of bromination reaction heat is removed by bromine or the heat of vaporization of the solvent as described above. The reaction is not limited to normal pressure, and can be performed under pressure or under reduced pressure. The reaction temperature is preferably 0 ° C. or higher, and more preferably 5 ° C. or higher. In addition, when the boiling point of the solvent used is lower than the boiling point of bromine, the reaction temperature can be increased by pressurization. When the boiling point of the solvent used is higher than the boiling point of bromine, the reaction is performed by reducing the pressure. The temperature can be lowered.
[0029]
Thus, the reaction temperature of the present invention can be controlled by the operating pressure in relation to the type of solvent used (boiling point) and the amount of bromine. Usually, the reaction temperature is advantageously in the range of 0-60 ° C, preferably in the range of 5-55 ° C, particularly preferably in the range of 10-50 ° C.
[0030]
In the method of the present invention, during the bromination reaction, a substantial amount of the bromination reaction heat is removed by the heat of vaporization of the solvent or bromine, but the vaporized vapor is removed from a condenser or the like installed at the top of the reactor. The method of cooling and liquefying the solution and returning it to the reaction system, that is, the method of refluxing is preferably used because it is easy to operate. The removal of reaction heat by vaporization can also be carried out by a method that does not use a condenser. This method will be described later.
[0031]
By removing a substantial amount of the heat of reaction for bromination with the heat of vaporization of the solvent or bromine, the produced bromine compound has a high purity. By simply reacting a compound having an aliphatic unsaturated bond with bromine at a high temperature, a by-product is likely to be generated and the purity is deteriorated as compared with a reaction at a low temperature. The bromine compound can be obtained. It is considered that this is because the compound having an aliphatic unsaturated bond and bromine are uniformly dispersed in the solution due to the stirring effect when the solvent or bromine is vaporized, and side reactions are unlikely to occur.
[0032]
In the method of the present invention, a method of mixing a solution in which a compound having an aliphatic unsaturated bond is dissolved in an inert solvent and bromine or a bromine solution is not particularly limited, and the bromine or bromine solution is mixed with an aliphatic unsaturated solution. A method of adding and mixing to a solution of a compound having a saturated bond, or a method of adding and mixing a solution of a compound having an aliphatic unsaturated bond to bromine or a bromine solution, or a bromine or bromine solution and an aliphatic unsaturated bond Any method of simultaneously adding and mixing a solution of a compound having s to a reactor can be employed.
[0033]
In the method of the present invention, the reaction between a compound having an aliphatic unsaturated bond and bromine is carried out in the presence of a solvent inert to the reaction, and the amount of heat of reaction is increased by the heat of vaporization of the solvent or bromine. Therefore, it is desirable to employ conditions and means for effectively discharging a large amount of reaction heat generated as a vapor to the outside of the reaction system by vaporization of the solvent or bromine. These conditions and means will be described in a specific and detailed manner below. The reaction components and the solvent are in uniform contact with each other, the vaporization of the solvent and bromine is carried out effectively, and the reaction heat is discharged out of the system. Is carried out smoothly, as a result, the reaction can be completed early, and it is desirable to obtain a bromine compound having excellent purity. Therefore, it is more preferable to adopt a means for sufficiently mixing the reaction mixture in the reaction system.
[0034]
Thus, it is industrially advantageous that the selection of the solvent and the proportion thereof, the proportion of bromine and the reaction temperature are set from the aforementioned ranges. Furthermore, it has been found that the presence of water and the addition of alcohol in the reaction system affects the purity and quality of the bromine compound. These points will be described next.
[0035]
In the reaction of the present invention, impurities present in the reaction solution are important factors for the purpose of efficiently carrying out the bromination reaction of the present invention and obtaining a bromine compound with high yield and purity. In particular, water present in the reaction solution reacts with bromine to form an active intermediate, and this active intermediate reacts with an aliphatic unsaturated group in a competitive reaction. The presence of water contained in the compound having an unsaturated bond, bromine and the solvent should be paid careful attention, and basically the coexistence of water should be avoided. Therefore, the concentration of water is preferably 10 molecules or less, more preferably 0.05 to 10 molecules, and even more preferably 0.05 to 5 molecules with respect to 100 unsaturated groups of the compound having an aliphatic unsaturated bond. When the concentration of water is high, the bromine compound obtained is of low purity, and is liable to adhere to each other, resulting in a solid lacking storage stability, which is not preferable. The water content is measured by the Karl Fischer method.
[0036]
The concentration of water in the reaction solution can be reduced to some extent by removing water contained in each of the compound having an aliphatic unsaturated bond, bromine and the solvent. However, when the reaction is performed on an industrial scale, it is extremely difficult to avoid a certain amount of moisture from being mixed into the reaction system due to restrictions on the apparatus and operation. Accordingly, the present inventors have conducted research on a method that does not have a significant adverse effect on the handling and utilization of the obtained bromine compound even when a trace amount of water is present in the reaction system. It has been found that the method of adding a specific alcohol is excellent.
The alcohol added to the reaction system is represented by the following general formula (3).
R ^Five -(OH) _n (3)
(Wherein R ^Five Represents an n-valent aliphatic group having 1 to 6 carbon atoms, and n represents an integer of 1 to 4. )
[0037]
In the general formula (3), R ^Five Is an aliphatic group having 1 to 4 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an oxygen-containing saturated hydrocarbon group having 1 to 4 carbon atoms, or a group having 1 to 4 carbon atoms. Sulfur saturated hydrocarbon. N is an integer of 1 to 4, preferably an integer of 1 to 2. Specific examples of the alcohol represented by the general formula (3) include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, allyl alcohol, and ethylene. Glycol, diethylene glycol and the like, and methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol and tert-butanol are preferable, and methanol, ethanol and i-propanol are particularly preferable. .
[0038]
The alcohol has 0.5 to 20, preferably 0.8 to 18, more preferably 1 to 100 hydroxyl groups per 100 unsaturated groups with respect to the compound having an aliphatic unsaturated bond. An amount corresponding to 15, particularly preferably 1 to 10, is used. When the amount of alcohol is less than the amount corresponding to 0.5 hydroxyl groups per 100 unsaturated groups with respect to the compound having an aliphatic unsaturated bond, it is produced by the reaction of water and bromine. The reaction between the active intermediate and the compound having an aliphatic unsaturated bond is likely to proceed, and the thermal stability of the resulting bromine compound is undesirably lowered. When the amount exceeds 20 equivalents, the alcohol and bromine The amount of by-products generated by the reaction of the intermediate produced by the reaction with a compound having an aliphatic unsaturated bond increases, resulting in insufficient purity of the bromine compound, and This is not preferable because it adversely affects the flame retardancy of the resin composition blended in the resin as a flame retardant.
[0039]
In the bromination reaction of the present invention, as described above, the alcohol represented by the general formula (3) is present in a solution obtained by mixing a solution of a compound having an aliphatic unsaturated bond with bromine or a bromine solution. Thereby, the production | generation of the by-product resulting from a water | moisture content is suppressed. However, if the amount of water present in the mixed solution is too large, a large amount of the compound having a hydroxyl group is used in order to suppress side reactions caused by moisture. The intermediate produced by the reaction with bromine produces a large amount of by-products that have reacted with the compound having an aliphatic unsaturated bond, resulting in an insufficient purity of the bromine compound, and making this bromine compound difficult. This will adversely affect the flame retardancy of the resin composition blended in the resin as a flame retardant. Therefore, the concentration of water in a solution of a compound having an aliphatic unsaturated bond in the bromination reaction, a reaction solution substantially consisting of a bromine or bromine solution and a compound having a hydroxyl group has an aliphatic unsaturated bond. As described above, the amount corresponding to 10 or less water molecules per 100 unsaturated groups is preferable for the compound, and the amount corresponding to 0.05 to 10 is more preferable, and 0.05 to 5 is preferable. An amount corresponding to an individual is more preferable.
[0041]
In the following explanation, explanation of the control of moisture in the reaction system and the addition of alcohol is omitted. In particular, when an alcohol is added, it may be added alone or in any of a compound having an aliphatic unsaturated bond, bromine or a solvent. Moreover, you may add to these mixtures.
In the following description, a compound having an aliphatic unsaturated bond is simply abbreviated as “unsaturated compound”, and a solvent inert to the reaction is simply abbreviated as “solvent”.
[0055]
In the continuous method of the present invention, the compound represented by the general formula (1), bromine and a solvent inert to the reaction are continuously supplied separately or as a mixture of any combination. At that time, since the compound (unsaturated compound) represented by the general formula (1) and bromine react rapidly when they are brought into contact with each other, it should be avoided that they are mixed in advance and supplied to the reactor. It is.
[0056]
In carrying out the continuous system, the supply system of the unsaturated compound, bromine and solvent to each reactor is classified into the following (i) to (iii).
(I) A solution of unsaturated compound and bromine are supplied separately.
(Ii) Supplying the unsaturated compound solution and the bromine solution separately.
(Iii) The unsaturated compound, bromine and solvent are supplied separately.
[0057]
The above (i) to (iii) are for explaining a combination of means for supplying unsaturated compounds, bromine and a solvent necessary for carrying out the continuous system of the present invention, and these partial modifications Of course, this is also included in the present invention. When there are other components to be added, the components may be added independently, may be added as a solvent solution, or may be added to a solution of an unsaturated compound or a bromine solution. In addition to this, for example, there is an alcohol represented by the above general formula.
[0058]
Next, the proportions of unsaturated compound, bromine and solvent inert to the reaction supplied to the reactor will be described, but these proportions do not substantially differ from the aforementioned proportions. That is, the solvent is used in a ratio of at least 2 molecules, preferably at least 2.5 molecules, more preferably at least 3 molecules, and most preferably 4 molecules per unsaturated group to the unsaturated compound.
[0059]
The upper limit is limited from an economic point of view, and is generally 1000 molecules or less, preferably 800 molecules or less, and particularly preferably 700 molecules or less. Most advantageously, it is 500 molecules or less.
Further, bromine is advantageously in the range of 1 to 5 molecules, more preferably in the range of 1.1 to 3 molecules, per unsaturated group in the unsaturated compound. In particular, a range of 1.2 to 3 molecules is industrially advantageous.
[0060]
In the continuous system of the present invention, one or more molecules, preferably 1 to 5 molecules, more preferably 1.1 to 1 bromine per aliphatic unsaturated group in the unsaturated compound in the reaction solution in the reactor. It is important to keep it in the range of 3 molecules. In order to obtain a bromine compound having high purity and high quality, bromine always maintains the above ratio during the reaction in the reaction solution. Instantaneously (on the order of several seconds), there is no particular problem even if the bromine ratio is smaller than the above range, but the substantial reaction time and bromine ratio should be maintained within the above range. If the proportion of bromine is kept below the above range for a long time, the unsaturated group in the unsaturated compound causes a side reaction, an undesirable side reaction product is generated, and the purity of the target bromine compound is lowered. This side reaction is considered to occur mainly when an active intermediate formed by the reaction of water and bromine in the reaction solution reacts with an unsaturated group.
[0061]
In order to keep the ratio of bromine in the reaction solution in the continuous system to 1 molecule or more, preferably 1.1 molecules or more per unsaturated group in the unsaturated compound, the unsaturated compound and bromine fed into the reactor What is necessary is just to maintain the said supply ratio always at the said ratio.
[0062]
The bromination reaction occurs rapidly in the reactor, and the generated heat of reaction needs to be removed by vaporization of the solvent or bromine. A method in which the vaporized solvent or bromine vapor is cooled and liquefied by a condenser or the like installed in the upper part of the reactor and returned to the reaction solution, that is, a method of refluxing is preferably used because it is easy to operate. By removing the reaction heat of bromination with the heat of vaporization of the solvent or bromine, the produced bromine compound has a high purity. By simply reacting an unsaturated compound and bromine at a high temperature, a by-product is likely to be generated and the purity is deteriorated as compared with a reaction at a low temperature. However, in the method of the present invention, a high-purity bromine compound is obtained. be able to. This is presumably because the unsaturated compound and bromine are uniformly dispersed in the solution due to the stirring effect due to reflux, and side reactions are unlikely to occur.
[0063]
The addition amount of the solution in which the unsaturated compound is dissolved in the solvent is A (L / min), the addition amount of bromine or bromine solution is B (L / min), and the reaction solution amount in the reaction tank is C (L). In this case, it is desirable to carry out the bromination reaction so that the residence time represented by the following formula is 0.1 to 200 minutes, preferably 0.2 to 100 minutes.

[0064]
Here, the total amount of the addition amount (L / min) of a solution in which an unsaturated compound is dissolved in a solvent and the addition amount (L / min) of bromine or a bromine solution is strictly a reaction derived outside the reactor. Although it is different from the derived amount of the solution (L / min), the amount of bromine added (L / min) is usually considerably smaller than the amount of the unsaturated compound added to bromine (L / min). The volume change due to is almost negligible. Further, since the amount of the solvent scattered outside the reactor is very small, the addition amount of the unsaturated compound dissolved in bromine with respect to the bromine (L / min) and the addition amount of bromine or bromine solution (L / The total amount with (min) is close to the derived amount (L / min) of the reaction solution led out of the reactor.
[0065]
Circulating a part of the reaction solution to the reactor is advantageously employed because the reactor can be made more compact and the reaction efficiency is excellent. The circulation method is not particularly limited, and a separate dedicated circulation pipe may be attached to the reactor in addition to the reaction solution outlet, and a part of the derived reaction solution may be circulated to the reactor. . The circulated reaction solution may be added as it is to the reactor, or may be mixed with an unsaturated bond compound solution, bromine or bromine solution, or a mixture of both, and the resulting mixture may be returned to the reactor. Good.
[0066]
In the continuous system of the present invention, since the bromination reaction can be performed in a short time and the productivity is improved, the circulation method is preferable. Since the bromination reaction itself is almost completed in several tens of seconds, it is sufficient within the above-mentioned residence time range.
[0067]
The reaction temperature in the bromination reaction of the present invention may be any temperature as long as the heat of bromination described above is removed by bromine or the heat of vaporization of the solvent, and the bromination reaction is not limited to normal pressure. It can be performed under pressure or under reduced pressure. As described above, the reaction temperature is preferably in the range of 0 ° C to 60 ° C. In addition, when the boiling point of the solvent used is lower than the boiling point of bromine, the reaction temperature can be increased by pressurization. When the boiling point of the solvent used is higher than the boiling point of bromine, the reaction is performed by reducing the pressure. The temperature can be lowered.
[0068]
In carrying out the continuous mode of the present invention, the reactor contacts the unsaturated compound, bromine and solvent uniformly and effectively, and a substantial amount of heat of reaction is discharged out of the reactor by vaporization of the solvent or bromine. A stirrer is desirable, and a vaporized solvent or bromine is advantageously used with a condenser on top for refluxing.
[0069]
According to our research, in carrying out this continuous system, unsaturated compounds, bromine and solvent are uniformly contacted with each other in the reactor, and the bromination reaction and heat of reaction are removed by vaporization of the solvent or bromine. In order to make the process more effective, it is effective to supply the unsaturated compound and bromine, preferably together with at least a part of the solvent, in a short period of time immediately before being supplied to the reactor. It was found that there was.
[0070]
Mixing of the unsaturated compound and bromine immediately before feeding to the reactor (the solvent may be further mixed) should be performed in a short time and evenly. It is desirable to be fed to the reactor as a stream. Mixing in the flow mixer is an unsaturated compound and bromine, but some or all of the solvent is also mixed together.
[0071]
The mixed liquid flow in the flow mixer is desirably mixed uniformly and in a short time, and advantageously has a flow rate of 15 to 500 cm / second, preferably 50 to 400 cm / second. Further, the residence time of the mixed liquid flow in the flow mixer is 0.01 to 180 seconds, preferably 0.05 to 120 seconds, more preferably 0.1 to 60 seconds. In particular, 0.1 to 20 seconds is recommended.
[0072]
The flow mixer is not particularly limited as long as it can effectively and uniformly mix the liquid mixed stream in a short time, and a static mixer is particularly preferable. As this static mixer, one having 4 to 20 elements, preferably 5 to 15 elements, is advantageously used.
[0073]
A static mixer is a chemical engineering device commonly known as a mixer or heat exchanger. A static mixer is a mixer commercially available from Kenix, Inc. in the United States, and is a tube-type mixer that does not have a drive unit. Inside, a rectangular plate called an element is twisted at right angles in the opposite direction. An object of a different structure is built in, and the torsional direction is arranged so that each cross section intersects at right angles alternately left and right.
[0074]
In the continuous mode of the present invention, when the unsaturated compound, bromine and solvent are continuously fed to the reactor, carrying out these feeds using a flow mixer, particularly a static mixer, makes the bromination reaction extremely difficult. This is an extremely effective means for completing in a short time, suppressing side reactions, and obtaining a high purity bromine compound.
[0075]
The mixed solution mixed in the flow mixer is immediately supplied to the reactor. The solution mixed in the flow mixer starts part of the bromination reaction, but the residence time in the mixer is controlled to be short, so the mixed solution that has passed through the mixer is immediately discharged into the reactor. . In the reactor, the solution is further stirred so that it is thoroughly mixed. Stirring is preferably performed using a stirrer, but may be a method of circulating a part of the solution from the reactor.
[0076]
The reactor preferably has a capacity of 30 times or more and 50 times or more the mixer capacity. Further, the upper limit of the size of the reactor is not particularly limited, but 200,000 times or less of the mixer capacity is sufficient, and the use of the reactor exceeding 200,000 times is not economically preferable. Such a large-capacity reactor has a function to suppress scattering due to boiling of the solvent and bromine by dissipating the reaction heat generated when reacting in the mixer in the reactor, and promotes stirring and mixing. To complete the bromination reaction.
[0077]
At this time, a method of removing the reaction heat of bromination with the heat of vaporization of the solvent or bromine can be adopted, and a condenser is attached to the reactor, and the vaporized vapor is cooled and liquefied to form a reaction solution again. The returning method, that is, the refluxing method is more preferably used because it is easy to operate. In this method, the unsaturated compound and bromine are uniformly dispersed in the solution due to the stirring effect by reflux, side reactions are unlikely to occur, and a high-purity bromine compound is easily obtained, and the reaction temperature is kept constant. However, since the bromination reaction proceeds stably without causing scattering of the solvent or bromine, it is preferably used.
[0078]
Odor Separation and recovery of elemental compounds;
The target bromine compound can be separated and recovered from the reaction mixture obtained by the bromination reaction by a method known per se. However, unreacted bromine remains in the reaction mixture. Therefore, a method is generally employed in which residual bromine is treated with a reducing agent, once bromine is converted to hydrobromic acid, and then an alkaline neutralizing agent is added. ing.
[0079]
However, this method requires at least two steps of reduction treatment and neutralization treatment, and the operation is complicated and the treatment takes a long time. Moreover, the purity and quality of the bromine compound recovered by this treatment method is not fully satisfactory.
[0080]
Accordingly, the present inventors have improved the method for separating and recovering the bromine compound from the reaction mixture in a short time by a simple means. As a result, the reducing agent and alkalinity more than a specific amount with respect to the residual bromine in the reaction mixture. It has been found that the neutralizing agent can be treated easily and in a short time by a method in which the reaction mixture is simultaneously mixed.
[0081]
That is, a method has been found in which 2 moles or more of a reducing agent and 2 moles or more of an alkaline neutralizing agent are simultaneously added to and mixed with the reaction mixture after completion of the reaction per mole of bromine remaining therein. This method is hereinafter referred to as “processing method”.
[0082]
The reducing agent used in this treatment method is a reducing agent used in a normal reduction reaction. Specifically, sodium bisulfite, sodium dithionite, sodium sulfite, oxalic acid, hydrogen sulfide, nitrous acid Examples thereof include sodium, potassium nitrite, hydroxylamine sulfate, tin, stannous oxide and hydrazine, and sodium hydrogen sulfite, sodium dithionite, sodium sulfite, oxalic acid and sodium nitrite are preferably used. These reducing agents can also be used as an aqueous solution. These reducing agents may be used alone or in combination of two or more.
[0083]
Examples of the alkaline neutralizing agent include alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, and the like. Specifically, sodium hydroxide Potassium hydroxide, sodium carbonate, potassium carbonate, calcium hydroxide, calcium carbonate and the like are preferable, and sodium hydroxide is particularly preferably used. These alkaline neutralizers are preferably used as an aqueous solution. These alkaline neutralizing agents are used alone or in combination of two or more.
[0084]
In the treatment method of the present invention, 2 moles or more, preferably 2 to 30 moles, more preferably 2.2 to 15 moles, and further preferably 2.5 to 10 moles per mole of residual bromine in the reaction mixture. A reducing agent is added to the reaction mixture. When the reducing agent to be added is less than 2 moles, bromine remains in the mixture, which is not preferable because a bromine compound colored brown with low purity is obtained. In addition, 2 moles or more, preferably 2 to 50 moles, more preferably 2.2 to 30 moles, and even more preferably 2.5 to 20 moles of an alkaline neutralizer with respect to 1 mole of residual bromine in the reaction mixture. Is added to the reaction mixture. When the neutralizing agent to be added is less than 2 moles, hydrogen bromide remains in the aqueous solution, and the strong acid aqueous solution cannot be discarded as it is, and part of the hydrogen bromide remains in the mixture, which easily corrodes the metal. Furthermore, this hydrogen bromide has a strong irritating odor and is not preferable in the working environment.
[0085]
The reducing agent and the alkaline neutralizing agent are simultaneously added to the reaction mixture containing the bromine compound and bromine. Such a reducing agent and a neutralizing agent may be added separately or in advance, but it is preferable to add them separately because the reducing agent does not cause a side reaction due to alkali. Further, here, the simultaneous addition does not mean that both are strictly added at the same time, but at least 10 minutes, preferably within 5 minutes after the addition of one agent and the addition of this agent is completed. This means that the other agent finishes addition. As the addition method, a method of adding a reducing agent and immediately adding a neutralizing agent is preferably employed.
[0086]
In the treatment method, the reaction mixture to which the reducing agent and the alkaline neutralizing agent are added is mixed so that the reduction and neutralization reactions proceed smoothly. As a mixing method, various mixers can be used, for example, a method of stirring by rotating a stirring blade (a method in which a central axis of a tank is aligned with a stirring shaft, a method in which a stirring shaft is inclined, a tank In-line mixers such as stirring tanks and static mixers using a system that stirs by shaking the tank, a system that circulates the liquid in the tank using a pump, etc. Of these, a stirring tank is preferably used.
[0087]
Moreover, 20: 80-80: 20 are preferable, as for the weight ratio of the reaction mixture at the time of performing this reduction and neutralization reaction, 30: 70-70: 30 are more preferable, and 40: 60-60: 40 is particularly preferred. Within this range, the reduction and neutralization reactions proceed efficiently and bromine is removed in a short time. Therefore, it is preferable to add water or a solvent to the reaction mixture so as to be within the above range during the reduction and neutralization reaction.
[0088]
The time required for the reduction and neutralization reaction of bromine in the reaction mixture is preferably 2 minutes or more, more preferably 2 to 90 minutes, further preferably 5 to 60 minutes, and particularly preferably 10 to 45 minutes.
Thus, in the present invention, the number of washings with water is only one step after the reduction and neutralization reactions are completed. Therefore, in the reduction and neutralization reaction, process operations are reduced, and therefore process management becomes easy.
[0089]
From the reaction mixture treated by the above-described method, the target bromine compound is recovered by a method known per se, for example, precipitation with a poor solvent.
The separation and recovery of the target bromine compound from the reaction mixture obtained by the bromination reaction described above can also be carried out by reducing using a static mixer and then neutralizing as described below. it can.
[0090]
That is, this method is a method in which a reaction mixture containing a target bromine compound and residual bromine and an aqueous solution containing a reducing agent are mixed to reduce and treat bromine, and the solution containing the bromine compound and bromine and the reduction are mixed. The aqueous solution containing the agent is introduced into a static mixer having 4 to 20 elements so that the flow rate of the mixed solution is 5 cm / second or more, and the residence time in the static mixer is within 300 seconds. Then, the mixed solution derived from the static mixer is charged into a stirring tank having a capacity of 20 times or more of the static mixer, and then neutralized.
[0091]
As the reducing agent used in this treatment method, those exemplified above are used, and the amount of the reducing agent is preferably 2 mol or more, more preferably 2 to 100 mol, relative to 1 mol of residual bromine. -50 mol is more preferable, and 2-20 mol is particularly preferable. When the amount is less than 2 mol, the reduction reaction becomes insufficient and bromine tends to remain.
[0092]
In the reduction reaction for bromine, the reaction mixture and an aqueous solution containing a reducing agent must be mixed efficiently. Therefore, when a normal stirring apparatus is used, the stirring efficiency is not sufficient, and it is necessary to repeat the process in several steps in order to complete the reduction reaction. Therefore, by using a static mixer as a mixer, mixing is performed efficiently, and bromine can be processed in a short time with a simple apparatus.
[0093]
As a condition when using a static mixer, the degree of substantial mixing can be determined by the number of elements in the pipe, and it is considered that mixing is usually performed by dividing the number of elements as a power of two. The mixing efficiency may be determined by factors such as the flow rate, viscosity, and Reynolds number of the liquid component into the tube, but the flow rate is particularly important. In this treatment method, the mixed solution of the reaction mixture and the aqueous solution containing the reducing agent is introduced into the static mixer so that the flow rate at the static mixer inlet is 5 cm / second or more, preferably 10 cm / second or more. To do. When the flow rate is less than 5 cm / sec, the mixing efficiency is insufficient and the reduction reaction is not sufficiently performed. Further, even if the flow rate exceeds 500 cm / second and is introduced into the static mixer, the mixing efficiency is not substantially different and no further flow rate is required. Here, the flow rate is defined as A (mL / second) for the addition rate of the reaction mixture introduced into the static mixer, B (mL / second) for the aqueous solution containing the reducing agent, and the cross-sectional area of the static mixer. C (cm ² ), The calculation formula is (A + B) / C (cm / sec).
[0094]
The method for introducing the reaction mixture and the aqueous solution containing the reducing agent into the static mixer is not particularly limited, and may be introduced using a dropping funnel, or may be determined by a pump in order to easily give a desired flow rate. It is also preferable to supply a constant volume in time.
[0095]
In addition, the number of elements of the static mixer is in the range of 4 to 20, the mixing is insufficient when the number of elements is 3 or less, the purity of the bromine compound obtained is low, and the number of elements of 21 or more from the mixing efficiency is Not necessary.
[0096]
The residence time in the static mixer of the mixed solution of the reaction mixture introduced into the static mixer and the aqueous solution containing the reducing agent is within 300 seconds, preferably 0.001 to 300 seconds, preferably 0.005 to 180 seconds. Is more preferable, 0.01 to 120 seconds is further preferable, 0.05 to 60 seconds is further preferable, and 0.1 to 10 seconds is particularly preferable. If the residence time is too long, it becomes difficult to separate the organic solvent phase and the aqueous phase later, which is not preferable. Here, the residence time is defined as A (mL / second) for the addition rate of the reaction mixture introduced into the static mixer, B (mL / second) for the aqueous solution containing the reducing agent, and the contents of the static mixer. The product is X (cm ^Three ), The calculation formula is X / (A + B) (seconds).
[0097]
In the treatment method, a reaction mixture mixed in the static mixer and an aqueous solution containing a reducing agent are led out from the static mixer, and the mixed solution has a capacity of 20 times or more the capacity of the static mixer. Put in the stirring tank.
[0098]
At that time, by mixing the reaction mixture and the aqueous solution containing the reducing agent in the static mixer, a part of the reduction reaction proceeds, but further reduction reaction is performed and the reaction heat in the static mixer is dissipated. In order to do this, it is necessary to introduce such a mixed solution into another stirring tank. Here, the stirring tank is not limited as long as the solution mixed in the static mixer is continuously maintained in a mixed solution state, and the stirring method is not limited. For example, the stirring blade is rotated. (A method in which the central axis of the tank and the agitation axis are aligned, an inclination of the agitation axis, an agitation axis provided on the side wall of the tank, etc.), a method of agitation by rocking the tank, A method of circulating the liquid in the tank with a pump is used.
[0099]
The capacity of the stirring tank is 20 times or more of the static mixer capacity, and preferably has a capacity of 30 times or more. The upper limit of the size of the stirring tank is not particularly limited, but a stirring tank having a capacity of 200,000 times or less of the static mixer capacity is sufficient, and the use of a stirring tank exceeding 200,000 times is economical. It is not preferable. Such a large capacity stirring tank has a function of completing the reduction reaction by stirring and mixing, and also has a function of dissipating the reaction heat generated when reacting in the static mixer in the stirring tank. Alternatively, a pipe from the stirring tank to the introduction port of the static mixer may be installed, and the solution in the stirring tank may be reintroduced into the static mixer.
[0100]
The stirring time of the solution in the stirring tank is preferably 2 minutes or more, more preferably 2 to 90 minutes, further preferably 3 to 60 minutes, and particularly preferably 5 to 45 minutes. The reduction reaction is completed by stirring and mixing for such time.
[0101]
After the reduction reaction is completed, bromine becomes hydrogen bromide, most of which is dissolved in an aqueous solution containing a reducing agent, and becomes acidic water having a relatively low pH. In such a state, the target bromine compound may be recovered. However, since the reaction apparatus is usually made of metal, it often causes safety problems such as acid corrosion and perforation. It is preferable to neutralize hydrogen fluoride, and an alkaline neutralizing agent is preferably used.
[0102]
Examples of such an alkaline neutralizer include alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, and the like, as described above. Sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, calcium hydroxide, calcium carbonate and the like are preferable, and sodium hydroxide is particularly preferably used. These alkaline neutralizers are preferably used as an aqueous solution. These alkaline neutralizing agents are used alone or in combination of two or more.
[0103]
In this case, 2 mol or more, preferably 2 to 100 mol, more preferably 2 to 50 mol, and further preferably 2 to 20 mol of an alkaline neutralizing agent is used with respect to 1 mol of residual bromine in the reaction mixture. The solution is mixed with the solution after the reduction reaction. At this time, the pH of the solution is preferably 7.5 or more, and more preferably 8 or more. When the neutralizing agent to be added is less than 2 moles, hydrogen bromide remains in the aqueous solution, and this strong acid aqueous solution cannot be discarded as it is, and some hydrogen bromide remains in the bromine compound, which corrodes the metal. Further, this bromine compound has a strong irritating odor and is not preferable in the working environment.
[0104]
The time required for the neutralization reaction is preferably 2 minutes or more, more preferably 2 to 90 minutes, further preferably 5 to 60 minutes, and particularly preferably 10 to 45 minutes.
The bromine compound obtained by the method of the present invention is recovered by an appropriate method well known to those skilled in the art, such as precipitation with a poor solvent.
[0105]
Thus, according to the method of the present invention, it is represented by the following general formula (2) in which the unsaturated group of the unsaturated compound is saturated with a bromine atom by the bromination reaction of the unsaturated compound represented by the general formula (1). The bromine compound to be obtained is obtained as high purity.
R ^Three -O-Ar ¹ -Y-Ar ² -O-R ^Four (2)
(Wherein Ar ¹ , Ar ² And Y are the same as defined in the general formula (1). R ^Three And R ^Four Are R in the general formula (1), respectively. ¹ And R ² The group in which the unsaturated group in is saturated with a bromine atom. )
[0106]
The bromine compound obtained by the present invention has a purity of 80% by weight or more, preferably 85% by weight or more, and particularly preferably 90% by weight or more. Such a high purity bromine compound is extremely excellent as a flame retardant for thermoplastic resins.
[0107]
The bromine compound obtained in the method of the present invention not only has excellent purity, but also has excellent quality in that it has a low content of impurities that have an adverse effect when used as a flame retardant.
[0108]
That is, in the obtained bromine compound, the following general formula (4)

(Wherein Ar ¹ , Ar ² And Y have the same definition as in general formula (1). R ⁶ And R ⁷ Are the same or different and represent a hydrocarbon group having 2 to 11 carbon atoms. p and q are each an integer of 0 to 10, (p + q) is 1 or more, preferably an integer of 2 to 10, s and t are each an integer of 0 to 5, and (s + t) is 1 or more. , Preferably an integer of 1 to 5. )
Is contained in a small amount.
[0109]
In the bromine compound of the present invention, the content of the hydroxy bromine compound represented by the formula (4) is 0.02 mol or less with respect to 1 mol of the bromine compound represented by the formula (1), and 0.0001 to 0 0.02 mol is preferable, 0.0001 to 0.015 mol is more preferable, and 0.0001 to 0.01 mol is more preferable. When the content of the compound represented by the formula (4) exceeds 0.02 mol with respect to 1 mol of the bromine compound represented by the formula (1), the thermal stability of the bromine compound of the present invention is lowered, which is not preferable. .
[0110]
When the compound represented by the formula (4) reacts with the unsaturated bond compound and bromine described above to synthesize the bromine compound represented by the formula (1), the solution of the unsaturated compound, bromine or bromine solution and alcohol The intermediate produced by the reaction of water and bromine present in the reaction solution consisting essentially of the compound is a by-product produced by reacting with the unsaturated bond compound.
[0111]
In particular, when the bromination reaction in the method of the present invention is carried out by adding the alcohol represented by the general formula (3), the obtained bromine compound not only has a high purity, but also adversely affects its thermal stability. A small proportion of an alkoxybromine compound represented by the following general formula (5).
[0112]

(Wherein Ar ¹ , Ar ² And Y have the same definition as in general formula (1). R ⁶ And R ⁷ Are the same or different and represent a hydrocarbon group having 2 to 11 carbon atoms. p, q, s, and t mean the same definition as in the general formula (4). R ⁸ And R ⁹ Each represents an aliphatic group having 1 to 6 carbon atoms. )
[0113]
The compound represented by the formula (5) is produced by reacting the intermediate produced by the reaction of the alcohol represented by the formula (3) and bromine with the aliphatic unsaturated group of the unsaturated compound as described above. This by-product does not adversely affect the thermal stability of the bromine compound. The content of the alkoxy bromine compound represented by the formula (5) is preferably 0.01 to 0.2 mol, preferably 0.01 to 0.15 mol, with respect to 1 mol of the bromine compound represented by the formula (1). Is more preferable, 0.01 to 0.1 mol is more preferable, and 0.01 to 0.05 mol is particularly preferable. When the content of the alkoxy bromine compound represented by the formula (5) is 0.2 mol or less with respect to 1 mol of the bromine compound represented by the formula (1), the bromine compound was blended into the resin as a flame retardant. It is preferable because it does not adversely affect the flame retardancy of the resin composition.
[0114]
【Example】
The present invention will be described in detail below with reference to examples.
Examples 1 to 39 shown below are not reference examples of the present invention, but are reference examples, and Examples 40 to 56 are examples of the present invention. Furthermore, Preparation Examples 1-4 and Examples 57-71 do not show Examples of the present invention but are Reference Examples. In the examples, a compound having an aliphatic unsaturated bond represented by the general formula (1) may be abbreviated as “raw material”. The purity, bromine content and specific gravity were measured according to the following method.
(1) Purity of bromine compound, impurities derived from water, impurities derived from a hydroxyl group-containing compound;
The purity of the bromine compound, impurities derived from water, and impurities derived from the hydroxyl group-containing compound were measured by a method of detecting absorption at 280 nm by high performance liquid chromatography (SCL-6B, manufactured by Shimadzu Corporation). For the purity of the bromine compound, the sum of the peak areas of the respective components obtained from this chromatography was taken as 100, and the peak area ratio of the bromine compound to this was determined. In addition, the measurement of impurities derived from water-derived impurities and hydroxyl group-containing compounds was carried out by determining the peak area of the bromine compound obtained from this chromatography, the sum of the peak areas of each component of the water-derived impurities and the hydroxyl group content. The sum of the peak areas of the respective components of impurities derived from the compound was determined, and the content (mol) relative to 1 mol of each bromine compound was calculated.
[0115]
(2) Analysis of bromine content
The sample was heated and decomposed with fuming nitric acid in a sealed container, and the generated hydrobromic acid was quantitatively analyzed using a method of titrating with silver nitrate (Carius method).
[0116]
(3) Specific gravity
It measured at 20 degreeC using the glass specific gravity bottle.
[0117]
(4) Analysis of water content
Using a coulometric titration-type moisture measuring device (CA-06 model manufactured by Mitsubishi Chemical Corporation), it was determined by the Karl Fischer method.
[0118]
(5) Inclination angle (after heating at 70 ° C for 4 hours)
0.5 g of the sample was placed in the center of a glass petri dish (Pyrex glass manufactured by Iwaki Glass Co., Ltd .; centerline average roughness at the bottom of 0.1 μm) and heated at 70 ° C. for 4 hours using a hot air circulation dryer. Thereafter, the petri dish was taken out and cooled to room temperature. When this petri dish is tilted by lifting the opposite side with one end in contact with the horizontal plane, and the solid sample in the petri dish slips, the angle of inclination of the petri dish relative to the horizontal plane viewed from the side is a protractor. (See FIG. 1). This inclination angle means the degree of aggregation of the solid accompanying heat treatment. If the inclination angle is larger than 70 °, it means that the sample has insufficient thermal stability and is likely to cause a blocking phenomenon.
[0119]
In the following examples and comparative examples, the raw material No. (1) to (6) each mean the following compound.

[0120]
Example 1
In a 1 L glass reaction vessel equipped with a stirrer, condenser, thermometer and dropping funnel, 135 g (0.216 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane and synthetic zeolite Then, 230 g of methylene chloride dehydrated was added and dissolved (the specific gravity of this solution was 1.47, and the concentration calculated from this was 0.87 mol / L). While stirring this solution, 72.7 g (0.455 mol) of bromine was dropped from the dropping funnel over 8 minutes while refluxing methylene chloride at a temperature of 39 to 41 ° C. (addition rate of bromine with respect to 1 mol of raw material). 4.4 mmol / sec). After completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes while refluxing methylene chloride at a temperature of 39 to 41 ° C. to complete the addition reaction of bromine.
[0121]
Next, excess bromine in the reaction solution was reduced with 50 g of a 15 wt% sodium bisulfite aqueous solution, and then the produced hydrogen bromide was neutralized with a 25 wt% sodium hydroxide aqueous solution. Thereafter, a methylene chloride layer is separated from this solution, and about 90% of the methylene chloride is evaporated and removed from the methylene chloride layer. To this, 500 mL of methanol is added to precipitate a reaction product, and this precipitate is filtered to form a lump. The solid was removed. The massive solid was pulverized in a mortar and dried under reduced pressure at 80 ° C. for 3 hours at 5 mmHg to obtain 198.5 g of the product (yield 97.2%).
[0122]
The resulting product ¹ As a result of analysis by H-NMR, a signal derived from —CHBr— was observed at 4.51 to 4.53 ppm, and —CHBr— at 3.94 to 4.09 ppm. ₂ A signal derived from Br was observed. From FT-IR analysis, -O-CH ₂ It was confirmed that no absorption of allyl groups was observed. From the above analysis results, it was confirmed that the product was 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. This bromine compound had a purity of 96.8%, a melting point of 110 ° C., and a bromine content of 67.5% (theoretical value: 67.8%).
[0123]
Example 2
The 1 L glass reaction vessel used in Example 1 was dehydrated with 140.8 g (0.216 mol) of 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane and synthetic zeolite. A mixed solvent of 163 g of methylene chloride and 70 g of 1,4-dioxane was added and dissolved (specific gravity of the solution 1.35). While this solution was stirred and the mixed solvent was refluxed, 79.5 g (0.497 mol) of bromine was added dropwise from the dropping funnel in 9 minutes (the addition rate of bromine was 1.09 mmol / sec with respect to 1 mol of the raw material). Met.). After completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes while refluxing the mixed solvent to complete the bromine addition reaction.
[0124]
The obtained reaction solution was subjected to the same operation as in Example 1 to obtain 203.3 g of a white solid product (yield 96.8%). The product obtained as in Example 1 is ¹ As a result of analysis using H-NMR and FT-IR, the product was 2,2-bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl} propane. It was confirmed. This bromine compound had a purity of 96.5% and a bromine content of 65.3% (theoretical value: 65.8%).
[0125]
Example 3
In Example 2, 128.7 g of bis {(3,5-dibromo-4-allyloxy) phenyl} methane instead of 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane (0.216 mol) was used (the specific gravity of the solution was 1.34), and bromination was carried out in the same manner as in Example 2 except that 79.5 g of bromine was dropped in 8.3 minutes instead of 9 minutes. And 191.4 g of product were obtained (yield 96.7%).
[0126]
The product obtained as in Example 1 is ¹ As a result of analysis using H-NMR and FT-IR, the product was confirmed to be bis {3,5-dibromo-4- (2,3-dibromo-propyloxy) phenyl} methane. This bromine compound had a purity of 96.7% and a bromine content of 69.5% (theoretical value: 69.8%).
[0127]
Example 4
In Example 1, instead of 135 g of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane, bis {(3,5-dibromo-4-isobutenyloxy) phenyl} methane 134. Bromination was carried out in the same manner as in Example 1 except that 8 g (0.216 mol) was used (specific gravity of the solution: 1.47) to obtain 197.6 g of the product (yield 96.9%).
[0128]
The product obtained as in Example 1 is ¹ As a result of analysis using 1 H-NMR and FT-IR, it was confirmed that the product was bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl} methane. It was. This bromine compound had a purity of 96.8% and a bromine content of 67.7% (theoretical value: 67.8%).
[0129]
Example 5
In Example 1, instead of 135 g of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane, (3,3 ′, 5,5′-tetrabromo-4,4′-diallyloxy) Bromination was carried out in the same manner as in Example 1 except that 125.7 g (0.216 mol) of biphenyl was used (specific gravity of solution: 1.47) to obtain 186.6 g of product (yield 95.8). %).
[0130]
The product obtained as in Example 1 is ¹ As a result of analysis using H-NMR and FT-IR, the product is {3,3 ′, 5,5′-tetrabromo-4,4 ′-(2,3-dibromo-propyloxy)} biphenyl. It was confirmed. The compound had a purity of 95.7%, a bromine content of 70.8% (theoretical value: 70.9%).
[0131]
Example 6
In Example 1, bromination was carried out in the same manner as in Example 1 except that 230 g of methylene chloride was replaced with 86 g (specific gravity of the solution: 1.42), and 72.7 g of bromine was replaced with 75 g (0.469 mol). 199.5 g of product was obtained (yield 97.7%).
The product obtained as in Example 1 is ¹ Analysis using H-NMR and FT-IR confirmed the product to be 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. It was. This bromine compound had a purity of 96.7%.
[0132]
Example 7
In Example 1, 135 g of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was replaced with 268 g (0.430 mol), and 230 g of methylene chloride was replaced with 493 g (specific gravity of the solution 1 .42), bromination was carried out in the same manner as in Example 1 except that 72.7 g of bromine was replaced with 80 g (0.500 mol) to obtain 392.8 g of product (yield 96.9%).
[0133]
The product obtained as in Example 1 is ¹ Analysis using H-NMR and FT-IR confirmed the product to be 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. It was. This bromine compound had a purity of 96.8%.
[0134]
Example 8
In Example 1, 135 g of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was changed to 162 g (0.260 mol), and 230 g of methylene chloride was changed to 234 g (specific gravity of the solution 1). .47) and bromination was carried out in the same manner as in Example 1 except that 72.7 g of bromine was replaced with 95 g (0.594 mol) to obtain 234.7 g of the product (yield 95.8%).
[0135]
The product obtained as in Example 1 is ¹ Analysis using H-NMR and FT-IR confirmed the product to be 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. It was. This bromine compound had a purity of 96.6%.
[0136]
Example 9
In Example 1, instead of 140.8 g of 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane, bis {3,5-dibromo-4-isobutenyloxy) phenyl } Examples were used except that 148 g (0.220 mol) of sulfone was used, 230 g of methylene chloride was changed to 121 g (specific gravity of the solution 1.41), and 72.7 g of bromine was changed to 72.0 g (0.451 mol). Bromination was carried out in the same manner as in Example 1 to obtain 206.9 g of the product (yield 94.8%).
[0137]
The product obtained as in Example 1 is ¹ As a result of analysis using H-NMR and FT-IR, it was confirmed that the product was bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy)} sulfone. . The compound had a purity of 95.3% and a bromine content of 64.1% (theoretical value: 64.4%).
[0138]
Comparative Example 1
In Example 1, except that bromine was added dropwise over 120 minutes and the reaction temperature was 20 ° C. while cooling, and bromination reaction was performed without refluxing methylene chloride (the addition rate of bromine was 1 mol of the raw material). , 0.29 mmol / sec), and in the same manner as in Example 1, the obtained 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane was obtained. The yield was 96.5%, but the purity was as low as 89.7%.
[0139]
Comparative Example 2
In Example 1, except that bromine was added dropwise over 120 minutes to cause bromination reaction (the addition rate of bromine was 0.29 mmol / sec with respect to 1 mol of raw material), the same method as in Example 1 was performed. It was. At this time, the solution temperature at the start of the addition of bromine was 20 ° C., but as the bromine was added dropwise, the solution temperature gradually increased due to the heat of reaction, and the solution temperature reached 37 ° C. at the end of the addition. The reaction vessel was not cooled, and methylene chloride reflux did not occur. The purity of the obtained 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane was as low as 63.0%.
[0140]
The results of Examples 1 to 9 and Comparative Example 1 are shown in Tables 1 and 2. Here, solvent (A) and (B) show the following composition.
(A) Methylene chloride
(B) Methylene chloride / 1,4-dioxane = 70/30 (weight ratio)
The addition rate is the addition rate of bromine with respect to 1 mol of the raw material.
[0141]
[Table 1]

[0142]
[Table 2]

[0143]
Example 10
In a 1 L glass reaction vessel equipped with a stirrer, condenser, thermometer and dropping funnel, 135 g (0.216 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane and synthetic zeolite Then, 230 g of methylene chloride dehydrated was added and dissolved. Further, 0.36 g (0.0113 mol) of methanol was added to the solution (2.6 hydroxyl groups per 100 aliphatic unsaturated groups). The water content in this solution was 200 ppm (the number of water molecules per 100 aliphatic unsaturated groups was 0.94). Next, this solution was cooled to about 2 ° C., and 72.7 g (0.455 mol) of bromine was dropped from the dropping funnel over 60 minutes while stirring. At the end of dropping, the temperature of the reaction solution was 16 ° C. After completion of the dropwise addition, the reaction solution was stirred for 30 minutes to complete the bromine addition reaction.
[0144]
Next, excess bromine in the reaction solution was reduced with 50 g of a 15 wt% sodium bisulfite aqueous solution, and then the produced hydrogen bromide was neutralized with a 25 wt% sodium hydroxide aqueous solution. Thereafter, a methylene chloride layer is separated from the solution, and about 90% of the methylene chloride is evaporated and removed from the methylene chloride layer. To this, 500 mL of methanol is added to precipitate a reaction product, and the precipitate is filtered to form a lump. The solid was removed. This massive solid was pulverized in a mortar and dried under reduced pressure at 80 ° C. for 3 hours at 5 mmHg to obtain 198.5 g of the product (yield 97.0%).
[0145]
The resulting product ¹ As a result of analysis by H-NMR, a signal derived from —CHBr— was observed at 4.51 to 4.53 ppm, and —CHBr— was observed at 3.94 to 4.09 ppm. ₂ A signal derived from Br was observed. From FT-IR analysis, -O-CH ₂ It was confirmed that no absorption of allyl groups was observed. From the above analysis results, it was confirmed that the product was mainly 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. This bromine compound has a purity of 95.1%, and impurities derived from water are 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. The impurity derived from 0.004 mol and methanol was 0.015 mol. The inclination angle of the bromine compound was 44 °.
[0146]
Example 11
In Example 10, the same method as in Example 10 was performed, except that 0.36 g of ethanol (0.000078 mol, number of hydroxyl groups per 100 aliphatic unsaturated groups) was used instead of methanol. 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane was obtained. This bromine compound has a purity of 95.3%, 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane per mole of water, and impurities derived from water are 0. The amount of impurities derived from 004 mol and ethanol was 0.013 mol.
[0147]
Example 12
In Example 10, 2.33 g of i-propanol (0.0388 mol, the number of hydroxyl groups per 100 aliphatic unsaturated groups: 9.0) was used instead of methanol, and the initial temperature of the reaction solution was 25 ° C. The same method as in Example 10 was performed. At the end of the bromine addition, the temperature of the reaction solution was 36 ° C. After completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to complete the bromine addition reaction, and was treated in the same manner as in Example 1. Mainly 2,2-bis {3,5-dibromo-4- (2,3- Dibromopropyloxy) phenyl} propane was obtained. This bromine compound has a purity of 95.0% and 1,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane has 1 mol of water, and impurities derived from water have a purity of 0. The impurity derived from 003 mol and i-propanol was 0.037 mol.
[0148]
Example 13
In Example 12, 1.13 g (0.015 mol, 3.5 hydroxyl groups per 100 aliphatic unsaturated groups) was used in place of i-propanol instead of i-propanol. The process was carried out to obtain mainly 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. The bromine compound has a purity of 94.9%, 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane per mole of water, and impurities derived from water are 0. The impurity derived from 003 mol and n-butanol was 0.021 mol.
[0149]
Example 14
In a glass reaction vessel used in Example 10, 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane 135 g (0.216 mol) and methylene chloride 230 g were added and dissolved. Further, 0.72 g (0.0157 mol) of ethanol was added to this solution (number of hydroxyl groups per 100 aliphatic unsaturated groups: 3.6). The water content in this solution was 500 ppm (number of water molecules per 100 aliphatic unsaturated groups: 2.4). Next, this solution was cooled to about 2 ° C., and 72.7 g (0.455 mol) of bromine was dropped from the dropping funnel over 60 minutes while stirring. At the end of dropping, the temperature of the reaction solution was 16 ° C. After completion of the dropwise addition, the reaction solution was stirred for 30 minutes to complete the bromine addition reaction.
[0150]
Next, this reaction solution was treated in the same manner as in Example 10 to obtain mainly 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. The bromine compound has a purity of 94.9%, 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane per mole of water, and impurities derived from water are 0. The impurity derived from 005 mol and ethanol was 0.016 mol. The inclination angle of the bromine compound was 45 °.
[0151]
Example 15
In Example 10, except that the dropping time of bromine was 120 minutes, the stirring of the reaction solution was continued for 30 minutes after the dropping was completed, and the reaction solution was cooled to maintain the temperature of the reaction solution at 20 ° C. during the bromination reaction. The same method as in Example 10 was performed to mainly obtain 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. This bromine compound has a purity of 95.2%, 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane per mole of water, and impurities derived from water are 0. The impurities derived from 003 mol and methanol were 0.015 mol.
[0152]
Example 16
In Example 10, instead of methanol, 0.72 g of ethanol (0.016 mol, number of hydroxyl groups per 100 aliphatic unsaturated groups: 3.6) was used, and 230 g of methylene chloride was changed to 615 g (water content in this solution). Is 200 ppm, the number of water molecules per 100 unsaturated aliphatic groups is 1.9), the reaction temperature is set to 39 to 41 ° C., and while refluxing the solvent, 80.0 g (0.501 mol) of bromine is about 5%. Dropped in minutes. After completion of the bromine addition, the reaction solution was continuously stirred for 60 minutes to complete the addition reaction of bromine. This reaction solution was treated in the same manner as in Example 10 to obtain mainly 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. This bromine compound has a purity of 96.1%, 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane per mole of water, and impurities derived from water are 0. The impurities derived from 003 mol and methanol were 0.016 mol. The inclination angle of the bromine compound was 41 °.
[0153]
Example 17
Methylene chloride dehydrated with 135 g (0.207 mol) of 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane and synthetic zeolite was added to the glass reaction vessel used in Example 10. 230 g was added and dissolved. Further, 0.36 g (0.0113 mol) of methanol was added to this solution (number of hydroxyl groups per 100 aliphatic unsaturated groups: 2.7). The water content in this solution was 200 ppm (number of water molecules per 100 aliphatic unsaturated groups: 0.98). Next, this solution was cooled to about 2 ° C., and 72.0 g (0.419 mol) of bromine was dropped from the dropping funnel over 60 minutes while stirring. At the end of dropping, the temperature of the reaction solution was 16 ° C. After completion of the dropwise addition, the reaction solution was stirred for 30 minutes to complete the bromine addition reaction.
[0154]
Next, this reaction solution was treated in the same manner as in Example 10 to obtain mainly 2,2-bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl} propane. It was. This bromine compound is 94.9% pure and is derived from water per mole of 2,2-bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl} propane. The impurity was 0.003 mol, and the impurity derived from methanol was 0.019 mol.
[0155]
Example 18
In a glass reaction vessel used in Example 10, 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} sulfone 135 g (0.209 mol) and methylene chloride 230 g were placed and dissolved. Further, 1.54 g (0.0335 mol) of ethanol was added to this solution (number of hydroxyl groups per 100 aliphatic unsaturated groups: 8.0). The water content in this solution was 500 ppm (number of water molecules per 100 aliphatic unsaturated groups: 2.4). Next, this solution was cooled to about 2 ° C., and 80.0 g (0.501 mol) of bromine was dropped from the dropping funnel over 60 minutes while stirring. At the end of dropping, the temperature of the reaction solution was 16 ° C. After completion of the dropwise addition, the reaction solution was stirred for 30 minutes to complete the bromine addition reaction.
[0156]
Next, this reaction solution was treated in the same manner as in Example 10 to obtain mainly 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} sulfone. The bromine compound has a purity of 93.7%, 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} sulfone per mole of water, and impurities derived from water are 0. The impurity derived from 005 mol and ethanol was 0.040 mol.
[0157]
Example 19
In a glass reaction vessel used in Example 10, 135 g (0.227 mol) of bis {(3,5-dibromo-4-allyloxy) phenyl} methane and 230 g of chloroform dehydrated with synthetic zeolite were dissolved. Further, 2.33 g (0.0388 mol) of n-propanol was added to this solution (number of hydroxyl groups per 100 aliphatic unsaturated groups: 8.5). The water content in this solution was 200 ppm (the number of water molecules per 100 unsaturated aliphatic groups was 0.90). Next, this solution was set to 25 ° C., and 80.0 g (0.501 mol) of bromine was dropped from the dropping funnel over 100 minutes while stirring. At the end of dropping, the temperature of the reaction solution was 35 ° C. After completion of the dropwise addition, the reaction solution was stirred for 30 minutes to complete the bromine addition reaction.
[0158]
Next, this reaction solution was treated in the same manner as in Example 10 to obtain mainly 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} methane. The bromine compound has a purity of 94.5%, 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} methane per mole of water, and impurities derived from water are 0. The impurity derived from 003 mol and n-propyl alcohol was 0.036 mol.
[0159]
Example 20
The glass reaction vessel used in Example 10 was dehydrated with 135 g (0.232 mol) of (3,3 ′, 5,5′-tetrabromo-4,4′-diallyloxy) biphenyl and synthetic zeolite 1,4. -615 g of dioxane was added and dissolved. Further, 1.54 g (0.0335 mol) of ethanol was added to this solution (number of hydroxyl groups per 100 aliphatic unsaturated groups: 7.2). The water content in this solution was 400 ppm (number of water molecules per 100 aliphatic unsaturated groups: 3.6). Next, this solution was set to 25 ° C., and 80.0 g (0.501 mol) of bromine was dropped from the dropping funnel over 100 minutes while stirring. At the end of dropping, the temperature of the reaction solution was 35 ° C. After completion of the dropwise addition, the reaction solution was stirred for 30 minutes to complete the bromine addition reaction.
[0160]
Next, this reaction solution was treated in the same manner as in Example 10 to obtain mainly {3,3 ′, 5,5′-tetrabromo-4,4 ′-(2,3-dibromopropyloxy)} biphenyl. . This bromine compound has a purity of 94.0% and is an impurity derived from water with respect to 1 mole of {3,3 ′, 5,5′-tetrabromo-4,4 ′-(2,3-dibromopropyloxy)} biphenyl. Was 0.005 mol, and impurities derived from ethanol were 0.032 mol.
[0161]
The results of Examples 10 to 20 are shown in Table 3 and Table 4.
In Tables 3 and 4, the concentration of the compound having a hydroxyl group indicates the number of hydroxyl groups (100) per 100 unsaturated groups of the compound having an aliphatic unsaturated bond, and the concentration of water is the aliphatic unsaturated bond. The number of water molecules (100) per 100 unsaturated groups of a compound having Moreover, the impurity (mol) derived from water and the impurity (mol) derived from the compound having a hydroxyl group represent an amount relative to 1 mol of the obtained bromine compound.
[0162]
[Table 3]

[0163]
[Table 4]

[0164]
Example 21
72.6 g (0.454 mol) of bromine was placed in a 1 L glass reaction vessel equipped with a stirrer, condenser, thermometer and dropping funnel. In addition, a solution was prepared by dissolving 135 g (0.216 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane in 230 g of methylene chloride (the water content in this solution was 200 ppm). , 0.94 water molecules per 100 aliphatic unsaturated groups). Next, 365 g of a methylene chloride solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was added dropwise over 60 minutes at a temperature of 15 to 20 ° C. while stirring the reaction vessel. It was dripped at bromine from the funnel. After completion of the dropwise addition, the reaction solution was continuously stirred at a temperature of 15 to 20 ° C. for 30 minutes to complete the bromine addition reaction.
[0165]
Next, excess bromine in the reaction solution was reduced with 100 g of a 15 wt% sodium bisulfite aqueous solution, and then the produced hydrogen bromide was neutralized with a 25 wt% sodium hydroxide aqueous solution. Thereafter, a methylene chloride layer is separated from the solution, and about 90% of the methylene chloride is evaporated and removed from the methylene chloride layer. To this, 500 mL of methanol is added to precipitate a reaction product, and the precipitate is filtered to form a lump. The solid was removed. This massive solid was pulverized in a mortar and dried under reduced pressure at 5 mmHg at 80 ° C. for 3 hours to obtain a product.
[0166]
The resulting product ¹ As a result of analysis by H-NMR, a signal derived from —CHBr— was observed at 4.51 to 4.53 ppm, and —CHBr— was observed at 3.94 to 4.09 ppm. ₂ A signal derived from Br was observed. From FT-IR analysis, -O-CH ₂ It was confirmed that no absorption of allyl groups was observed. From the above analysis results, it was confirmed that the product was 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. This bromine compound had a purity of 96.5% and a bromine content of 67.5% (theoretical value: 67.8%).
[0167]
Example 22
In a 1 L glass reaction vessel equipped with a stirrer, condenser, thermometer and dropping funnel, 72.6 g (0.454 mol) bromine and 58.1 g methylene chloride were placed. Next, while stirring the inside of the reaction vessel, 135 g (0.216 mol) g of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane at a temperature of 15 to 20 ° C. in 60 minutes. It was dripped at the bromine solution from the dropping funnel. After completion of the dropwise addition, the reaction solution was continuously stirred at a temperature of 15 to 20 ° C. for 30 minutes to complete the bromine addition reaction.
[0168]
The obtained reaction solution was subjected to the same operation as in Example 21 to obtain a white solid product. The product obtained as in Example 21 is ¹ Analysis using H-NMR and FT-IR confirmed the product to be 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. It was. This bromine compound had a purity of 96.3% and a bromine content of 67.5% (theoretical value: 67.8%).
[0169]
Example 23
In a 1 L glass reaction vessel equipped with a stirrer, condenser, thermometer and dropping funnel, 72.6 g (0.454 mol) bromine and 58.1 g methylene chloride were placed. In addition, a solution was prepared by dissolving 140.8 g (0.216 mol) of 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane in 230 g of methylene chloride. Next, 370.8 g of a methylene chloride solution of 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane at a temperature of 15 to 20 ° C. while stirring in the reaction vessel. Was added dropwise to the bromine solution from the dropping funnel in 120 minutes. After completion of the dropwise addition, the reaction solution was continuously stirred at a temperature of 15 to 20 ° C. for 30 minutes to complete the bromine addition reaction.
[0170]
The obtained reaction solution was subjected to the same operation as in Example 21 to obtain a white solid product. The product obtained as in Example 21 is ¹ As a result of analysis using H-NMR and FT-IR, the product was 2,2-bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl} propane. It was confirmed. This bromine compound had a purity of 96.5% and a bromine content of 65.3% (theoretical value was 65.8%).
[0171]
Example 24
In a 1 L glass reaction vessel equipped with a stirrer, condenser, thermometer and dropping funnel, 72.6 g (0.454 mol) bromine and 58.1 g methylene chloride were placed. A solution was prepared by dissolving 128.7 g (0.216 mol) of bis {(3,5-dibromo-4-allyloxy) phenyl} methane in a mixed solvent of 161 g of methylene chloride and 69 g of 1,4-dioxane. Next, 358.7 g of the solution of bis {(3,5-dibromo-4-allyloxy) phenyl} methane is added to the bromine solution from the dropping funnel in 60 minutes at a temperature of 15 to 20 ° C. while stirring the reaction vessel. It was dripped. After completion of the dropwise addition, the reaction solution was continuously stirred at a temperature of 15 to 20 ° C. for 30 minutes to complete the bromine addition reaction.
[0172]
The obtained reaction solution was subjected to the same operation as in Example 21 to obtain a white solid product. The product obtained as in Example 21 is ¹ As a result of analysis using H-NMR and FT-IR, the product was confirmed to be bis {3,5-dibromo-4- (2,3-dibromo-propyloxy) phenyl} methane. This bromine compound had a purity of 96.0% and a bromine content of 69.5% (theoretical value: 69.8%).
[0173]
Example 25
In a 1 L glass reaction vessel equipped with a stirrer, condenser, thermometer and dropping funnel, 7.26 g (0.045 mol) of bromine and 217.7 g of methylene chloride were placed. Further, a solution in which 13.5 g (0.0216 mol) of bis {(3,5-dibromo-4-isobutenyloxy) phenyl} methane was dissolved in 23 g of methylene chloride was prepared. Next, 36.5 g of a methylene chloride solution of bis {(3,5-dibromo-4-isobutenyloxy) phenyl} methane was added in 60 minutes at a temperature of 15 to 20 ° C. while stirring the reaction vessel. It was dripped at the bromine solution from the dropping funnel. After completion of the dropwise addition, the reaction solution was continuously stirred at a temperature of 15 to 20 ° C. for 30 minutes to complete the bromine addition reaction.
[0174]
The obtained reaction solution was subjected to the same operation as in Example 21 to obtain a white solid product. The product obtained as in Example 21 is ¹ As a result of analysis using 1 H-NMR and FT-IR, it was confirmed that the product was bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl} methane. It was. This bromine compound had a purity of 96.2% and a bromine content of 67.7% (theoretical value: 67.8%).
[0175]
Example 26
In a 1 L glass reaction vessel equipped with a stirrer, condenser, thermometer and dropping funnel, 72.6 g (0.454 mol) bromine and 300 g methylene chloride were placed. In addition, a solution was prepared by dissolving 125.7 g (0.216 mol) of (3,3 ′, 5,5′-tetrabromo-4,4′-diallyloxy) biphenyl in 230 g of methylene chloride. Next, 355.7 g of a methylene chloride solution of the (3,3 ′, 5,5′-tetrabromo-4,4′-diallyloxy) biphenyl was added at a temperature of 15 to 20 ° C. while stirring the reaction vessel. The solution was added dropwise to the bromine solution from the dropping funnel in 60 minutes. After completion of the dropwise addition, the reaction solution was continuously stirred at a temperature of 15 to 20 ° C. for 30 minutes to complete the bromine addition reaction.
[0176]
The obtained reaction solution was subjected to the same operation as in Example 21 to obtain a white solid product. The product obtained as in Example 21 is ¹ As a result of analysis using H-NMR and FT-IR, the product is {3,3 ′, 5,5′-tetrabromo-4,4 ′-(2,3-dibromo-propyloxy)} biphenyl. It was confirmed. This bromine compound had a purity of 95.7% and a bromine content of 70.7% (theoretical value: 70.9%).
[0177]
Example 27
A 1 L glass reaction vessel equipped with a stirrer, condenser, thermometer and dropping funnel was charged with 72.6 g (0.454 mol) of bromine and 14.5 g of methylene chloride. Moreover, the solution which melt | dissolved 139.5 g (0.216 mol) of bis {(3,5-dibromo-4-allyloxy) phenyl} sulfone in 230 g of methylene chloride was prepared. Next, while stirring the reaction vessel, 369.5 g of methylene chloride solution of bis {3,5-dibromo-4-allyloxy) phenyl} sulfone at a temperature of 15 to 20 ° C. is bromine from the dropping funnel in 60 minutes. Dropped into the solution. After completion of the dropwise addition, the reaction solution was continuously stirred at a temperature of 15 to 20 ° C. for 30 minutes to complete the bromine addition reaction.
[0178]
The obtained reaction solution was subjected to the same operation as in Example 21 to obtain a white solid product. The product obtained as in Example 21 is ¹ As a result of analysis using 1 H-NMR and FT-IR, it was confirmed that the product was bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} sulfone. This bromine compound had a purity of 95.4% and a bromine content of 66.0% (theoretical value: 66.2%).
[0179]
Example 28
In a 1 L glass reaction vessel equipped with a stirrer, condenser, thermometer and dropping funnel, 72.6 g (0.454 mol) bromine and 58.1 g methylene chloride were placed. A solution prepared by dissolving 145.6 g (0.216 mol) of bis {(3,5-dibromo-4-isobutenyloxy) phenyl} sulfone in a mixed solvent of 161 g of methylene chloride and 69 g of 1,4-dioxane was prepared. did. Next, 375.6 g of a solution of the bis {3,5-dibromo-4-isobutenyloxy) phenyl} sulfone is added from a dropping funnel in 120 minutes at a temperature of 15 to 20 ° C. while stirring the reaction vessel. Dropped into bromine solution. After completion of the dropwise addition, the reaction solution was continuously stirred at a temperature of 15 to 20 ° C. for 30 minutes to complete the bromine addition reaction.
[0180]
The obtained reaction solution was subjected to the same operation as in Example 21 to obtain a white solid product. The product obtained as in Example 21 is ¹ As a result of analysis using H-NMR and FT-IR, it was confirmed that the product was bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy)} sulfone. . This bromine compound had a purity of 95.0% and a bromine content of 64.1% (theoretical value: 64.4%). The results of Examples 21 to 28 are shown in Tables 5 and 6.
[0181]
[Table 5]

[0182]
[Table 6]

[0183]
Example 29
In a 500 mL glass reaction vessel equipped with a stirrer, a condenser, a thermometer, and a dropping funnel, 72.7 g (0.455 mol) of bromine was placed. Further, 135 g (0.216 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was dissolved in 230 g of methylene chloride dehydrated with synthetic zeolite, and 0.36 g (0 A solution was prepared by adding 0.0113 mol and 2.6 hydroxyl groups per 100 aliphatic unsaturated groups. Next, the bromine in the reaction vessel is cooled to 2 ° C., and the methylene chloride solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane is added dropwise over 60 minutes while stirring. It was dripped at bromine from the funnel. At the end of dropping, the temperature of the reaction solution was 16 ° C. After completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to complete the bromine addition reaction. The water content in this reaction solution was 200 ppm (number of water molecules per 100 aliphatic unsaturated groups: 1.1).
[0184]
Next, excess bromine in the reaction solution was reduced with 50 g of a 15 wt% sodium bisulfite aqueous solution, and then the produced hydrogen bromide was neutralized with a 25 wt% sodium hydroxide aqueous solution. Thereafter, 100 g of ion-exchanged water is added, and after stirring, the methylene chloride layer is separated from this solution. About 90% of the methylene chloride is evaporated and removed from the methylene chloride layer, and 500 mL of methanol is added thereto to precipitate the reaction product. The precipitate was filtered to remove a blocky solid. This massive solid was pulverized in a mortar and dried under reduced pressure at 5 mmHg at 80 ° C. for 3 hours to obtain a product.
[0185]
The resulting product ¹ As a result of analysis by H-NMR, a signal derived from —CHBr— was observed at 4.51 to 4.53 ppm, and —CHBr— was observed at 3.94 to 4.09 ppm. ₂ A signal derived from Br was observed. From FT-IR analysis, -O-CH ₂ It was confirmed that no absorption of allyl groups was observed. From the above analysis results, it was confirmed that the product was mainly 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. This bromine compound has a purity of 96.7% and is an impurity derived from water with respect to 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. Was 0.0027 mol, and the impurity derived from methanol was 0.0155 mol. The inclination angle of the bromine compound was 40 °.
[0186]
Example 30
In Example 29, the same procedure as in Example 29 was performed, except that 0.36 g of ethanol (0.000078 mol, number of hydroxyl groups per 100 aliphatic unsaturated groups) was used instead of methanol. The addition reaction was performed. The water content in the reaction solution was 210 ppm (1.2 water molecules per 100 aliphatic unsaturated groups).
[0187]
This reaction solution was treated in the same manner as in Example 29 to obtain mainly 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. This bromine compound has a purity of 96.1% and is an impurity derived from water with respect to 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. Was 0.00025 mol and impurities derived from ethanol were 0.0124 mol. The inclination angle of the bromine compound was 41 °.
[0188]
Example 31
A 1 L glass reaction vessel equipped with a stirrer, condenser, thermometer and dropping funnel was charged with 72.6 g (0.454 mol) bromine and 230 g methylene chloride. In addition, 135 g (0.216 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was dissolved in 230 g of methylene chloride, and 0.36 g (0.000078 mol, aliphatic non-aliphatic) of ethanol was dissolved therein. A solution in which the number of hydroxyl groups (1.8 co) per 100 saturated groups was added was prepared. Next, the bromine solution in the reaction vessel is cooled to 2 ° C., and the methylene chloride solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane is added over 60 minutes while stirring. It was dripped at the bromine solution from the dropping funnel. At the end of dropping, the temperature of the reaction solution was 16 ° C. After completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to complete the bromine addition reaction. The water content in this reaction solution was 420 ppm (the number of water molecules per 100 aliphatic unsaturated groups was 3.6).
[0189]
The obtained reaction solution was treated in the same manner as in Example 29 to obtain a white solid product. The product obtained as in Example 29 is ¹ As a result of analysis using H-NMR and FT-IR, it was confirmed that the product was mainly 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. It was done. This bromine compound has a purity of 95.9% and is an impurity derived from water with respect to 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. Was 0.00041 mol, and impurities derived from ethanol were 0.0124 mol. The inclination angle of the bromine compound was 44 °.
[0190]
Example 32
A 1 L glass reaction vessel equipped with a stirrer, condenser, thermometer and dropping funnel was charged with 72.6 g (0.454 mol) bromine and 230 g methylene chloride. In addition, 135 g (0.216 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was dissolved in 230 g of methylene chloride, and 0.36 g (0.000078 mol, aliphatic non-aliphatic) of ethanol was dissolved therein. A solution in which the number of hydroxyl groups (1.8 co) per 100 saturated groups was added was prepared. Next, the methylene chloride solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane is stirred while refluxing methylene chloride at a temperature of 39 to 41 ° C. while stirring in the reaction vessel. Was added dropwise to the bromine solution from the dropping funnel over 10 minutes. After completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes while refluxing methylene chloride at a temperature of 39 to 41 ° C. to complete the addition reaction of bromine. The water content in this reaction solution was 420 ppm (the number of water molecules per 100 aliphatic unsaturated groups was 3.6).
[0191]
The obtained reaction solution was treated in the same manner as in Example 29 to obtain a white solid product. The product obtained as in Example 29 is ¹ As a result of analysis using H-NMR and FT-IR, it was confirmed that the product was mainly 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. It was done. This bromine compound has a purity of 96.4% and is an impurity derived from water with respect to 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. Was 0.0023 mol, and the impurity derived from ethanol was 0.0123 mol.
[0192]
Example 33
In a 500 mL glass reaction vessel equipped with a stirrer, condenser, thermometer and dropping funnel, 72.6 g (0.454 mol) of bromine, 230 g of methylene chloride dehydrated with synthetic zeolite and 0.36 g of ethanol (0.000078 mol, The number of hydroxyl groups 1.8 per 100 unsaturated aliphatic groups was added. Next, 135 g (0.216 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was obtained while refluxing methylene chloride at a temperature of 39 to 41 ° C. while stirring the reaction vessel. ) Was added to the bromine solution over 5 minutes. After completion of the addition, the reaction solution was continuously stirred for 30 minutes while refluxing methylene chloride at a temperature of 39 to 41 ° C. to complete the bromine addition reaction. The water content in this reaction solution was 210 ppm (number of water molecules per 100 aliphatic unsaturated groups: 1.2).
[0193]
The obtained reaction solution was treated in the same manner as in Example 29 to obtain a white solid product. The product obtained as in Example 29 is ¹ As a result of analysis using H-NMR and FT-IR, it was confirmed that the product was mainly 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. It was done. This bromine compound has a purity of 96.5% and is an impurity derived from water with respect to 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. Was 0.0021 mol, and impurities derived from ethanol were 0.0135 mol.
[0194]
Example 34
Into a 1 L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel was placed 72.7 g (0.455 mol) of bromine. Further, 135 g (0.216 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was dissolved in 230 g of methylene chloride dehydrated with synthetic zeolite, and 0.36 g of i-propanol was dissolved therein. A solution was prepared by adding (0.0006 mol, number of hydroxyl groups per 100 aliphatic unsaturated groups: 1.4). Next, the bromine in the reaction vessel is cooled to about 2 ° C., and while stirring, the solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane is added from the dropping funnel over 60 minutes. Added dropwise to bromine. At the end of dropping, the temperature of the reaction solution was 20 ° C. After completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to complete the bromine addition reaction. The water content in this reaction solution was 200 ppm (number of water molecules per 100 aliphatic unsaturated groups: 1.1).
[0195]
The obtained reaction solution was treated in the same manner as in Example 29 to obtain a white solid product. The product obtained as in Example 29 is ¹ As a result of analysis using H-NMR and FT-IR, it was confirmed that the product was mainly 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. It was done. This bromine compound has a purity of 96.3% and is an impurity derived from water with respect to 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. Was 0.0019 mol, and the impurity derived from i-propanol was 0.0146 mol. The inclination angle of the bromine compound was 40 °.
[0196]
Example 35
Into a 1 L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel was placed 72.7 g (0.455 mol) of bromine. Further, 135 g (0.216 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was dissolved in 615 g of chloroform dehydrated with synthetic zeolite, and 0.54 g (0.5. A solution was prepared by adding 0169 mol and 3.9 hydroxyl groups per 100 aliphatic unsaturated groups. Next, the bromine in the reaction vessel is cooled to 2 ° C., and while stirring, the chloroform solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane is added to the dropping funnel over 60 minutes. More dropwise to bromine. At the end of dropping, the temperature of the reaction solution was 16 ° C. After completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to complete the bromine addition reaction. The water content in this reaction solution was 100 ppm (number of water molecules per 100 aliphatic unsaturated groups: 1.1).
[0197]
Next, excess bromine in the reaction solution was reduced with 50 g of a 15 wt% sodium bisulfite aqueous solution, and then the produced hydrogen bromide was neutralized with a 25 wt% sodium hydroxide aqueous solution. Thereafter, 200 g of ion-exchanged water is added, and after stirring, the chloroform layer is separated from the solution. About 90% of the chloroform is evaporated and removed from the chloroform layer, and 500 mL of methanol is added thereto to precipitate the reaction product. The material was filtered to remove a blocky solid. This massive solid was pulverized in a mortar and dried under reduced pressure at 5 mmHg at 80 ° C. for 3 hours to obtain a product. As in Example 29, the product obtained is ¹ As a result of analysis using H-NMR and FT-IR, it was confirmed that the product was mainly 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. It was done. This bromine compound has a purity of 95.8% and is an impurity derived from water with respect to 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. Was 0.00022 mol, and the impurity derived from methanol was 0.0155 mol.
[0198]
Example 36
6500 g (0.435 mol) of bromine was placed in a 500 mL glass reaction vessel equipped with a stirrer, condenser, thermometer and dropping funnel. Further, 135 g (0.207 mol) of 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane was dissolved in 230 g of methylene chloride dehydrated with synthetic zeolite, and methanol was dissolved in 0.2 g of methanol. A solution to which 36 g (0.0113 mol, the number of hydroxyl groups per 100 aliphatic unsaturated groups: 2.7) was added was prepared. Next, the solution of 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane is stirred over 60 minutes while cooling the bromine in the reaction vessel to about 2 ° C. and stirring. The solution was added dropwise to bromine from the dropping funnel. At the end of dropping, the temperature of the reaction solution was 16 ° C. After completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to complete the bromine addition reaction. The water content in this reaction solution was 190 ppm (number of water molecules per 100 aliphatic unsaturated groups: 1.1).
[0199]
The obtained reaction solution was treated in the same manner as in Example 29 to obtain a white solid product. The product obtained as in Example 29 is ¹ As a result of analysis using 1 H-NMR and FT-IR, the product was mainly 2,2-bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl} propane. It was confirmed that there was. This bromine compound has a purity of 95.8%, and water per mole of 2,2-bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl} propane. The amount of impurities derived from was 0.0021 mol, and the amount of impurities derived from methanol was 0.0212 mol.
[0200]
Example 37
In a 500 mL glass reaction vessel equipped with a stirrer, condenser, thermometer and dropping funnel, 70.1 g (0.439 mol) of bromine was placed. Further, 135 g (0.209 mol) of bis {3,5-dibromo-4-allyloxy) phenyl} sulfone was dissolved in 230 g of methylene chloride dehydrated with synthetic zeolite, and 0.36 g (0.0113 mol, aliphatic) of methanol was dissolved therein. A solution was prepared by adding 2.7 hydroxyl groups per 100 unsaturated groups. Next, the bromine in the reaction vessel was cooled to about 2 ° C., and a solution of bis {3,5-dibromo-4-allyloxy) phenyl} sulfone was dropped into bromine from the dropping funnel over 60 minutes while stirring. At the end of dropping, the temperature of the reaction solution was 16 ° C. After completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to complete the bromine addition reaction. The water content in this reaction solution was 180 ppm (the number of water molecules per 100 aliphatic unsaturated groups was 1.0).
[0201]
The obtained reaction solution was treated in the same manner as in Example 29 to obtain a white solid product. The product obtained as in Example 29 is ¹ As a result of analysis using 1 H-NMR and FT-IR, it was confirmed that the product was mainly bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} sulfone. This bromine compound has a purity of 94.2%, and the impurity derived from water is 0.000020 with respect to 1 mol of bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} sulfone. Molar and impurities derived from methanol were 0.0328 mol.
[0202]
Example 38
In a 500 mL glass reaction vessel equipped with a stirrer, condenser, thermometer and dropping funnel was placed 76.2 g (0.477 mol) of bromine. Also, 135 g (0.227 mol) of bis {3,5-dibromo-4-allyloxy) phenyl} methane was dissolved in 615 g of chloroform dehydrated with synthetic zeolite, and 1.13 g (0.0157 mol, fat, n-butanol was dissolved in this. A solution having 3.5 hydroxyl groups per 100 unsaturated groups was added. Next, the bromine in the reaction vessel was cooled to about 2 ° C., and a solution of bis {3,5-dibromo-4-allyloxy) phenyl} methane was added dropwise to the bromine from the dropping funnel over 60 minutes while stirring. At the end of dropping, the temperature of the reaction solution was 16 ° C. After completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to complete the bromine addition reaction. The water content in the reaction solution was 100 ppm (the number of water molecules per 100 unsaturated aliphatic groups was 1.0).
[0203]
The obtained reaction solution was treated in the same manner as in Example 35 to obtain a white solid product. As in Example 29, the product obtained is ¹ As a result of analysis using H-NMR and FT-IR, it was confirmed that the product was mainly bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} methane. This bromine compound has a purity of 94.9%, and the impurity derived from water is 0.0013 with respect to 1 mol of bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} methane. The impurities derived from mol and n-butanol were 0.0353 mol.
[0204]
Example 39
A 1 L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel was charged with 77.9 g (0.487 mol) of bromine and 123 g of 1,4-dioxane dehydrated with synthetic zeolite. Further, 135 g (0.232 mol) of (3,3 ′, 5,5′-tetrabromo-4,4′-diallyloxy) biphenyl was dissolved in 615 g of 1,4-dioxane dehydrated with synthetic zeolite, and n A solution was prepared by adding 1.13 g of butanol (0.0157 mol, number of hydroxyl groups per 100 aliphatic unsaturated groups: 3.4). Next, the bromine solution in the reaction vessel was set to about 22 ° C., and the solution of (3,3 ′, 5,5′-tetrabromo-4,4′-diallyloxy) biphenyl was added over 10 minutes while stirring. It was dripped at the bromine solution from the dropping funnel. At the end of dropping, the temperature of the reaction solution was 50 ° C. After completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to complete the bromine addition reaction. The water content in this reaction solution was 120 ppm (number of water molecules per 100 aliphatic unsaturated groups: 1.4).
[0205]
Next, excess bromine in the reaction solution was reduced with 50 g of a 15 wt% sodium bisulfite aqueous solution, and then the produced hydrogen bromide was neutralized with a 25 wt% sodium hydroxide aqueous solution. Thereafter, 100 g of ion-exchanged water is added, and after stirring, a 1,4-dioxane layer is separated from this solution, and about 90% of 1,4-dioxane is evaporated and removed from the 1,4-dioxane layer. Was added to precipitate a reaction product, and this precipitate was filtered to take out a blocky solid. This massive solid was pulverized in a mortar and dried under reduced pressure at 5 mmHg at 80 ° C. for 3 hours to obtain a product. As in Example 29, the product obtained is ¹ As a result of analysis using 1 H-NMR and FT-IR, the product was mainly {3,3 ′, 5,5′-tetrabromo-4,4 ′-(2,3-dibromo-propyloxy)} biphenyl. It was confirmed that there was. This bromine compound has a purity of 94.6%, and water per mole of {3,3 ′, 5,5′-tetrabromo-4,4 ′-(2,3-dibromo-propyloxy)} biphenyl. The amount of impurities derived from this was 0.0019 mol, and the amount of impurities derived from n-butanol was 0.0254 mol.
[0206]
The results of Examples 29 to 39 are shown in Table 7 and Table 8.
In Tables 7 and 8, the concentration of the compound having a hydroxyl group indicates the number of hydroxyl groups (100) per 100 unsaturated groups of the compound having an aliphatic unsaturated bond, and the concentration of water is the aliphatic unsaturated bond. The number of water molecules (100) per 100 unsaturated groups of a compound having Moreover, the impurity (mol) derived from water and the impurity (mol) derived from the compound having a hydroxyl group represent an amount relative to 1 mol of the obtained bromine compound.
[0207]
[Table 7]

[0208]
[Table 8]

[0209]
Example 40
1000 g (1.60 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane (raw material No. (1)) was dissolved in 1703 g (20.0 mol) of methylene chloride. The specific gravity of this solution was 1.46, and as a result of measurement by the Karl Fischer method, it contained 160 ppm of water.
[0210]
In a glass reaction vessel equipped with a stirring blade 3, a condenser 4 and a thermometer 5 shown in FIG. ^-3 Bromine from the inlet 2 at a rate of L / min 0.58 × 10 ^-3 It was continuously added at a rate of L / min (bromine / compound (1) molar ratio 2.45). The solution mixed in the reaction vessel exothermed by the reaction heat of bromination, and the vaporized vapor was refluxed to the reaction vessel by the sufficiently cooled condenser 4. Raw material No. About 20 minutes after the start of the addition of the solution (1) and bromine, the reaction solution started to be led out from the outlet 8 and then continuously continued (residence time 20.4 minutes). The reaction solution in the reaction vessel (120 ml) was circulated in the reaction vessel at a rate of 0.03 L / min using the pump 6 from the time when the reaction solution started to be led out.
[0211]
In the reaction solution led out from the reaction vessel, excess bromine was reduced with an aqueous sodium disulfite solution (about 15% by weight), and then the produced hydrogen bromide was neutralized with an aqueous sodium hydroxide solution. Thereafter, 1000 g of ion-exchanged water is added to this solution and stirred, and the methylene chloride layer is separated, and about 90% of the methylene chloride is evaporated and removed from the methylene chloride layer. Methanol is added to this to precipitate the reaction product, This precipitate was filtered to take out a blocky solid. This massive solid was pulverized in a mortar and dried under reduced pressure at 80 ° C. for 10 hours to obtain 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. This bromine compound had a purity of 94.2% and a bromine content of 67.3% (theoretical value: 67.8%).
[0212]
Example 41
In Example 40, 1703 g of methylene chloride was replaced with 4405 g (51.8 mol) (specific gravity of the solution: 1.42, water content: 130 ppm), 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} The addition rate of the propane solution is 10.5 × 10 ^-3 The reaction was carried out in the same manner as in Example 40 except that L / min. The resulting 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane had a purity of 94.2%.
[0213]
Example 42
In Example 40, except that a mixed solvent of 900 g (10.6 mol) of methylene chloride and 803 g (6.7 mol) of chloroform was used in place of 1703 g of methylene chloride (the specific gravity of the solution was 1.48, the water content was 260 ppm), The reaction was carried out in the same manner as in Example 40. The obtained 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane had a purity of 94.0%.
[0214]
Example 43
In Example 40, the addition rate of a solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was 135.2 × 10 6. ^-3 L / min, bromine addition rate of 14.8 × 10 ^-3 The reaction was performed in the same manner as in Example 40 except that L / min. The obtained 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane had a purity of 94.1%.
[0215]
Example 44
1043 g (1.60 mol) of 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane (raw material No. (2)) was dissolved in 3400 g (40.0 mol) of methylene chloride. The specific gravity of this solution was 1.46, and as a result of measurement by the Karl Fischer method, it contained 120 ppm of water.
[0216]
Into a glass reaction vessel equipped with a stirring blade 3, a condenser 4 and a thermometer 5 shown in FIG. ^-3 Bromine from the inlet 2 at a rate of L / min 0.59 × 10 ^-3 It was added continuously at a rate of L / min (bromine / compound (2) molar ratio of 2.07). The solution mixed in the reaction vessel exothermed by the reaction heat of bromination, and the vaporized vapor was refluxed to the reaction vessel by the sufficiently cooled condenser 4. Raw material No. About 11 minutes after the start of the addition of the solution (2) and bromine, the reaction solution started to be led out from the outlet 8 and then continued to be continuously drawn out (residence time 10.8 minutes). The reaction solution in the reaction vessel (120 ml) was circulated in the reaction vessel at a rate of 0.03 L / min using the pump 6 from the time when the reaction solution started to be led out.
[0217]
The reaction solution derived from the reaction vessel was treated in the same manner as in Example 40 to give 2,2-bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl. } Propane was obtained. This bromine compound had a purity of 93.9%.
[0218]
Example 45
Bis {(3,5-dibromo-4-allyloxy) phenyl} methane (raw material No. (3)), 476 g (0.8 mol), 1700 g (20.0 mol) of methylene chloride and 1700 g (19.3 mol) of 1,4-dioxane ) And a mixed solvent. The specific gravity of this solution was 1.22, and as a result of measurement by the Karl Fischer method, it contained 320 ppm of water.
[0219]
Into a glass reaction vessel equipped with a stirring blade 3, a condenser 4 and a thermometer 5 shown in FIG. ^-3 Bromine from the inlet 2 at a rate of L / min 0.43 × 10 ^-3 It was continuously added at a rate of L / min (bromine / compound (3) molar ratio 3.13). The solution mixed in the reaction vessel exothermed by the reaction heat of bromination, and the vaporized vapor was refluxed to the reaction vessel by the sufficiently cooled condenser 4. Raw material No. About 11 minutes after the start of the addition of the solution (3) and bromine, the reaction solution started to be led out from the outlet 8 and then continued to be continuously drawn out (residence time 10.9 minutes). The reaction solution in the reaction vessel (120 ml) was circulated in the reaction vessel at a rate of 0.03 L / min using the pump 6 from the time when the reaction solution started to be led out.
[0220]
The reaction solution derived from the reaction vessel was treated in the same manner as in Example 40 to obtain bis {3,5-dibromo-4- (2,3-dibromo-propyloxy) phenyl} methane. This bromine compound had a purity of 93.3%.
[0221]
Example 46
Bis {(3,5-dibromo-4-isobutenyloxy) phenyl} methane (raw material No. (4)) 500 g (0.8 mol) was dissolved in 1700 g (20.0 mol) of methylene chloride. The specific gravity of this solution was 1.41, and as a result of measurement by the Karl Fischer method, it contained 160 ppm of water.
[0222]
Into a glass reaction vessel equipped with a stirring blade 3, a condenser 4 and a thermometer 5 shown in FIG. ^-3 Bromine from the inlet 2 at a rate of L / min 0.62 × 10 ^-3 It was continuously added at a rate of L / min (bromine / compound (4) molar ratio was 2.23). The solution mixed in the reaction vessel exothermed by the reaction heat of bromination, and the vaporized vapor was refluxed to the reaction vessel by the sufficiently cooled condenser 4. Raw material No. About 11 minutes after the start of the addition of the solution (4) and bromine, the reaction solution started to be led out from the outlet 8 and then continued to be continuously drawn out (residence time 10.8 minutes). The reaction solution in the reaction vessel (120 ml) was circulated in the reaction vessel at a rate of 0.03 L / min using the pump 6 from the time when the reaction solution started to be led out.
[0223]
The reaction solution derived from the reaction vessel is treated in the same manner as in Example 40 to obtain bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl} methane. It was. This bromine compound had a purity of 93.5%.
[0224]
Example 47
Bis {(3,5-dibromo-4-allyloxy) phenyl} sulfone (raw material No. (7)) 517 g (0.8 mol) was dissolved in 1700 g (20.0 mol) of methylene chloride. The specific gravity of this solution was 1.42, and it contained 180 ppm of water as a result of measurement by the Karl Fischer method.
[0225]
Into a glass reaction vessel equipped with a stirring blade 3, a condenser 4 and a thermometer 5 shown in FIG. ^-3 Bromine from the inlet 2 at a rate of L / min 0.59 × 10 ^-3 It was continuously added at a rate of L / min (bromine / compound (7) molar ratio 2.13). The solution mixed in the reaction vessel exothermed by the reaction heat of bromination, and the vaporized vapor was refluxed to the reaction vessel by the sufficiently cooled condenser 4. Raw material No. About 11 minutes after the start of the addition of the solution (7) and bromine, the reaction solution started to be led out from the outlet 8 and then continued continuously (residence time 10.8 minutes). The reaction solution in the reaction vessel (120 ml) was circulated in the reaction vessel at a rate of 0.03 L / min using the pump 6 from the time when the reaction solution started to be led out.
[0226]
The reaction solution derived from the reaction vessel was treated in the same manner as in Example 40 to obtain bis {3,5-dibromo-4- (2,3-dibromo-propyloxy) phenyl} sulfone. This bromine compound had a purity of 92.3%.
[0227]
Example 48
466 g (0.8 mol) of (3,3 ′, 5,5′-tetrabromo-4,4′-diallyloxy) biphenyl (raw material No. (5)) and 1700 g (20.0 mol) of methylene chloride and 1,4- Dissolved in a mixed solvent with 1700 g (19.3 mol) of dioxane. The specific gravity of this solution was 1.20, and as a result of measurement by the Karl Fischer method, it contained 320 ppm of water.
[0228]
Into a glass reaction vessel equipped with a stirring blade 3, a condenser 4 and a thermometer 5 shown in FIG. ^-3 Bromine from the inlet 2 at a rate of L / min 0.43 × 10 ^-3 It was continuously added at a rate of L / min (bromine / compound (5) molar ratio 3.16). The solution mixed in the reaction vessel exothermed by the reaction heat of bromination, and the vaporized vapor was refluxed to the reaction vessel by the sufficiently cooled condenser 4. Raw material No. About 11 minutes after the start of the addition of the solution (5) and bromine, the reaction solution started to be led out from the outlet 8 and then continued to be continuously drawn out (residence time 10.9 minutes). The reaction solution in the reaction vessel (120 ml) was circulated in the reaction vessel at a rate of 0.03 L / min using the pump 6 from the time when the reaction solution started to be led out.
[0229]
The reaction solution derived from the reaction vessel was treated in the same manner as in Example 40 to obtain {3,3 ′, 5,5′-tetrabromo-4,4 ′-(2,3-dibromo-propyloxy). } Biphenyl was obtained. This bromine compound had a purity of 93.0%.
[0230]
Example 49
In Example 40, the rate of addition of a solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was 0.57 × 10 ^-3 L / min, bromine addition rate of 0.062 × 10 ^-3 The reaction was performed in the same manner as in Example 1 except that L / min. The obtained 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane had a purity of 94.1%.
[0231]
Comparative Example 3
The addition rate of the solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was 5.3 × 10 ^-3 As a constant L / min, the bromine addition rate was 0.28 × 10 for the first 10 minutes. ^-3 L / min (bromine / compound (1) molar ratio is 1.18) and the next 10 min is 0.84 × 10 ^-3 L / min (bromine / compound (1) molar ratio was 3.55) was added continuously, and this was repeated, and the reaction was carried out for 40 minutes in the same manner as in Example 40. Raw material No. About 20 minutes after the start of the addition of the solution (1) and bromine, the reaction solution started to be led out from the outlet 8 and then continued to be continuously drawn out (residence time 20.5 minutes). The reaction solution in the reaction vessel (120 ml) was circulated in the reaction vessel at a rate of 0.03 L / min using the pump 6 from the time when the reaction solution started to be led out.
[0232]
The reaction solution derived from the reaction vessel was treated in the same manner as in Example 40 to obtain 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane. The purity of this bromine compound was 85.0%, and it was a powder with poor storage stability that easily adhered to each other.
[0233]
Comparative Example 4
In Example 40, the rate of addition of a solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was 5.3 × 10 ^-3 L / min, bromine addition rate is 0.4 × 10 ^-3 The reaction was carried out in the same manner as in Example 40 except that L / min (the molar ratio of bromine / raw material No. (1) was 1.69) and the same treatment as in Example 40 was carried out to give 2, Bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane was obtained. The purity of this bromine compound was 71.0%, and it was a powder with poor storage stability that would easily adhere to each other.
[0234]
Comparative Example 5
1,000 g (1.60 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was dissolved in 1703 g (20.0 mol) of methylene chloride. 1694 g of this solution was put into a 3000 ml glass container equipped with a stirring blade, a condenser, a thermometer and a dropping funnel, and 396 g of bromine was gradually dropped from the dropping funnel over 220 minutes with stirring. The solution temperature at the start of the addition of bromine was 20 ° C., but as the bromine was added dropwise, the solution temperature gradually increased due to the heat of reaction, and the solution temperature reached 37 ° C. at the end of the addition. While bromine was added dropwise, the reaction vessel was not cooled, and methylene chloride did not reflux. After completion of the dropwise addition of bromine, the reaction solution was treated in the same manner as in Example 40 to obtain 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. The purity of this bromine compound was as low as 82.1%, and the appearance was colored, and the storage stability easily adhered to each other was poor.
[0235]
The results of Examples 40 to 49 and Comparative Examples 3 to 4 are shown in Table 9 and Table 10.
In Tables 9 and 10, the solvents (A) to (C) are
(A) Methylene chloride
(B) Methylene chloride / chloroform = 53/47 (weight ratio)
(C) Methylene chloride / 1,4-dioxane = 50/50 (weight ratio)
The concentration of water is mol% with respect to the number of moles of unsaturated groups of the raw material compound.
[0236]
[Table 9]

[0237]
[Table 10]

[0238]
Example 50
In advance, 50 kg of a methylene chloride solution of 18.5 kg of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was prepared (the specific gravity of the solution was 1.47, and the water content was 150 ppm).
[0239]
Internal volume 20cm ^Three A static mixer consisting of 12 elements (cross-sectional area of 0.5 cm) ² The adjusted methylene chloride solution was added at a rate of 133.9 g / sec (91.1 mL / sec) and bromine was added at a rate of 25.7 g / sec (8.3 mL / sec), that is, the mixed solution flow rate was 199 cm / sec. After being continuously introduced into the static mixer and mixed so that the second {≈ (91.1 + 8.3) /0.5} [the residence time in this static mixer is 0.20 seconds {≈20 / (91.1 + 8.3)}], the mixed solution derived from the static mixer was put into a 30 L capacity stirring tank equipped with a condenser. In this agitation tank, heat of reaction was dissipated, and the scattering of bromine was suppressed by refluxing the vaporized vapor. In this stirring tank, the mixed solution was continuously stirred and allowed to stay in the stirring tank for about 5 minutes, and then was discharged from the overflow port of the stirring tank.
[0240]
About 10 ml of the reaction solution flowing out from the overflow port was collected, excess bromine was reduced with 5 g of 15% by weight sodium bisulfite aqueous solution, and then neutralized with 25% by weight sodium hydroxide aqueous solution. After most of methylene chloride was evaporated and removed from the obtained methylene chloride layer, 50 mL of methanol was added to precipitate the reaction product, and this precipitate was filtered to take out a bulk solid. This massive solid was pulverized in a mortar and dried under reduced pressure at 80 ° C. for 3 hours to obtain 1.7 g of a product.
[0241]
The resulting product ¹ As a result of analysis by H-NMR, a signal derived from —CHBr— was observed at 4.51 to 4.53 ppm, and —CHBr— was observed at 3.94 to 4.09 ppm. ₂ A signal derived from Br was observed. From FT-IR analysis, -O-CH ₂ It was confirmed that no absorption of allyl groups was observed. From the above analysis results, it was confirmed that the product was 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. This bromine compound had a purity of 96.3%, a melting point of 114 ° C., and a bromine content of 67.5% (theoretical value: 67.8%).
[0242]
Example 51
Internal volume of Example 50 20 cm ^Three A static mixer consisting of 12 elements (cross-sectional area of 0.5 cm) ² ) Instead of internal volume 10cm ^Three A static mixer consisting of 6 elements (cross-sectional area of 0.5 cm) ² ) Was used in the same manner as in Example 1 (the residence time in the static mixer was 0.10 seconds). This reaction product was analyzed in the same manner as in Example 1, and was confirmed to be 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. This bromine compound had a purity of 96.3%, a melting point of 114 ° C., and a bromine content of 67.5% (theoretical value: 67.8%).
[0243]
Example 52
In advance, 40 kg of a methylene chloride solution of 14.8 kg of 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane was prepared (the specific gravity of the solution was 1.47, and the water content was 150 ppm).
[0244]
In the same static mixer as used in Example 50, the adjusted methylene chloride solution was added at a rate of 98.9 g / second (67.3 mL / second), and bromine was added at a rate of 22.4 g / second (7.2 mL). / Second), that is, continuously introduced into the static mixer so that the flow rate of the mixed solution is 149 cm / second and mixed (the residence time in this static mixer is 0.27 seconds). The mixed solution derived from the static mixer was put into a stirring tank having a capacity of 23 L equipped with a condenser. In this agitation tank, heat of reaction was dissipated, and the scattering of bromine was suppressed by refluxing the vaporized vapor. In this stirring tank, the mixed solution was continuously stirred and allowed to stay in the stirring tank for about 5 minutes, and then was discharged from the overflow port of the stirring tank.
[0245]
This reaction solution was treated in the same manner as in Example 50 to obtain 1.6 g of a reaction product. The product obtained as in Example 50 is ¹ As a result of analysis using H-NMR and FT-IR, the product was 2,2-bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl} propane. It was confirmed. This bromine compound had a purity of 94.0% and a bromine content of 65.3% (theoretical value: 65.8%).
[0246]
Example 53
In advance, 40 kg of a methylene chloride solution of 14.8 kg of bis {(3,5-dibromo-4-allyloxy) phenyl} methane was prepared (the specific gravity of the solution was 1.47, the water content was 200 ppm).
[0247]
In the same static mixer as used in Example 50, the adjusted methylene chloride solution was added at a rate of 79.8 g / second (54.3 mL / second), and bromine was added at a rate of 16.6 g / second (5.4 mL). / Second), that is, after continuously introducing and mixing in the static mixer so that the flow rate of the mixed solution is 119 cm / second (the residence time in this static mixer is 0.34 seconds), The mixed solution derived from the static mixer was put into a 28 L stirring tank equipped with a condenser. In this agitation tank, heat of reaction was dissipated, and the scattering of bromine was suppressed by refluxing the vaporized vapor. In this stirring tank, the mixed solution was continuously stirred and retained in the stirring tank for about 8 minutes, and then was allowed to flow out from the overflow port of the stirring tank.
[0248]
This reaction solution was treated in the same manner as in Example 50 to obtain 1.8 g of a reaction product. The product obtained as in Example 50 is ¹ As a result of analysis using H-NMR and FT-IR, the product was confirmed to be bis {3,5-dibromo-4- (2,3-dibromo-propyloxy) phenyl} methane. This bromine compound had a purity of 91.8% and a bromine content of 69.1% (theoretical value: 69.8%).
[0249]
Example 54
In advance, a mixed solvent solution of bis {(3,5-dibromo-4-isobutenyloxy) phenyl} methane 14.8 kg of methylene chloride and 1,4-dioxane (methylene chloride / 1,4-dioxane = 70/30) The weight ratio was adjusted to 40 kg (the specific gravity of the solution was 1.35, and the water content was 250 ppm).
[0250]
In the same static mixer as used in Example 50, the adjusted mixed solvent solution was added at a rate of 126.8 g / sec (93.9 mL / sec), and bromine was added at a rate of 28.8 g / sec (9.3 mL). / Sec), that is, after continuously introducing and mixing in the static mixer so that the flow rate of the mixed solution is 206 cm / second (the residence time in this static mixer is 0.19 second), The mixed solution derived from the static mixer was put into a stirring tank having a capacity of 30 L equipped with a condenser. In this agitation tank, heat of reaction was dissipated, and the vaporized vapor was refluxed to suppress the scattering of bromine. In this stirring tank, the mixed solution was continuously stirred and allowed to stay in the stirring tank for about 5 minutes, and then was discharged from the overflow port of the stirring tank.
[0251]
This reaction solution was treated in the same manner as in Example 50 to obtain 1.8 g of a reaction product. The product obtained as in Example 50 is ¹ As a result of analysis using 1 H-NMR and FT-IR, it was confirmed that the product was bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl} methane. It was. This bromine compound had a purity of 92.0% and a bromine content of 67.0% (theoretical value: 67.7%).
[0252]
Example 55
In advance, (3,3 ′, 5,5′-tetrabromo-4,4′-diallyloxy) biphenyl 11.1 kg of a mixed solvent solution of methylene chloride and 1,4-dioxane (methylene chloride / 1,4-dioxane = 70 kg (70/30 weight ratio) was adjusted (the specific gravity of the solution was 1.35, and the water content was 250 ppm).
[0253]
In the same static mixer as used in Example 50, the adjusted mixed solvent solution was added at a rate of 140.0 g / sec (103.7 mL / sec), and bromine was added at a rate of 28.8 g / sec (9.3 mL). / Second), that is, after continuously introducing and mixing in the static mixer so that the flow rate of the mixed solution is 226 cm / second (the residence time in this static mixer is 0.18 seconds), The mixed solution derived from the static mixer was put into a stirring tank having a capacity of 20 L equipped with a condenser. In this agitation tank, heat of reaction was dissipated, and the vaporized vapor was refluxed to suppress the scattering of bromine. In this stirring tank, the mixed solution was continuously stirred and retained in the stirring tank for about 3 minutes, and then was allowed to flow out from the overflow port of the stirring tank.
[0254]
This reaction solution was treated in the same manner as in Example 50 to obtain 1.5 g of a reaction product. The product obtained as in Example 50 is ¹ As a result of analysis using H-NMR and FT-IR, the product is {3,3 ′, 5,5′-tetrabromo-4,4 ′-(2,3-dibromo-propyloxy)} biphenyl. It was confirmed. This bromine compound had a purity of 93.5% and a bromine content of 70.0% (theoretical value: 70.9%).
[0255]
Example 56
In advance, 40 kg of a methylene chloride solution of 14.8 kg of bis {(3,5-dibromo-4-allyloxy) phenyl} sulfone was prepared (the specific gravity of the solution was 1.47, and the water content was 600 ppm).
[0256]
In the same static mixer as used in Example 51, the adjusted methylene chloride solution was added at a rate of 99.3 g / second (67.6 mL / second), and bromine was added at a rate of 28.8 g / second (9.3 mL). / Second), that is, after continuously introducing and mixing in the static mixer so that the flow rate of the mixed solution is 154 cm / second (the residence time in this static mixer is 0.13 seconds), The mixed solution derived from the static mixer was put into a 15 L stirring tank equipped with a condenser. In this agitation tank, heat of reaction was dissipated, and the vaporized vapor was refluxed to suppress the scattering of bromine. In this stirring tank, the mixed solution was continuously stirred and retained in the stirring tank for about 3 minutes, and then was allowed to flow out from the overflow port of the stirring tank.
[0257]
This reaction solution was treated in the same manner as in Example 50 to obtain 1.5 g of a reaction product. The product obtained as in Example 50 is ¹ As a result of analysis using H-NMR and FT-IR, the product is {3,3 ′, 5,5′-tetrabromo-4,4 ′-(2,3-dibromo-propyloxy)} sulfone. It was confirmed. This bromine compound had a purity of 91.0% and a bromine content of 63.9% (theoretical value: 66.2%). The results of Examples 50 to 56 are shown in Table 11.
[0258]
[Table 11]

[0259]
Adjustment example 1
In a 10 L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 2,700 g (4.33 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane and synthetic zeolite were added. 4600 g of methylene chloride dehydrated in 1 was added and dissolved. While this solution was stirred, 1394 g (8.72 mol) of bromine was dropped from the dropping funnel over 8 minutes while refluxing methylene chloride at a temperature of 39 to 41 ° C. After completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes while refluxing methylene chloride at a temperature of 39 to 41 ° C. to complete the addition reaction of bromine. From this reaction solution, 10 mL was collected with a whole pipette, and the residual bromine in the bromine compound solution was measured and found to be 3.68 g / L.
[0260]
Adjustment example 2
In a 10 L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 2,700 g (4.33 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane and synthetic zeolite were added. 460 g of chlorobenzene dehydrated in 1 was added and dissolved. While stirring this solution, 1394 g (8.72 mol) of bromine was dropped from the dropping funnel at a temperature of 15 ° C. over 120 minutes. After completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes at a temperature of 15 ° C. to complete the bromine addition reaction. From this reaction solution, 10 mL was collected with a whole pipette, and the residual bromine in the bromine compound solution was measured and found to be 3.60 g / L.
[0261]
Adjustment example 3
In Preparation Example 1, 2,2-bis {(3,5-dibromo-4-isobutenyloxy) instead of 2,700 g of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane A bromination reaction was carried out in the same manner as in Preparation Example 1 except that 2820 g (4.33 mol) of phenyl} propane was used, and the result of measuring the residual bromine in the bromine compound solution was 3.05 g / L.
[0262]
Adjustment example 4
In Preparation Example 1, instead of 2,700 g of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane, 2580 g of bis {(3,5-dibromo-4-allyloxy) phenyl} methane (4. Except for using 33 mol), the bromination reaction was carried out in the same manner as in Preparation Example 1, and the residual bromine in the bromine compound solution was measured and found to be 3.05 g / L.
[0263]
Example 57
To 328 g of the bromine compound solution obtained in Preparation Example 1 was added 12.5 g of a 15.6 wt% aqueous sodium hydrogen sulfite solution (3.7 mol of sodium hydrogen sulfite per 1 mol of bromine), and immediately 25 wt% 3.8 g of sodium hydroxide aqueous solution (4.7 mol of sodium hydroxide with respect to 1 mol of bromine) and 300 g of water so that the weight ratio of the methylene chloride phase to the aqueous phase is approximately 1: 1. In addition, stirring was performed at 20 ° C. for 30 minutes. After completion of stirring, the methylene chloride phase and the aqueous phase were separated. The aqueous phase was removed, 100 mL of water was added to the methylene chloride phase, and the mixture was stirred and washed for 15 minutes. The pH of the aqueous phase was 7.2, and bromine was not detected in both phases.
[0264]
Next, 100 mL of this reduced and neutralized methylene chloride phase is taken, and about 90% of the methylene chloride is evaporated and removed from the methylene chloride phase. To this, 250 mL of methanol is added to precipitate the reaction product. A massive solid was removed by filtration. This massive solid was pulverized in a mortar and dried under reduced pressure at 5 mmHg at 80 ° C. for 3 hours to obtain 114.7 g of a product.
[0265]
The resulting product ¹ As a result of analysis by H-NMR, a signal derived from —CHBr— was observed at 4.51 to 4.53 ppm, and —CHBr— was observed at 3.94 to 4.09 ppm. ₂ A signal derived from Br was observed. From FT-IR analysis, -O-CH ₂ It was confirmed that no absorption of allyl groups was observed. From the above analysis results, it was confirmed that the product was 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. 1 g of this bromine compound was added to 10 g of water and stirred at 20 ° C. for 24 hours. Then, the bromine compound was filtered and the bromine concentration in the aqueous phase was measured, and bromine was not detected.
[0266]
Example 58
In Example 57, 12.5 g of 15.6 wt% aqueous sodium hydrogen sulfite solution was replaced with 24.5 g (7.3 mol of sodium hydrogen sulfite per 1 mol of bromine), and 25 wt% aqueous sodium hydroxide solution 3. Reduction and neutralization were performed in the same manner as in Example 57 except that 8 g was changed to 13.1 g (16.3 mol of sodium hydroxide per 1 mol of bromine). The methylene chloride phase and the aqueous phase were separated, the aqueous phase was removed, 100 mL of water was added to the methylene chloride phase, and the mixture was stirred and washed for 15 minutes. The pH of the aqueous phase was 7.2, and bromine was not detected in both phases.
[0267]
Next, in the same manner as in Example 57, 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane was obtained from the methylene chloride phase. 1 g of this bromine compound was added to 10 g of water and stirred at 20 ° C. for 24 hours. Then, the bromine compound was filtered and the bromine concentration in the aqueous phase was measured, and bromine was not detected.
[0268]
Example 59
In Example 57, except that 12.5 g of 15.6 wt% aqueous sodium hydrogen sulfite solution was replaced with 9.7 g of 15.6 wt% aqueous oxalic acid solution (3.3 mol of oxalic acid per 1 mol of bromine), Reduction and neutralization were performed in the same manner as in Example 57. The methylene chloride phase and the aqueous phase were separated, the aqueous phase was removed, 100 mL of water was added to the methylene chloride phase, and the mixture was stirred and washed for 15 minutes. The pH of the aqueous phase was 7.2, and bromine was not detected in both phases.
[0269]
Next, in the same manner as in Example 57, 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane was obtained from the methylene chloride phase. 1 g of this bromine compound was added to 10 g of water and stirred at 20 ° C. for 24 hours. Then, the bromine compound was filtered and the bromine concentration in the aqueous phase was measured, and bromine was not detected.
[0270]
Example 60
In Example 57, 12.5 g of the 15.6 wt% sodium hydrogen sulfite aqueous solution is replaced with 7.1 g of the 15.6 wt% sodium nitrite aqueous solution (3.2 mol of sodium nitrite with respect to 1 mol of bromine). Was reduced and neutralized in the same manner as in Example 57. The methylene chloride phase and the aqueous phase were separated, the aqueous phase was removed, 100 mL of water was added to the methylene chloride phase, and the mixture was stirred and washed for 15 minutes. The pH of the aqueous phase was 7.2, and bromine was not detected in both phases.
[0271]
Next, in the same manner as in Example 57, 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane was obtained from the methylene chloride phase. 1 g of this bromine compound was added to 10 g of water and stirred at 20 ° C. for 24 hours. Then, the bromine compound was filtered and the bromine concentration in the aqueous phase was measured, and bromine was not detected.
[0272]
Example 61
To 328 g of the bromine compound solution obtained in Preparation Example 2 was added 12.5 g of a 15.6 wt% aqueous sodium hydrogen sulfite solution (3.0 mol of sodium hydrogen sulfite per 1 mol of bromine), and immediately 25 wt% 3.8 g of sodium hydroxide aqueous solution (3.9 mol of sodium hydroxide to 1 mol of bromine) was added, and 300 g of water was added so that the weight ratio of the chlorobenzene phase to the aqueous phase was approximately 1: 1. The mixture was stirred at 20 ° C. for 30 minutes. After completion of stirring, the chlorobenzene phase and the aqueous phase were separated. The aqueous phase was removed, 100 mL of water was added to the chlorobenzene phase, and the mixture was stirred and washed for 15 minutes. The pH of the aqueous phase was 7.2, and bromine was not detected in both phases.
[0273]
Next, 100 mL of the reduced and neutralized chlorobenzene phase is taken, and about 90% of chlorobenzene is evaporated and removed from the chlorobenzene phase. To this, 250 mL of methanol is added to precipitate a reaction product, and the precipitate is filtered. The bulk solid was removed. The massive solid was pulverized in a mortar and dried under reduced pressure at 80 ° C. for 3 hours at 5 mmHg to obtain 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. . 1 g of this bromine compound was added to 10 g of water and stirred at 20 ° C. for 24 hours. Then, the bromine compound was filtered and the bromine concentration in the aqueous phase was measured, and bromine was not detected.
[0274]
Example 62
To 324 g of the bromine compound solution obtained in Preparation Example 3, 13.0 g of a 15.6 wt% aqueous sodium hydrogen sulfite solution (4.7 mol of sodium hydrogen sulfite per 1 mol of bromine) was added and immediately 25 wt% 4.0 g of sodium hydroxide aqueous solution (6.1 mol of sodium hydroxide per 1 mol of bromine) and 300 g of water so that the weight ratio of the methylene chloride phase to the aqueous phase is approximately 1: 1. In addition, stirring was performed at 20 ° C. for 30 minutes. After completion of stirring, the methylene chloride phase and the aqueous phase were separated. The aqueous phase was removed, 100 mL of water was added to the methylene chloride phase, and the mixture was stirred and washed for 15 minutes. The pH of the aqueous phase was 7.2, and bromine was not detected in both phases.
[0275]
Next, 100 mL of this reduced and neutralized methylene chloride phase is taken, and about 90% of the methylene chloride is evaporated and removed from the methylene chloride phase. To this, 250 mL of methanol is added to precipitate the reaction product. A massive solid was removed by filtration. The massive solid was pulverized in a mortar, dried under reduced pressure at 80 ° C. for 3 hours and 5 mmHg, and then 2,2-bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl} Propane was obtained. 1 g of this bromine compound was added to 10 g of water and stirred at 20 ° C. for 24 hours. Then, the bromine compound was filtered and the bromine concentration in the aqueous phase was measured, and bromine was not detected.
[0276]
Example 63
To 328 g of the bromine compound solution obtained in Preparation Example 4 was added 12.5 g of a 15.6 wt% aqueous sodium hydrogen sulfite solution (4.5 mol of sodium hydrogen sulfite per 1 mol of bromine), and immediately 25 wt% 3.9 g of sodium hydroxide aqueous solution (5.8 mol of sodium hydroxide per 1 mol of bromine) was added, and 300 g of water was added so that the weight ratio of the methylene chloride phase to the aqueous phase was approximately 1: 1. In addition, stirring was performed at 20 ° C. for 30 minutes. After completion of stirring, the methylene chloride phase and the aqueous phase were separated. The aqueous phase was removed, 100 mL of water was added to the methylene chloride phase, and the mixture was stirred and washed for 15 minutes. The pH of the aqueous phase was 7.2, and bromine was not detected in both phases.
[0277]
Next, 100 mL of this reduced and neutralized methylene chloride phase is taken, and about 90% of the methylene chloride is evaporated and removed from the methylene chloride phase. To this, 250 mL of methanol is added to precipitate the reaction product. A massive solid was removed by filtration. This massive solid was pulverized with a mortar and dried under reduced pressure at 5 mmHg at 80 ° C. for 3 hours to obtain bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} methane. 1 g of this bromine compound was added to 10 g of water and stirred at 20 ° C. for 24 hours. Then, the bromine compound was filtered and the bromine concentration in the aqueous phase was measured, and bromine was not detected.
[0278]
Example 64
Internal volume 20cm ^Three A static mixer consisting of 12 elements (cross-sectional area of 0.5 cm) ² ), The methylene chloride solution prepared in Preparation Example 1 was added at an addition rate of 10.7 g / second (7.2 mL / second), and an aqueous solution of 15.6% by weight of sodium bisulfite was added at an addition rate of 0.4 g / second (0. 38 mL / second), that is, after continuously introducing the mixed solution into the static mixer so that the flow rate of the mixed solution is 15.3 cm / second and mixing (the residence time in this static mixer is 2.6 seconds) And 3.7 mol of sodium hydrogen sulfite with respect to 1 mol of bromine), and the mixture was put into a stirring tank having a bottom valve with a volume of 30 L. The mixed solution was continuously stirred in this stirring tank, and after being allowed to stay in the stirring tank for about 10 minutes, a part was taken out from the bottom. When bromine concentration in the methylene chloride solution phase was measured, bromine was not detected.
[0279]
Next, 14 L of the reduced mixed solution taken out from the bottom of the stirring tank was added to 3000 g of an aqueous solution of 2.5 wt% sodium hydroxide with vigorous stirring (5.9 mol of sodium hydroxide per 1 mol of bromine). Is). This stirring was performed for 20 minutes. After completion of stirring, the methylene chloride phase and the aqueous phase were separated. The aqueous phase was removed, 2000 g of pure water was added to the methylene chloride phase, and the mixture was stirred and washed for 20 minutes. The time required to complete the reduction and neutralization reaction was about 1 hour.
[0280]
Example 65
The internal volume of Example 64 is 20 cm. ^Three A static mixer consisting of 12 elements (cross-sectional area of 0.5 cm) ² ) Instead of 30cm internal volume ^Three A static mixer consisting of 18 elements (cross-sectional area 0.5 cm ² ), The concentration of the aqueous sodium hydrogen sulfite solution was 5.2 wt%, and the addition rate was 0.8 g / second (0.75 mL / second). (The flow rate of the mixed solution was 15.9 cm / second, the residence time in the static mixer was 3.8 seconds, and 2.5 moles of sodium bisulfite per mole of bromine). When the bromine concentration in the methylene chloride solution phase after the reduction reaction was measured in the same manner as in Example 64, bromine was not detected.
[0281]
Example 66
The internal volume of Example 64 is 20 cm. ^Three A static mixer consisting of 12 elements (cross-sectional area of 0.5 cm) ² ) Instead of 30cm internal volume ^Three A static mixer consisting of 18 elements (cross-sectional area 0.5 cm ² ), The methylene chloride solution was added at a rate of 26.9 g / sec (18.2 mL / sec), and the rate of addition of the aqueous sodium hydrogen sulfite solution was 1.04 g / sec (0.95 mL / sec). The same operation as in Example 1 was performed (the flow rate of the mixed solution was 38.3 cm / second, the residence time in the static mixer was 1.5 seconds, and sodium bisulfite with respect to 1 mol of bromine. 3.7 moles). When the bromine concentration in the methylene chloride solution phase after the reduction reaction was measured in the same manner as in Example 64, bromine was not detected.
[0282]
Example 67
The same operation as in Example 1 was performed except that the addition rate of the aqueous solution of sodium hydrogen sulfite was changed to 0.8 g / second (0.75 mL / second) (the flow rate of the mixed solution was 16.0 cm). / Second, residence time in the static mixer is 2.6 seconds, 7.4 moles of sodium hydrogen sulfite per mole of bromine). When the bromine concentration in the methylene chloride solution phase after the reduction reaction was measured in the same manner as in Example 64, bromine was not detected.
[0283]
Example 68
In Example 64, the methylene chloride solution prepared in Preparation Example 1 was replaced with the chlorobenzene solution prepared in Preparation Example 2, and the addition rate was changed to 10.9 g / second (9.9 mL / second). The same operation was performed (the flow rate of the mixed solution was 20.7 cm / second, the residence time in the static mixer was 1.9 seconds, and 3.0 moles of sodium hydrogen sulfite per mole of bromine. Is). When bromine concentration in the chlorobenzene solution phase after the reduction reaction was measured in the same manner as in Example 1, bromine was not detected.
[0284]
Example 69
The same operation as in Example 64 was performed except that the methylene chloride solution prepared in Preparation Example 1 was replaced with the methylene chloride solution prepared in Preparation Example 4 (the flow rate of the mixed solution was 15.2 cm / second). And the residence time in the static mixer is 2.7 seconds, 3.7 moles of sodium hydrogen sulfite per mole of bromine). When the bromine concentration in the methylene chloride solution phase after the reduction reaction was measured in the same manner as in Example 64, bromine was not detected.
[0285]
Example 70
In Example 64, except that the methylene chloride solution was added at a rate of 5.4 g / sec (3.6 mL / sec) and the sodium bisulfite aqueous solution was added at a rate of 0.2 g / sec (0.19 mL / sec). The same operation as in Example 1 was performed (the flow rate of the mixed solution was 7.6 cm / second, the residence time in the static mixer was 5.3 seconds, and sodium bisulfite with respect to 1 mol of bromine. 3.7 moles). When the bromine concentration in the methylene chloride solution phase after the reduction reaction was measured in the same manner as in Example 64, bromine was not detected.
[0286]
Example 71
In Example 64, an aqueous solution of 15.6% by weight sodium dithionite was used instead of an aqueous solution of sodium bisulfite, and the addition rate was 0.4 g / sec (0.38 mL / sec). The same operation as in Example 1 was performed (the flow rate of the mixed solution was 15.2 cm / second, the residence time in the static mixer was 2.6 seconds, and dithione relative to 1 mole of bromine. Acid sodium 2.5 mol). When the bromine concentration in the methylene chloride solution phase after the reduction reaction was measured in the same manner as in Example 64, bromine was not detected.
[Brief description of the drawings]
FIG. 1 is a diagram showing an inclination angle in evaluation of an inclination angle (after heating at 70 ° C. for 4 hours).
[Explanation of symbols]
1 Glass surface
2 samples
3 horizontal plane
FIG. 2 shows an example of a reaction apparatus for performing a bromination reaction in the present invention.
FIG. 3 shows another example of a reaction apparatus for performing bromination reaction in the present invention.
[Explanation of symbols]
1 Raw material compound solution inlet
2 Bromine or bromine solution inlet
3 Stirring blade
4 condenser
5 Thermometer
6 Pump
7 Circulating fluid inlet
8 Reaction solution inlet
9 Reaction solution

Claims (6)

A method of producing bromine compound represented by the following general formula by reacting a compound having an aliphatic unsaturated bond represented by the (1) and the bromine represented by the following general formula (2), in the general formula (1) The compound represented by formula (1), bromine and a solvent inert to the reaction are continuously fed into the reactor separately or as a mixture in any combination. On the other hand, bromine in an amount of 1 to 5 molecules per unsaturated group in the compound is supplied, and the reaction is carried out while removing a substantial amount of heat of reaction by the heat of vaporization of the solvent or bromine in the reactor. The continuous production method of a bromine compound characterized by taking out the reaction mixture from the reactor and then recovering the bromine compound represented by the general formula (2) from the reaction mixture.
R ¹ —O—Ar ¹ —Y—Ar ² —O—R ² (1)
(In the formula, Ar ¹ and Ar ² may be the same or different and represent an aromatic hydrocarbon group having 5 to 16 carbon atoms or a saturated alicyclic hydrocarbon group having 5 to 12 carbon atoms, and these hydrocarbon groups May be substituted by at least one halogen atom; Y is a saturated hydrocarbon group having 1 to 6 carbon atoms, sulfone group, sulfide group, ketone group, alkylene oxide group having 2 to 6 carbon atoms or a single bond R ¹ and R ² may be the same or different and each represents a hydrocarbon group having 2 to 11 carbon atoms having at least one aliphatic unsaturated group, and one of R ¹ and R ² is A part of the unsaturated group may be added with a halogen atom.)
R ³ —O—Ar ¹ —Y—Ar ² —O—R ⁴ (2)
(In the formula, Ar ¹ , Ar ² and Y are the same as defined in the general formula (1). R ³ and R ⁴ are unsaturated groups in R ¹ and R ² in the general formula (1), respectively. Means a group saturated by a bromine atom.) The continuous process compounds and bromine, bromine compounds of continuously fed claim 1, wherein in the reactor through a flow mixer as a mixture stream with a solvent of at least one part if necessary with the aliphatic unsaturated group . The continuous production method of a bromine compound according to claim 2, wherein the flow rate of the liquid flow in the flow mixer is 15 to 500 cm / sec. The continuous production method of a bromine compound according to claim 2, wherein the residence time of the liquid flow in the flow mixer is 0.01 to 180 seconds. The continuous production method of a bromine compound according to claim 2 , wherein the flow mixer is a static mixer. The continuous production method of a bromine compound according to claim 2, wherein the flow mixer is a static mixer having 4 to 20 elements.

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