JPS5929175B2 - Production method of hexabrom diphenyl ether - Google Patents
Production method of hexabrom diphenyl etherInfo
- Publication number
- JPS5929175B2 JPS5929175B2 JP52055484A JP5548477A JPS5929175B2 JP S5929175 B2 JPS5929175 B2 JP S5929175B2 JP 52055484 A JP52055484 A JP 52055484A JP 5548477 A JP5548477 A JP 5548477A JP S5929175 B2 JPS5929175 B2 JP S5929175B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- diphenyl ether
- bromine
- catalyst
- ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fireproofing Substances (AREA)
Description
【発明の詳細な説明】
本発明は、選択的にヘキサブロムジフェニルエーテルを
製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for selectively producing hexabromidiphenyl ether.
ヘキサブロムジフェニルエーテルの製造法としては、ジ
フェニルエーテルを原料としてジブロムエタン、テトラ
クロルエタン、四塩化炭素等の有機溶媒中で臭素とジフ
ェニルエーテルのモル比を６として、あるいは発煙硫酸
中で臭素とジフェニルエーテルのモル比を３として反応
させる方法が知られている。しかし、これらの方法では
、有機溶媒の臭素化、有機溶媒の回収精製、廃硫酸の処
理等が必要であり、又、同一規模の製造に際して、大き
な製造装置が必要である等、工業的に不利な点が多く、
そのうえ、ペンタブロムジフェニルエーテル、ヘプタブ
ロムジフェニルエーテル等の副生物が多く、ヘキサブロ
ムジフェニルエーテルを選択的に高収率で製造すること
は出来なかつた。一方、臭素中でジフェニルエーテルを
臭素化する方法については、本発明者らの検討の結果、
鉄を含有する触媒の存在下で反応を行うか、あるいは、
鉄を含有する触媒と、アルカリおよびアルカリ土類金属
の硫酸塩、リン酸塩、ポリリン酸塩等との共存下で反応
を行う方法により、ヘキサブロムジフェニルエーテルを
選択的に製造しうることが判明し先に特許出願した（特
願昭５２一２７６２１号及び特願昭５２−３０３１０号
）。Hexabrom diphenyl ether can be produced using diphenyl ether as a raw material in an organic solvent such as dibromoethane, tetrachloroethane, or carbon tetrachloride with a molar ratio of bromine and diphenyl ether of 6, or in fuming sulfuric acid with a molar ratio of bromine and diphenyl ether of 6. Method 3 is known. However, these methods require bromination of organic solvents, recovery and purification of organic solvents, treatment of waste sulfuric acid, etc., and also have industrial disadvantages such as the need for large production equipment for the same scale of production. There are many points,
Furthermore, there were many by-products such as pentabromidiphenyl ether and heptabromidiphenyl ether, making it impossible to selectively produce hexabromidiphenyl ether in high yield. On the other hand, as a result of the studies conducted by the present inventors regarding the method of brominating diphenyl ether in bromine,
The reaction is carried out in the presence of an iron-containing catalyst, or
It has been found that hexabromidiphenyl ether can be selectively produced by a method in which the reaction is carried out in the presence of an iron-containing catalyst and alkali and alkaline earth metal sulfates, phosphates, polyphosphates, etc. We have previously filed patent applications (Japanese Patent Application No. 52-27621 and Japanese Patent Application No. 30310/1983).
鉄を含有する触媒の存在下で反応を行う方法については
、反応速度が極めて速く、しかも反応熱が大きいため、
反応の制御が困難であるという欠点があつた。これに対
し鉄を含有する触媒とアルカリおよびアルカリ土類金属
の硫酸塩、リン酸塩、ポリリン酸塩等との共存下で反応
する方法は、反応制御が極めて容易であり、ヘキサブロ
ムジフェニルエーテルの優れた製造法の一つである。又
、本発明者らは、最近臭素中でジフェニルエーテルを臭
素化して２ ・ ４ ・ ２’・ ４’・−テトラブロ
ムジフェニルエーテルを定量的に製造する方法を見出し
特許出願した（昭和５２年４月１２日出願）。今回更に
２ ・ ４ ・ ２’ ・ ４’ ・ −テトラブロム
ジフェニルエーテルを臭素溶媒中で臭素化するならば、
へキサブロムジフェニルエーテルの製造反応の制御が容
易であることを見出し、本発明に達・ したものである
。而して、本発明は過剰の臭素を溶媒として鉄粉並びに
無水状態の鉄の塩化物及び硫酸塩の一種又は２種以上の
存在下に３５℃以下の温度で２・４・２′・４′−テト
ラプロムジフエニルエーテルを臭素と反応させることを
特徴とするヘキサプロムジフエニルエーテルの製造法に
関するものである。Regarding the method of conducting the reaction in the presence of an iron-containing catalyst, the reaction rate is extremely fast and the heat of reaction is large.
The drawback was that it was difficult to control the reaction. On the other hand, the method of reacting in the coexistence of an iron-containing catalyst with an alkali or alkaline earth metal sulfate, phosphate, polyphosphate, etc. is extremely easy to control the reaction, and has the advantages of hexabromidiphenyl ether. This is one of the manufacturing methods. In addition, the present inventors recently discovered a method for quantitatively producing 2,4,2',4'-tetrabromidiphenyl ether by brominating diphenyl ether in bromine, and filed a patent application for this method (April 12, 1972). ). This time, if we further bromine 2 4 2'4' -tetrabromidiphenyl ether in a bromine solvent,
The present invention was achieved by discovering that the reaction for producing hexabrom diphenyl ether can be easily controlled. Therefore, the present invention provides 2, 4, 2', 4 in excess bromine as a solvent in the presence of iron powder and one or more of anhydrous iron chloride and sulfate at a temperature of 35°C or lower. The present invention relates to a method for producing hexaprom diphenyl ether, which comprises reacting '-tetraprom diphenyl ether with bromine.
本発明によつて得られるヘキサプロムジフエニルエーテ
ルは、主成分として２・４・５・グ・ｌ・５′−ヘキサ
プロムジフエニルエーテル８５〜９５％、その異性体３
〜１０％を含み、その他にペンタプロムジフエニルエー
テル、ヘプタプロムジフエニルエーテル２〜５％を含む
固体である。本発明は、臭素中で選択的にヘキサプロム
ジフエニルエーテルを製造することを可能とし、工業的
、経済的に優れたヘキサプロムジフエニルエーテルの製
造を可能にした。本発明に於いて、溶媒として使用する
臭素の使用量は反応当量の２〜１５倍量、好ましくは４
〜１０倍量である。Hexaprom diphenyl ether obtained by the present invention has 85 to 95% of 2,4,5,g,l,5'-hexaprom diphenyl ether as a main component, and 3 isomers thereof.
It is a solid containing ~10% of pentaprom diphenyl ether and 2-5% of heptaprom diphenyl ether. The present invention makes it possible to selectively produce hexaprom diphenyl ether in bromine, making it possible to produce industrially and economically superior hexaprom diphenyl ether. In the present invention, the amount of bromine used as a solvent is 2 to 15 times the reaction equivalent, preferably 4
~10 times the amount.
２倍量以下では反応により臭素が消費されるにつれて臭
素の溶媒効果がうすれ均一な混合が保たれなくなるため
、ヘキサプロムジフエニルエーテルを選択的に製造する
ことが困難となり、一方反応当量の１５倍量以上では反
応後の臭素の回収等、経済的に不利となるので好ましく
ない。If the amount is less than twice the amount, as the bromine is consumed by the reaction, the solvent effect of bromine will weaken and homogeneous mixing will not be maintained, making it difficult to selectively produce hexaprom diphenyl ether. If the amount exceeds this amount, it is not preferable because it will be economically disadvantageous, such as recovery of bromine after the reaction.
反応に使用する触媒は前記した様に鉄粉又は無水状態の
鉄の塩化物もしくは硫酸塩であるが、鉄の塩化物として
は塩化第１鉄及び塩化第２鉄、硫酸塩としては硫酸第１
鉄及び硫酸第２鉄のどちらを使用してもよい。As mentioned above, the catalyst used in the reaction is iron powder or anhydrous iron chloride or sulfate. Iron chlorides include ferrous chloride and ferric chloride, and sulfates include ferrous sulfate and iron chloride.
Either iron or ferric sulfate may be used.
触媒の使用量は使用する臭素量に対して０．０１〜５重
量％、好ましくは０．１〜２重量％である。０．０１重
量％以下では触媒効果が弱く、５重量％以上では製品中
への触媒の混入等があり好ましくない。The amount of catalyst used is 0.01 to 5% by weight, preferably 0.1 to 2% by weight, based on the amount of bromine used. If it is less than 0.01% by weight, the catalytic effect is weak, and if it is more than 5% by weight, the catalyst may be mixed into the product, which is not preferable.
触媒およびテトラプロムジフエニルエーテルの添加は微
粉砕した粉体として、あるいは一部の臭素に溶解または
懸濁しておいて臭素中に添加する。The catalyst and tetraprom diphenyl ether are added in the form of finely pulverized powder, or dissolved or suspended in some bromine.
反応は３５℃以下好ましくは３０℃以下で１時間以上行
う。反応のさせかたは次の二方法のいづれで行なつても
よい。１臭素中にテトラプロムジフエニルエーテルを加
え所定の温度でよく撹拌した後、触媒を加える。The reaction is carried out at 35°C or lower, preferably 30°C or lower for 1 hour or more. The reaction may be carried out by either of the following two methods. 1. Tetraprom diphenyl ether is added to bromine, stirred well at a predetermined temperature, and then a catalyst is added.
２臭素中に触媒を加え、所定の温度でテトラプロムジフ
エニルエーテルを加える。Add the catalyst to the dibromine solution and add the tetraprom diphenyl ether at a given temperature.
本発明に於いて原料として使用するテトラプロムジフエ
ニルエーテルは、たとえばジフエニルエーテルを過剰の
臭素中で（ａ） ３５℃乃至常圧下の臭素の沸点温度に
於いて無触媒で、もしくは
（ｂ）亜鉛および錫の塩化物および硫酸塩；チタンの塩
化物，結晶水を有する鉄の塩化物、硫酸塩およびりん酸
塩；並びにアルミニウムの硫酸塩およびりん酸塩の１種
又は２種以上の存在下３５℃以下の温度で反応させるこ
とによつて製造される。Tetraprom diphenyl ether used as a raw material in the present invention can be obtained by, for example, preparing diphenyl ether in excess bromine (a) without a catalyst at the boiling point temperature of bromine at 35°C to normal pressure, or (b) In the presence of one or more of chlorides and sulfates of zinc and tin; chlorides of titanium, chlorides, sulfates and phosphates of iron with water of crystallization; and sulfates and phosphates of aluminum. It is produced by reacting at a temperature below 35°C.
この際使用する臭素の量は、反応当量の１．５〜５倍量
、好ましくは２〜４倍量である。反応当量の１．５倍量
以下の臭素では反応により臭素が消費されるにつれて臭
素の溶媒効果がうすれ均一な混合が保たれなくなるため
テトラプロムジフエニルエーテルの選択率が低下し、一
方反応当量の５倍量以上では反応後の臭素の回収等経済
的に不利となるので好ましくない。ジフエニルエーテル
からテトラプロムジフエニルエーテルを得る反応は、触
媒を用いなくてもよいが、触媒を用いない場合には触媒
を用いる場合に比べ、高温下でかつ長時間反応させるこ
とが必要であり、従つて工業的には触媒を用いることが
好ましい。The amount of bromine used at this time is 1.5 to 5 times the reaction equivalent, preferably 2 to 4 times the reaction equivalent. If the amount of bromine is less than 1.5 times the reaction equivalent, as the bromine is consumed by the reaction, the solvent effect of bromine will weaken and homogeneous mixing will not be maintained, resulting in a decrease in the selectivity of tetraprom diphenyl ether. If the amount is 5 times or more, it is not preferable because it will cause economical disadvantages such as recovery of bromine after the reaction. The reaction to obtain tetraprom diphenyl ether from diphenyl ether does not require the use of a catalyst, but when a catalyst is not used, it is necessary to carry out the reaction at a higher temperature and for a longer time than when a catalyst is used. Therefore, industrially it is preferable to use a catalyst.
反応は触媒を用いない場合には３５℃以上、好ましくは
４０℃以上常圧下の臭素の沸点以下の温度で３時間以上
、触媒を用いる場合には３５℃以下好ましくは３０℃以
下で１時間以上行う。尚、触媒を用いる場合の触媒の量
は、使用する臭素に対して０．０１重量％〜５重量％、
好ましくは０．１重量％〜２重量％である。０．０１重
量％以下では触媒効果が弱く、５重量％以上では製品中
への触媒の混入等があり好ましくない。When a catalyst is not used, the reaction is carried out at a temperature of 35°C or higher, preferably 40°C or higher and below the boiling point of bromine under normal pressure for 3 hours or more, and when a catalyst is used, the reaction is carried out at a temperature of 35°C or lower, preferably 30°C or lower for 1 hour or more. conduct. In addition, when using a catalyst, the amount of the catalyst is 0.01% to 5% by weight based on the bromine used,
Preferably it is 0.1% to 2% by weight. If it is less than 0.01% by weight, the catalytic effect is weak, and if it is more than 5% by weight, the catalyst may be mixed into the product, which is not preferable.
本発明では、上述の如き反応方法で得られた反応液から
、触媒を用いた場合には反応液中に水又は塩酸、硫酸等
の酸性水溶液を加え触媒を水層に抽出した後、過剰の臭
素を留出除去し、一方触媒を用いない場合は反応液中に
水を加えて後過剰の臭素を留出除去することによつて水
中に析出するテトラプロムジフエニルエーテルを分離し
て本発明の原料として使用すればよいが、好ましい本発
明の実施態様は上述の如き反応方法で得られた反応液を
そのまま引続いて本発明の反応液として使用することで
ある。In the present invention, when a catalyst is used, water or an acidic aqueous solution such as hydrochloric acid or sulfuric acid is added to the reaction solution obtained by the reaction method as described above, and the catalyst is extracted into the aqueous layer. In the present invention, bromine is removed by distillation, and when a catalyst is not used, water is added to the reaction solution, and then excess bromine is removed by distillation to separate tetraprom diphenyl ether precipitated in water. However, a preferred embodiment of the present invention is to use the reaction solution obtained by the above-mentioned reaction method directly as the reaction solution of the present invention.
但し本発明では反応液中に水分が存在することは好まし
くないので、反応液のまま引続いて本発明に使用する上
述の実施態様に於いてはテトラブロムジフエニルエーテ
ルを得る第１段の反応に結晶水を有する鉄の塩化物、硫
酸塩又はりん酸塩を触媒として使用することは避けるべ
きである。反応液のまま引続いて本発明に使用する土述
の実施態様に於いては、テトラブロム体を得る第１段の
反応の終了後、本発明で使用する触媒を粉体として、あ
るいは少量の臭素またはジフエニルエーテルに溶解しあ
るいは懸濁して一度にもしくは分割して該反応液中に加
えられる。However, in the present invention, the presence of water in the reaction solution is not preferred, so in the above-mentioned embodiment in which the reaction solution is used in the present invention subsequently, the first stage reaction to obtain tetrabrom diphenyl ether is The use of iron chlorides, sulfates or phosphates with water of crystallization as catalysts should be avoided. In the embodiment described above, in which the reaction solution is used in the present invention, after the first stage reaction to obtain the tetrabromine compound is completed, the catalyst used in the present invention is used in the form of a powder or a small amount of bromine is added. Alternatively, it is dissolved or suspended in diphenyl ether and added to the reaction solution all at once or in portions.
本実施態様に於いては、テトラブロムジフエニルエーテ
ルを製造する一段目の反応は、比較的反応速度が遅く、
反応制御が容易であり、そのうえ、反応生成物中の２・
４・２５・４′・−テトラブロムジフエニルエーテル含
量が９８〜１００％であり、定量的なテトラブロムジフ
エニルエーテルの製造法であり、ヘキサブロムジフエニ
ルエーテルを製造する二段目の反応は、反応速度が速い
が、テトラブロムジフエニルエーテルを出発原料とする
ことにより、ジフエニルエーテルを出発原料とする場合
に比べ、反応熱が小さく、それ故二段目の反応において
もその制御は極めて容易である。In this embodiment, the first stage reaction for producing tetrabrom diphenyl ether has a relatively slow reaction rate;
The reaction is easy to control, and in addition, 2.
4,25,4'--Tetrabrom diphenyl ether content is 98-100%, this is a quantitative method for producing tetrabrom diphenyl ether, and the second stage reaction to produce hexabrom diphenyl ether is , the reaction rate is fast, but by using tetrabrom diphenyl ether as the starting material, the heat of reaction is smaller than when using diphenyl ether as the starting material, so it is extremely difficult to control the second reaction. It's easy.
反応終了後、反応液中に水又は、塩酸、硫酸等の酸性水
溶液を加えて触媒等の無機塩類を水層に抽出し、その後
、過剰の臭素を留出除去することにより、反応生成物を
水中に固体として析出させる。析出した反応生成物は、
既知の方法で分離、水洗、乾燥を行う。本発明により得
られた反応生成物は、そのままでも十分使用可能である
が、必要に応じてジクロルエタン、ジクロルベンゼン、
トルエン、キシレン等の溶媒を用いて再結晶させ、２・
４・５・２ζ４′・５仁ヘキサブロムジフエニルエーテ
ルを単離する。After the reaction is complete, water or an acidic aqueous solution such as hydrochloric acid or sulfuric acid is added to the reaction solution to extract inorganic salts such as catalysts into the aqueous layer, and then excess bromine is removed by distillation to remove the reaction product. Precipitates as a solid in water. The precipitated reaction product is
Separation, washing and drying are carried out using known methods. The reaction product obtained by the present invention can be used as it is, but if necessary, dichloroethane, dichlorobenzene,
Recrystallize using a solvent such as toluene or xylene to obtain 2.
4.5.2ζ4'.5 hexabrom diphenyl ether is isolated.
この場合、再結晶母液を濃縮することにより、２・４・
５・２′・４ζ５′−ヘキサブロムジフエニルエーテル
およびその異性体を５０重量％以上含む、ブロム化ジフ
エニルエーテルの混合物が得られる。本発明により得ら
れた２・４・５・２ζ４′・５ζーヘキサブロムジフエ
ニルエーテルは、ポリスチレン、ポリエチレン等のポリ
オレフイン用の難燃剤として優れた性能を示すと同時に
耐光性についても極めて優れた性能を有することが本発
明者らの検討で明らかとなつた。In this case, by concentrating the recrystallization mother liquor, 2.4.
A mixture of brominated diphenyl ethers is obtained containing more than 50% by weight of 5,2',4ζ5'-hexabrom diphenyl ether and its isomers. The 2,4,5,2ζ4',5ζ-hexabrom diphenyl ether obtained by the present invention exhibits excellent performance as a flame retardant for polyolefins such as polystyrene and polyethylene, and at the same time exhibits extremely excellent light resistance. It has become clear from the studies conducted by the present inventors that
さらにまた、２・４・５・２′・４′・５′・−ヘキサ
ブロムジフエニルエーテルの精製の際に再結晶母液から
得られるヘキサブロムジフエニルエーテル５０重量％以
上のブロム化ジフエニルエーテルは、溶媒除去後粉砕し
て電線被覆用のポリエチレン用難燃剤として、あるいは
トルエン等の溶媒に溶解した状態で、プリン卜配線用の
銅張フエノ一ル積層板あるいはテントシート類の難燃剤
として極めて優れた効果を有する。その他にも、ポリエ
ステル、ナイロン等の繊維、塗料、ポリウレタン等の難
燃剤として有効なことが判明した。Furthermore, brominated diphenyl ether containing 50% by weight or more of hexabrom diphenyl ether obtained from the recrystallization mother liquor during the purification of 2,4,5,2',4',5'-hexabrom diphenyl ether After removal of the solvent, it is crushed and used as a flame retardant for polyethylene for covering electric wires, or when dissolved in a solvent such as toluene, it is extremely effective as a flame retardant for copper-clad phenol laminates for printed wiring or tent sheets. Has excellent effects. In addition, it has been found to be effective as a flame retardant for fibers such as polyester and nylon, paints, and polyurethane.
以下に例をあげて詳しく説明する。This will be explained in detail using an example below.
なお実施例中の部および％はいづれも重量部、および重
量％を示す。実施例 １〜５
撹拌機、温度計、還流冷却器、滴下ロートを付した四ツ
ロフラスコに表−１に示す臭素および触媒を入れ、所定
の温度でジフエニルエーテルを滴下し、テトラブロムジ
フエニルエーテルを製造する一段目の反応を行わせた。Note that all parts and percentages in the examples indicate parts by weight and percentages by weight. Examples 1 to 5 Bromine and catalyst shown in Table 1 were placed in a four-way flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel, and diphenyl ether was added dropwise at a predetermined temperature to obtain tetrabrom diphenyl ether. The first stage reaction was carried out to produce .
次いで、反応液中に表−１に示す触媒を加え、所定の温
度で二段目の反応を行わせヘキサブロムジフエニルエー
テルを製造した。反応終了後、水又は塩酸水溶液を加え
、５０〜６０℃で３０分間攪拌して触媒を抽出した。次
いで還流冷却器を留出装置にとりかえて過剰の臭素を留
出除去した。得られた反応生成物を沢過、水洗し、乾燥
した。反応条件および結果を表−１に示した。なお反応
生成物の組成はガスクロで分析を行つた。表−１の組成
欄の略号は次の通りである。Next, the catalyst shown in Table 1 was added to the reaction solution, and a second reaction was carried out at a predetermined temperature to produce hexabrom diphenyl ether. After the reaction was completed, water or an aqueous hydrochloric acid solution was added, and the mixture was stirred at 50 to 60°C for 30 minutes to extract the catalyst. Next, the reflux condenser was replaced with a distillation device to distill off excess bromine. The obtained reaction product was filtered, washed with water, and dried. The reaction conditions and results are shown in Table-1. The composition of the reaction product was analyzed using gas chromatography. The abbreviations in the composition column of Table 1 are as follows.
ＰＢＤＰＥ：ぺンタブロムジフエニルエーテル２・４・
５・−ＨＢＤＰＥ：２・４・５・２ζ４ζ５′−ヘキサ
ブロムジフエニルエーテル） ＨＢＤＰＥ：ヘキサブロ
ムジラエニルエーテルの異性体ＨＰＢＤＰＥ：ヘプタブ
ロムジフエニルエーテル実施例 ６臭素８００部に粉砕
したテトラプロムジフエニルエーテル２４３部を加え、
温度２０〜２５℃で１時間撹拌した後ＦｅＣｌ３４部を
加え、１時間反応を行なわせ、ヘキサプロムジフエニル
エーテルを製造した。PBDPE: Pentabrom diphenyl ether 2.4.
5.-HBDPE: 2.4.5.2ζ4ζ5'-hexabromdiphenyl ether) HBDPE: Isomer of hexabromdilaenyl ether HPBDPE: heptabromdiphenyl ether Example 6 Tetrapromdiphenyl ground to 800 parts of bromine Add 243 parts of ether,
After stirring for 1 hour at a temperature of 20 to 25°C, 34 parts of FeCl was added and the reaction was allowed to proceed for 1 hour to produce hexaprom diphenyl ether.
反応終了後、実施例１に準じて後処理を行なつた。After the reaction was completed, post-treatment was performed according to Example 1.
Claims (1)
塩化物及び硫酸塩の一種又は２種以上の存在下に３５℃
以下の温度で２・４・２′・４′・−テトラブロムジフ
ェニルエーテルを臭素と反応させることを特徴とするヘ
キサブロムジフェニルエーテルの製造法。1 At 35°C in the presence of iron powder and one or more iron chlorides and sulfates in an anhydrous state using excess bromine as a solvent.
A method for producing hexabromidiphenyl ether, which comprises reacting 2,4,2',4'-tetrabromidiphenyl ether with bromine at the following temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52055484A JPS5929175B2 (en) | 1977-05-16 | 1977-05-16 | Production method of hexabrom diphenyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52055484A JPS5929175B2 (en) | 1977-05-16 | 1977-05-16 | Production method of hexabrom diphenyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS53141229A JPS53141229A (en) | 1978-12-08 |
| JPS5929175B2 true JPS5929175B2 (en) | 1984-07-18 |
Family
ID=12999887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP52055484A Expired JPS5929175B2 (en) | 1977-05-16 | 1977-05-16 | Production method of hexabrom diphenyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5929175B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62153855U (en) * | 1986-03-19 | 1987-09-30 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61271334A (en) * | 1985-05-25 | 1986-12-01 | Matsushita Electric Works Ltd | Production of laminated sheet |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5037735A (en) * | 1973-07-13 | 1975-04-08 | ||
| JPS53112822A (en) * | 1977-03-15 | 1978-10-02 | Mitsui Toatsu Chem Inc | Preparation of hexabromodiphenyl ether |
-
1977
- 1977-05-16 JP JP52055484A patent/JPS5929175B2/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5037735A (en) * | 1973-07-13 | 1975-04-08 | ||
| JPS53112822A (en) * | 1977-03-15 | 1978-10-02 | Mitsui Toatsu Chem Inc | Preparation of hexabromodiphenyl ether |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62153855U (en) * | 1986-03-19 | 1987-09-30 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS53141229A (en) | 1978-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2008001637A (en) | 1,4-dihydro-9,10-anthracenediyl (meth)acrylate compound, and method for producing the same | |
| CA2102289C (en) | Process for high purity tetrabromobisphenol-a | |
| CA1049560A (en) | Process for the production of 4-hydroxy-3,5-dibromobenzaldehyde | |
| JPS5929175B2 (en) | Production method of hexabrom diphenyl ether | |
| JPH07110827B2 (en) | Method for producing tetrabromobisphenol A | |
| JPS581090B2 (en) | Production method of hexabrom diphenyl ether | |
| JPS5840933B2 (en) | Method for producing 2,4,2',4'-tetrabromidiphenyl ether | |
| Mosher et al. | Preparation of Technical DDT. | |
| US3142701A (en) | Preparation of 2:5-dibromoterephthalic acid | |
| PL144334B1 (en) | Method of isolating and purifying crude 5-/2-chloro-4-(trifluoromethyl)-phenoxy/-2-nitrobenzoic acid | |
| Shoesmith et al. | CCCVIII.—Alternating reactive positions in the nucleus of tert.-butylbenzene | |
| DE2144259A1 (en) | Process for the nuclear bromination of aromatic compounds | |
| CN113461566B (en) | Preparation method of dicyan compound | |
| CN100357245C (en) | Prepn process of 2,5-dihalogeno benzoic acid | |
| JPS59137429A (en) | Nucleus halogenated 3-fluorotoluenes and manufacture | |
| US2558862A (en) | Manufacture of brominated phthalic anhydride | |
| CN115784856B (en) | Method for synthesizing 4,4' -dihalogenated benzophenone | |
| US4067887A (en) | Method of preparing dichloromaleic anhydride | |
| JPH05286898A (en) | Production of 4-acryloxy-4'-bromobiphenyl | |
| JPH06737B2 (en) | Method for producing alkyl- [3chlorophenyl] -sulfone | |
| SU159842A1 (en) | ||
| DE1793325C2 (en) | ||
| JPS6348234A (en) | Production of 2,5-di(chloromethyl)-p-xylene | |
| RU2247105C2 (en) | Environmentally safe method for production of high- purity tetrabromobisphenol a | |
| JPS5835186B2 (en) | 4- Benzoylpyrazole |