JPS581090B2 - Production method of hexabrom diphenyl ether - Google Patents
Production method of hexabrom diphenyl etherInfo
- Publication number
- JPS581090B2 JPS581090B2 JP52027621A JP2762177A JPS581090B2 JP S581090 B2 JPS581090 B2 JP S581090B2 JP 52027621 A JP52027621 A JP 52027621A JP 2762177 A JP2762177 A JP 2762177A JP S581090 B2 JPS581090 B2 JP S581090B2
- Authority
- JP
- Japan
- Prior art keywords
- diphenyl ether
- hexabrom
- reaction
- bromine
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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
- Electrochemical Coating By Surface Reaction (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明はヘキサブロムジフエニルエーテルの製造法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing hexabrom diphenyl ether.
ヘキサブロムジフエニルエーテルの製造法としては従来
ジブロムエタン、テトラクロルエタン、四塩化炭素等の
有機溶媒中もしくは発煙硫酸等の無機溶媒中で臭素とジ
フエニルエーテルの比率を変えることによって製造する
方法が知られている。Conventionally, hexabrom diphenyl ether is produced by varying the ratio of bromine and diphenyl ether in an organic solvent such as dibromoethane, tetrachloroethane, or carbon tetrachloride, or in an inorganic solvent such as fuming sulfuric acid. It is being
しかしこれらの方法では有機溶媒の臭素化が起る、有機
溶媒の回収、精製が必要である、廃硫酸の処理が必要で
ある、同一規模の製造に対して大きな装置が必要である
等の理由により、いづれの方法を採用しても高価なもの
になるという欠点があった。However, these methods cause bromination of the organic solvent, require recovery and purification of the organic solvent, require treatment of waste sulfuric acid, and require large equipment for the same scale of production. Therefore, no matter which method is adopted, the disadvantage is that it is expensive.
一方過剰の臭素を溶媒としてジフエニルエーテを臭素化
する方法についてもよく知られてはいるが、この場合に
は反応のコントロールが極めて困難であり、臭素化率の
異る種々の臭素化ジフエニルエーテルカ生成シ、ヘキサ
ブロムジフエニルエーテルのみを選択的に製造すること
は出来なかった。On the other hand, a method of brominating diphenyl ether using excess bromine as a solvent is well known, but in this case it is extremely difficult to control the reaction, and various brominated diphenyl ether molecules with different bromination rates are used. However, it was not possible to selectively produce only hexabrom diphenyl ether.
本発明者らは、過剰の臭素を溶媒としてヘキサブロムジ
フエニルエーテルを選択的に製造する方法について鋭意
検討を行った結果、鉄系触媒を用いる場合にヘキサブロ
ムジフエニルエーテルが選択的に得られることを見出し
本発明に達したものである。The present inventors have conducted intensive studies on a method for selectively producing hexabrom diphenyl ether using excess bromine as a solvent, and have found that hexabrom diphenyl ether can be selectively obtained when an iron-based catalyst is used. This discovery led to the present invention.
而して本発明はヘキサブロムジフエニルエーテルを製造
するにあたり、過剰の臭素を溶媒として鉄粉、無水状態
の鉄の塩化物及び硫酸塩から選ばれた一種又は二種以上
からなる触媒の存在下に、３５℃以下の温度で反応させ
ることを特徴とするヘキサブロムジフエニルエーテルの
製造法に関スるものである。Therefore, in producing hexabrom diphenyl ether, the present invention uses excess bromine as a solvent in the presence of a catalyst consisting of one or more selected from iron powder, anhydrous iron chloride, and sulfate. The present invention relates to a method for producing hexabrom diphenyl ether, which is characterized in that the reaction is carried out at a temperature of 35° C. or lower.
本発明で得られるヘキサブロムジフエニルエーテルは、
主成分として２・４・５・２′・４′・５′−ヘキサブ
ロムジフエニルエーテル６０〜８５重量％、その異性体
５〜２０重量％を含み、その他にペンタフロムジフエニ
ルエーテル、ヘプタブロムジフエニルエーテル５〜２０
重量％を含む固体である。The hexabrom diphenyl ether obtained in the present invention is
Contains 60 to 85% by weight of 2,4,5,2',4',5'-hexabrom diphenyl ether and 5 to 20 wt% of its isomers as main components, and also contains pentafurom diphenyl ether, heptabrom diphenyl ether, and heptabrom diphenyl ether. Diphenyl ether 5-20
% solids by weight.
本発明により従来臭素溶媒中での製造が困難であったヘ
キサブロムジフエニルエーテルの製造が可能となり、安
価に供給することが可能にった。The present invention has made it possible to produce hexabrom diphenyl ether, which was conventionally difficult to produce in a bromine solvent, and to supply it at low cost.
本発明は、反応尚量以上の過剰の臭素を反応溶媒とし、
この臭素中に触媒を加え、所定の温度でジフエニルエー
テルを添加することによって行われる。The present invention uses excess bromine in excess of the reaction amount as a reaction solvent,
This is carried out by adding a catalyst to the bromine and adding diphenyl ether at a predetermined temperature.
本発明で用いる臭素の量は反応当量の１．５〜５倍量好
ましくは２〜３倍量である。The amount of bromine used in the present invention is 1.5 to 5 times, preferably 2 to 3 times the reaction equivalent.
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としての効果がうすれ、
均一な混合が保たれなくなるため、ヘキサブロムジフエ
ニルエーテルを選択的に製造することが困難になり一方
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。If the amount of bromine is less than 1.5 times the reaction equivalent, as the bromine is consumed by the reaction, the effect of bromine as a solvent decreases.
Uniform mixing is no longer maintained, making it difficult to selectively produce hexabrom diphenyl ether. On the other hand, if the amount is more than 5 times the reaction equivalent, it will be economically disadvantageous due to the recovery of bromine after the reaction, which is not preferable. .
本発明で用いる触媒は鉄粉および無水状態の塩化第一鉄
、塩化第二鉄、硫酸第一鉄、硫酸第二鉄等である。Catalysts used in the present invention include iron powder and anhydrous ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, and the like.
触媒量は使用する臭素量に対して、０．０１〜５重量％
、好ましくは０．０５〜２重量％であり、反応開始の際
一度に加えてもよく、あるいは反応中に分割して加えて
もよい。The amount of catalyst is 0.01 to 5% by weight based on the amount of bromine used.
, preferably 0.05 to 2% by weight, and may be added all at once at the start of the reaction, or may be added in portions during the reaction.
触媒量が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が起りうるため好ま
しくない。If the catalyst amount is less than 0.01% by weight, the catalytic effect will be weak, and if it is more than 5% by weight, the catalyst may be mixed into the product, which is not preferable.
本発明では反応は温度０〜３５℃好ましくは１０〜３０
℃で行う。In the present invention, the reaction is carried out at a temperature of 0 to 35°C, preferably 10 to 30°C.
Perform at °C.
温度０℃以下では臭素含量のより低い臭素化ジフエニル
エーテルが、又３５℃以上では臭素含量のより高い臭素
化ジフエニルエーテルが副生ずるためヘキサブロムジフ
エニルエーテルの選択率が低下するので好ましくない。If the temperature is below 0°C, brominated diphenyl ether with a lower bromine content will be produced as a by-product, and if it is above 35°C, a brominated diphenyl ether with a higher bromine content will be produced as a by-product, resulting in a decrease in the selectivity of hexabrom diphenyl ether, which is undesirable. .
ジフエニルエーテルの臭素中への添加方法は、一度にあ
るいは分割して加えることが可能であるが一度に添加す
る場合には反応温度の制御が困難で広範囲の臭素化ジフ
エニルエーテルの生成を起す危険性があるためへキサブ
ロムジフエニルエーテルの選択率をあげるためにはジフ
エニルエーテルは分割して加えることが好ましい。Diphenyl ether can be added to bromine all at once or in parts, but if it is added all at once, it is difficult to control the reaction temperature and a wide range of brominated diphenyl ethers are produced. Because of the danger, it is preferable to add diphenyl ether in portions in order to increase the selectivity of hexabrom diphenyl ether.
本発明における反応は反応速度が大きく反応は短時間で
終了するためヘキサブロムジフエニルエーテルの選択率
を上げるには反応時間は５時間以下好ましくは３時間以
下であり熟成反応は必ずしも必要としない。The reaction in the present invention has a high reaction rate and is completed in a short time. Therefore, in order to increase the selectivity of hexabrom diphenyl ether, the reaction time is 5 hours or less, preferably 3 hours or less, and an aging reaction is not necessarily required.
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。After the reaction is complete, add water or an acidic aqueous solution such as hydrochloric acid or sulfuric acid to the reaction solution to extract the catalyst into the aqueous layer, and then remove excess bromine by distillation to precipitate the reaction product as a solid in water. .
反応生成物は既知の方法で分離、洗浄後乾燥する。The reaction product is separated, washed and dried by known methods.
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、必要な場合はジクロルエタン、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・２′・４′・５′−ヘキサブロム
ジフエニルエーテルを単離する。The reaction product obtained by the present invention can be used as it is, but if necessary, it can be recrystallized using a solvent such as dichloroethane, dichlorobenzene, toluene, or xylene. - Isolate 4',5'-hexabrom diphenyl ether.
この場合再結晶母液を濃縮することにより、２・４・５
・２′・４′・５′−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。In this case, by concentrating the recrystallization mother liquor, 2, 4, 5
- A mixture of brominated diphenyl ethers containing 2', 4', 5'-hexabrominated diphenyl ether and its isomers in an amount of 50% by weight or more is obtained.
本発明により得られた２・４・５・２′・４′・５′ー
ヘキサブロムジフエニルエーテルはホリスチレン、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った。The 2,4,5,2',4',5'-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 has extremely high light resistance. The inventors' studies have revealed that this material has excellent performance.
さらにまた２・４・５・２′・４′・５′−ヘキサフロ
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そのまゝ粉砕して電線被
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ト配線用の銅張フェノ
ー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。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'-hexafrom diphenyl ether is It has excellent effects when crushed and used as a flame retardant for polyethylene used to coat electric wires, or when dissolved in a solvent such as toluene as a flame retardant for copper-clad phenol laminates for printed wiring or tent sheets.
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。It has also been found to be effective as a flame retardant for fibers such as polyester and nylon, paints, and polyurethane.
以下に実施例をあげて詳しく説明する。A detailed explanation will be given below using examples.
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。Note that all parts and percentages in the examples indicate parts by weight and percentages by weight.
実施例 １〜４
攪拌機、温度計、環流冷却器、滴下ロートを付した四ツ
ロフラスコに臭素と触媒を入れ所定の温度でジフエニル
エーテルを滴下した。Examples 1 to 4 Bromine and a catalyst were placed in a four-way flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, and diphenyl ether was added dropwise at a predetermined temperature.
ジフエニルエーテル滴下後熟成反応を行った。After dropwise addition of diphenyl ether, a ripening reaction was carried out.
その後、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。After that, water or aqueous hydrochloric acid solution was added, and 30
The catalyst was extracted by stirring for a minute.
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。Next, the reflux condenser was replaced with a distillation device to distill off excess bromine.
得られた反応生成物を沢過、水洗、乾燥した。The obtained reaction product was filtered, washed with water, and dried.
乾燥した反応生成物についてガスクロマトラフイー分析
を行い、その組成を求めた。Gas chromatography analysis was performed on the dried reaction product to determine its composition.
反応条件および結果を表−１に示した。The reaction conditions and results are shown in Table-1.
なお表−１組成欄の略号は次の通りである。The abbreviations in the composition column of Table 1 are as follows.
ＰＢＤＰＥ：ペンタブロムジフエニルエーテル２・４・
５−ＨＢＤＰＥ： ２・４・５・２′・４′・５′−ヘ
キサフロムジフエニルエーテル
ＨＢＤＰＥ：ヘキサフロムジフエニルエーテルの異性体PBDPE: Pentabrom diphenyl ether 2.4.
5-HBDPE: 2,4,5,2',4',5'-hexafrom diphenyl etherHBDPE: isomer of hexafrom diphenyl ether
Claims (1)
ブロムジフエニルエーテルを製造するにあたり、過剰の
臭素を溶媒として、鉄粉、無水状態の鉄の塩化物及び硫
酸塩から選ばれた一種又は二種以上からなる触媒の存在
下に０〜３５℃の温度で反応させることを特徴とするヘ
キサブロムジフエニルエーテルノ製造法。1. When producing hexabrom diphenyl ether by reacting diphenyl ether with bromine, one or two selected from iron powder, anhydrous iron chloride, and sulfate are added using excess bromine as a solvent. A method for producing hexabrom diphenyl ether, which is characterized by carrying out the reaction at a temperature of 0 to 35°C in the presence of the catalyst described above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52027621A JPS581090B2 (en) | 1977-03-15 | 1977-03-15 | Production method of hexabrom diphenyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52027621A JPS581090B2 (en) | 1977-03-15 | 1977-03-15 | Production method of hexabrom diphenyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS53112822A JPS53112822A (en) | 1978-10-02 |
| JPS581090B2 true JPS581090B2 (en) | 1983-01-10 |
Family
ID=12226006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP52027621A Expired JPS581090B2 (en) | 1977-03-15 | 1977-03-15 | Production method of hexabrom diphenyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS581090B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5929175B2 (en) * | 1977-05-16 | 1984-07-18 | 三井東圧化学株式会社 | Production method of hexabrom diphenyl ether |
| JPS6354337A (en) * | 1987-01-13 | 1988-03-08 | Dai Ichi Kogyo Seiyaku Co Ltd | Production of liquid brominated diphenyl ether |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5037735A (en) * | 1973-07-13 | 1975-04-08 |
-
1977
- 1977-03-15 JP JP52027621A patent/JPS581090B2/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5037735A (en) * | 1973-07-13 | 1975-04-08 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS53112822A (en) | 1978-10-02 |
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