JPH02196747A - Production of tetrabromobisphenol a - Google Patents
Production of tetrabromobisphenol aInfo
- Publication number
- JPH02196747A JPH02196747A JP1506589A JP1506589A JPH02196747A JP H02196747 A JPH02196747 A JP H02196747A JP 1506589 A JP1506589 A JP 1506589A JP 1506589 A JP1506589 A JP 1506589A JP H02196747 A JPH02196747 A JP H02196747A
- Authority
- JP
- Japan
- Prior art keywords
- tetrabromobisphenol
- bisphenol
- bromine
- water
- methanol
- 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.)
- Pending
Links
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 19
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 17
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 16
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003063 flame retardant Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000004593 Epoxy Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 238000006757 chemical reactions by type Methods 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
テトラブロモビスフェノールAは、エポキシ積層板用の
反応型難燃剤、又ABS等の汎用樹脂用の添加型難燃剤
として、有用な化合物である。Detailed Description of the Invention (Field of Industrial Application) Tetrabromobisphenol A is a compound useful as a reactive flame retardant for epoxy laminates and as an additive flame retardant for general-purpose resins such as ABS.
(従来の技術)
テトラブロモビスフェノールAの製造法としては、大別
して次の2つの方法が知られているが、それらのいずれ
も純度が良くかつ色層の改善された製品を得るには再結
晶法等の2次的な改善方法を要する。(Prior art) The following two methods are known for producing tetrabromobisphenol A, but in both of them, recrystallization is required to obtain a product with good purity and an improved color layer. Secondary improvement methods such as methods are required.
(1)無水メタノール中でビスフェノールAを臭素化し
、この後、その還流温度に加熱し、副生成物として、臭
化メチルの製造が可能な方法。(特公昭41−3376
号公報)(特公昭53−20494号公報)
(2)メタノール中でビスフェノールAを臭素化する工
程において、同時に強酸化剤として、Cj、HO等を加
え、副生ずるHBr
を臭素源として回収しつつ、テトラブロモビスフェノー
ルAを製造する方法。(特公昭50−21465号公報
)
(発明が解決しようとする課題)
従来のノj法では、製造されたの色相としての白色度が
充分といえず、着色による不都合をきたしていた。(1) A method in which bisphenol A is brominated in anhydrous methanol, then heated to its reflux temperature, and methyl bromide can be produced as a by-product. (Tokuko Sho 41-3376
(Japanese Patent Publication No. 53-20494) (2) In the step of brominating bisphenol A in methanol, Cj, HO, etc. are added as strong oxidizing agents at the same time, and HBr as a by-product is recovered as a bromine source. , a method for producing tetrabromobisphenol A. (Japanese Patent Publication No. 50-21465) (Problems to be Solved by the Invention) In the conventional Noj method, the whiteness of the produced product could not be said to be sufficient in terms of hue, causing problems due to coloration.
(課題を解決するための手段)
本発明の目的は、このような従来の方法に比べ、臭素化
工程後の晶析工程に至る中で、色相を改善する方法、よ
り高品質(色相)のテトラブロモビスフェノールAを製
造することができる方法を提出することにある。(Means for Solving the Problems) The purpose of the present invention is to provide a method for improving the hue during the crystallization step after the bromination step, and a method for achieving higher quality (hue) than such conventional methods. The object of the present invention is to provide a method by which tetrabromobisphenol A can be produced.
すなわち、本発明は、ビスフェノールAをメタノール溶
媒中で臭素化し、テトラブロモビスフェノールAを製造
する方法において、反応終了後のテトラブロモビスフェ
ノールA含有メタノール中にヒドラジン水溶液を添加し
、余剰の臭素を還元した後、水を加えてテトラブロモビ
スフェノールAを晶析することにより色相の改良された
テトラブロモビスフェノールAの製造法に関するもので
ある。That is, the present invention provides a method for producing tetrabromobisphenol A by brominating bisphenol A in a methanol solvent, in which an aqueous hydrazine solution is added to methanol containing tetrabromobisphenol A after the reaction is completed to reduce excess bromine. The present invention relates to a method for producing tetrabromobisphenol A with improved hue by adding water and crystallizing tetrabromobisphenol A.
以下その詳細について説明する。The details will be explained below.
本発明による臭素化反応は、ビスフェノールAに対しほ
とんど無水のメタノールを用い完全に溶解させ、臭素を
低温にてできるだけ穏やかな条件のもとで滴下させる。In the bromination reaction according to the present invention, bisphenol A is completely dissolved using almost anhydrous methanol, and bromine is added dropwise at a low temperature under as mild conditions as possible.
滴下する臭素の量は、ビスフェノール1モルに対し、4
.0〜4.06が好ましい。反応後のテトラブロモビス
フェノールA含有液は黄〜淡かっ色を有しており、これ
は反応に関与しなかった余剰臭素による着色である。こ
の為、このまま水を加えてテトラブロモビスフェノール
Aを晶析させるとテトラブロモビスフェノールAの結晶
中に該臭素を抱き込んでしまう為、製品の色は著しく悪
くなる。The amount of bromine added dropwise is 4 to 1 mole of bisphenol.
.. 0 to 4.06 is preferred. The tetrabromobisphenol A-containing liquid after the reaction has a yellow to light brown color, and this coloring is due to excess bromine that did not participate in the reaction. For this reason, if water is added as is to crystallize tetrabromobisphenol A, the bromine will be incorporated into the crystals of tetrabromobisphenol A, resulting in a significantly poor color of the product.
この為、本発明では、この余剰臭素を分解させることに
より製品品質に悪影響を及ぼさないようにせねばならず
、そのためにヒドラジン水溶液を使用するものである。Therefore, in the present invention, it is necessary to decompose this excess bromine so as not to adversely affect product quality, and for this purpose, an aqueous hydrazine solution is used.
本発明でのこのヒドラジン水溶液の添加方法としては、
テトラブロモビスフェノールA含a反応液にあらかじめ
水で希釈したヒドラジン水溶液をゆっくり添加するのが
好ましい。The method of adding this hydrazine aqueous solution in the present invention is as follows:
It is preferable to slowly add a hydrazine aqueous solution previously diluted with water to the tetrabromobisphenol A-containing reaction solution.
ヒドラジン水溶故により余剰臭素を分解させ、この後、
水を添加し、テトラブロモビスフェノールA結晶を晶I
iさせることにより、ヒドラジンで余剰臭素を完全に分
解させ、着色原因となる臭素色を全くの透明にすること
で、色相の改善されたテトラブロモビスフェノールAが
得られる。Excess bromine is decomposed by the hydrazine solution, and then,
Add water and crystallize tetrabromobisphenol A crystals.
By doing so, excess bromine is completely decomposed with hydrazine, and the bromine color that causes coloration is made completely transparent, thereby obtaining tetrabromobisphenol A with improved hue.
(発明の効果)
以上の説明から明らかなように、本発明によれば、
(1)精製工程が不要で反応器中で結晶化でき(2)か
つ、純白のテトラブロモビスフェノールAを製造するこ
とができる。(Effects of the Invention) As is clear from the above explanation, according to the present invention, (1) a purification step is not required and crystallization is possible in a reactor, and (2) pure white tetrabromobisphenol A can be produced. Can be done.
(実施例)
以下本発明を実施例により説明するが、本発明はこれら
によりのみ限定されるものではない。(Examples) The present invention will be explained below with reference to Examples, but the present invention is not limited only by these.
実施例1
ビスフェノールA57g(0,4モル)をメタノール3
36gに溶解させ、この溶液を15〜20℃に冷却し、
臭素164.8g’(1,03モル)をこの温度に保ち
ながら2.5〜3.5時間かけて撹拌液面上に滴下し、
さらにこの後3時間撹拌した。次に純水100g滴下後
ヒドラジン水溶液(20w/w%)を15〜25℃で撹
拌液面上にゆっくり滴下し、余剰の臭素を分解させる。Example 1 57 g (0.4 mol) of bisphenol A was mixed with 3 methanol
36g and cooled this solution to 15-20°C,
164.8 g' (1.03 mol) of bromine was dropped onto the stirring liquid surface over 2.5 to 3.5 hours while maintaining this temperature.
After this, the mixture was further stirred for 3 hours. Next, after dropping 100 g of pure water, a hydrazine aqueous solution (20 w/w %) is slowly dropped onto the stirring liquid surface at 15 to 25°C to decompose excess bromine.
この後、純水200gを滴下し、テトラブロモビスフみ
ノールAを析出させ、濾過し、形成した結晶を純水にて
洗浄し、乾燥した。得られた結晶は純度99%以」−の
純白度のテトラブロモビスフェノールAであった。Thereafter, 200 g of pure water was added dropwise to precipitate tetrabromobisphinol A, which was filtered, and the formed crystals were washed with pure water and dried. The obtained crystals were white tetrabromobisphenol A with a purity of 99% or higher.
Claims (1)
トラブロモビスフェノールAを製造する方法において、
反応終了後のテトラブロモビスフェノールA含有メタノ
ール中にヒドラジン水溶液を添加し、余剰の臭素を還元
した後、水を加えてテトラブロモビスフェノールAを晶
析することを特徴とするテトラブロモビスフェノールA
の製造法。In a method for producing tetrabromobisphenol A by brominating bisphenol A in a methanol solvent,
Tetrabromobisphenol A characterized by adding a hydrazine aqueous solution to tetrabromobisphenol A-containing methanol after completion of the reaction to reduce excess bromine, and then adding water to crystallize tetrabromobisphenol A.
manufacturing method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1506589A JPH02196747A (en) | 1989-01-26 | 1989-01-26 | Production of tetrabromobisphenol a |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1506589A JPH02196747A (en) | 1989-01-26 | 1989-01-26 | Production of tetrabromobisphenol a |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02196747A true JPH02196747A (en) | 1990-08-03 |
Family
ID=11878442
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1506589A Pending JPH02196747A (en) | 1989-01-26 | 1989-01-26 | Production of tetrabromobisphenol a |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02196747A (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5527971A (en) * | 1995-04-24 | 1996-06-18 | Albemarle Corporation | Process for the preparation of tetrabromobisphenol-A |
US5847232A (en) * | 1995-03-06 | 1998-12-08 | Albemarle Corporation | Process for the preparation of tetrabromobisphenol-A |
US6002050A (en) * | 1995-03-06 | 1999-12-14 | Albemarle Corporation | Process for the preparation of tetrabromobisphenol-A |
US6084136A (en) * | 1995-03-06 | 2000-07-04 | Albmarle Corporation | Process for the preparation of tetrabromobisphenol-A |
US6084137A (en) * | 1995-03-06 | 2000-07-04 | Albemarle Corporation | Process for the preparation of tetrabromobisphenol-A |
US6147264A (en) * | 1999-04-08 | 2000-11-14 | Albemarle Corporation | Process for producing tetrabromobisphenol-A |
US6218584B1 (en) | 1995-03-06 | 2001-04-17 | Albemarle Corporation | Process for the preparation of tetrabromobisphenol-A |
US6235946B1 (en) | 1995-03-06 | 2001-05-22 | Albemarle Corporation | Process for the preparation of tetrabromobisphenol-A |
JP2001322964A (en) * | 2000-05-16 | 2001-11-20 | Tosoh Corp | Method for continuously crystallizing tetrabromobisphenol a |
-
1989
- 1989-01-26 JP JP1506589A patent/JPH02196747A/en active Pending
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6235946B1 (en) | 1995-03-06 | 2001-05-22 | Albemarle Corporation | Process for the preparation of tetrabromobisphenol-A |
US6218584B1 (en) | 1995-03-06 | 2001-04-17 | Albemarle Corporation | Process for the preparation of tetrabromobisphenol-A |
US5847232A (en) * | 1995-03-06 | 1998-12-08 | Albemarle Corporation | Process for the preparation of tetrabromobisphenol-A |
US6002050A (en) * | 1995-03-06 | 1999-12-14 | Albemarle Corporation | Process for the preparation of tetrabromobisphenol-A |
US6084136A (en) * | 1995-03-06 | 2000-07-04 | Albmarle Corporation | Process for the preparation of tetrabromobisphenol-A |
US6084137A (en) * | 1995-03-06 | 2000-07-04 | Albemarle Corporation | Process for the preparation of tetrabromobisphenol-A |
US6313355B1 (en) | 1995-03-06 | 2001-11-06 | Thanikavelu Manimaran | Process for the preparation of tetrabromobisphenol-A |
US6162953A (en) * | 1995-03-06 | 2000-12-19 | Albemarle Corporation | Process for the preparation of tetrabromobisphenol-A |
US6300527B1 (en) | 1995-03-06 | 2001-10-09 | Albemarle Corporation | Process for the preparation of tetrabromobisphenol-A |
US5527971A (en) * | 1995-04-24 | 1996-06-18 | Albemarle Corporation | Process for the preparation of tetrabromobisphenol-A |
US5723690A (en) * | 1995-04-24 | 1998-03-03 | Albemarle Corporation | Process for the preparation of tetrabromobisphenol-A |
US6147264A (en) * | 1999-04-08 | 2000-11-14 | Albemarle Corporation | Process for producing tetrabromobisphenol-A |
JP2001322964A (en) * | 2000-05-16 | 2001-11-20 | Tosoh Corp | Method for continuously crystallizing tetrabromobisphenol a |
JP4631129B2 (en) * | 2000-05-16 | 2011-02-16 | 東ソー株式会社 | Method for continuous crystallization of tetrabromobisphenol A |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPH02196747A (en) | Production of tetrabromobisphenol a | |
US6204394B1 (en) | Method for preparing oxy-diphthalic anhydrides | |
US3448119A (en) | Producing tetramethylisoindolenine by heating acetonylacetone in aqueous ammonium salt | |
RU2026280C1 (en) | Method of synthesis of 2,2-bis-(3',5'-dibromo-4'-hydroxyphenyl)-propane | |
JP2897372B2 (en) | Production method of high quality tetrabromobisphenol A | |
JPS6124559A (en) | Method of purifying dihydroxydiphenylsulfone | |
JPH05213804A (en) | Production of tetrafluorobisphenol a | |
US6307091B1 (en) | Trifluoro-substituted benzoic acid, esters thereof and processes for preparing the same | |
JPS6157536A (en) | Preparation of 2-nitro-4,6-dichloro-5-ethylphenol | |
US3597414A (en) | Process for the reduction of nitrobenzene-3,4-dicarboxylic acid to azo and azoxy compounds | |
US4519953A (en) | Process for preparing stilbenedicarbonitriles | |
JP3208458B2 (en) | Method for producing 1,4-dihydroxy-2-naphthoic acid | |
US5068409A (en) | Bis(4-halo-phthalic acid) quarter salt, process for their preparation and their use | |
JP4689803B2 (en) | Process for producing (2S, 4S) -N, N-dimethyl-1-allyloxycarbonyl-4-benzoylthio-2-pyrrolidinecarboxamide | |
KR910001436B1 (en) | Process for the preparation of para position substitude 2,6-dibromobenzeneamine | |
JPS627910B2 (en) | ||
JPH0413657A (en) | Production of 2,4-diaminobenzenesulfonic acid | |
JP2500316B2 (en) | 1,4,5,8-Tetrakis (halogenomethyl) naphthalene derivative and method for producing the same | |
US4621154A (en) | Process for preparing 4-(4-biphenylyl)-4-oxo-butanoic acid | |
RU1436456C (en) | Process for producing potassium 2,5-dioxybenzene sulfonate | |
JPH04202148A (en) | Production of 3,5-di-t butyl-2,6-dichlorotoluene | |
KR920009575B1 (en) | Process for the preparation of p-substituted 6-bromo-2-cyano benzeneamine | |
JP2560431B2 (en) | Method for producing 2,4-dihydroxyacetophenone | |
RU2058302C1 (en) | Method for production of 3,3′-dibrom-4,4′-diacetamido diphenyl methane | |
DE2019196B2 (en) | Process for the preparation of 4-meftoxy-2,6-di-tert-butylphenoL |