JPH013139A - Method for purifying tetrabromubisphenol A - Google Patents
Method for purifying tetrabromubisphenol AInfo
- Publication number
- JPH013139A JPH013139A JP62-157371A JP15737187A JPH013139A JP H013139 A JPH013139 A JP H013139A JP 15737187 A JP15737187 A JP 15737187A JP H013139 A JPH013139 A JP H013139A
- Authority
- JP
- Japan
- Prior art keywords
- bromine
- water
- tea
- tba
- ppm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 7
- 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 claims description 4
- 238000010992 reflux Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 36
- 229910052794 bromium Inorganic materials 0.000 description 36
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- -1 bromine ions Chemical class 0.000 description 11
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 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 description 4
- 238000000746 purification Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 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 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229940006460 bromide ion Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- MARCAKLHFUYDJE-UHFFFAOYSA-N 1,2-xylene;hydrate Chemical compound O.CC1=CC=CC=C1C MARCAKLHFUYDJE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
「産業上の利用分野」
本発ｑ＃″ｉ加水分解性臭素及び臭素イオンの低減を目
的としたテトラブロムビスフェノールＡの精製方法に関
する。DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a method for purifying tetrabromobisphenol A for the purpose of reducing q#''i hydrolyzable bromine and bromine ions.
「従来技術」
テトラブロムビスフェノールＡ（以下ＴＥＡと略記）は
エポキシ樹脂、ＡＢＳ樹脂等の難燃剤として多量に使用
されて−る。近年の電子機器の発展はめざ捷しｂものか
あり−コンピュータはもちろんのこと家電、自動車等に
も難燃剤として使用されて因るものである。これら電子
機器の絶縁材、保護材及び電子機器を取りつける基板等
の用途には、主としてエポキシ樹脂成形材料、エポキシ
樹脂積層板等のエポキシ樹脂組成物が用因られて粘る。"Prior Art" Tetrabromobisphenol A (hereinafter abbreviated as TEA) is used in large quantities as a flame retardant for epoxy resins, ABS resins, and the like. The recent development of electronic equipment has been remarkable - this is due to its use as a flame retardant not only in computers but also in home appliances, automobiles, etc. Epoxy resin compositions such as epoxy resin molding materials and epoxy resin laminates are mainly used for applications such as insulating materials and protective materials for electronic devices, and substrates on which electronic devices are attached.
一般にこれらエポキシ樹脂組成物には難燃化剤としてＴ
ＢＡ単独またはＴＢＡを骨格とするエポキシ樹脂が配合
されて粘る。Generally, these epoxy resin compositions contain T as a flame retardant.
BA alone or an epoxy resin with TBA as a backbone is blended to make it sticky.
しかしながら、ＴＥＡを電子機器の用途に使用した場合
、ＴＢＡ中に残存する加水分解性臭素及び臭素イオンが
問題となる。例えば加水分解性臭素含量の多いＴＢＡを
電子機器の保護剤として使用した場合、吸湿により臭素
分が臭素イオンとして遊離してくることになり、金属の
腐蝕等の各種トラブルを発生するととｖｃなる。However, when TEA is used for electronic devices, hydrolyzable bromine and bromine ions remaining in TBA become a problem. For example, when TBA with a high hydrolyzable bromine content is used as a protective agent for electronic equipment, the bromine content will be liberated as bromine ions due to moisture absorption, causing various problems such as corrosion of metals.
Ａ常ＴＢＡはビスフェノールＡをハロゲン化炭化水素及
び水に溶解又は分散させ、これに臭素を添加することに
より製造し、場合によってはさらに該ＴＥＡをメタノー
ル等の低級アルコール類やベンゼン等の芳香族炭化水素
類に溶解し、該溶液からＴＥＡを晶析させる等の精製を
行うものである。A Normal TBA is produced by dissolving or dispersing bisphenol A in a halogenated hydrocarbon and water, and adding bromine to this. Purification is performed by dissolving it in hydrogen and crystallizing TEA from the solution.
上記方法で得られたＴＢＡは通常１，０００〜２，００
０ｐｐｍの７１０水分解性臭素と】０〜５０ｐｐｍの臭
素イオンを含んでおり、このまま電子機器の用途に使用
することは困難である。The TBA obtained by the above method is usually 1,000 to 2,000
It contains 0 ppm of 710 water-decomposable bromine and 0 to 50 ppm of bromine ions, making it difficult to use it as is for electronic devices.
「発明が解決しようとする問題点」
本発明は上記従来方法では満足されなかった加水分解性
臭素及び臭素イオンを減じ、主として電子機器用のＴＢ
Ａを工業的に製造する方法を見す出そうとするものであ
る。"Problems to be Solved by the Invention" The present invention reduces hydrolyzable bromine and bromine ions, which were not satisfied with the above conventional methods, and mainly uses TB for electronic equipment.
The aim is to find a method for producing A industrially.
本発明で問題としている加水分解性臭素分はＴＢＡをジ
オキサンに溶解し、水酸化カリウムのエタノール溶液を
加え、還流状態で３０分間加熱した時に脱離する臭素イ
オンを硝酸銀水溶液にて電位差滴定で定量し、ＴＢＡの
重量に対するｐｐｍで表わしたものである。The hydrolyzable bromine component that is the problem in the present invention is determined by dissolving TBA in dioxane, adding an ethanol solution of potassium hydroxide, and heating the mixture under reflux for 30 minutes.The bromine ions released are determined by potentiometric titration using an aqueous silver nitrate solution. It is expressed in ppm based on the weight of TBA.
また、臭素イオンＦｉＴＢＡ ｆｔアセトンに溶解し遊
離の臭素イオンを硝酸銀水溶液にて電位差滴定で足貴し
、ＴＥＡの重量に対するｐｐｍで表わしたものである。Furthermore, free bromine ions dissolved in FiTBA ft acetone were titrated potentiometrically with an aqueous silver nitrate solution, and expressed in ppm relative to the weight of TEA.
「問題を解決するための手段」
本発明者らは加水分解性臭素及び臭素イオン含量の少な
ＬＡＴＢＡｋ工業的に製造すべく努力した結果、ＴＢＡ
を芳香族炭化水素溶媒に加熱溶解させ、】００〜１５０
℃でアルカリ金属水酸化物水溶液を滴下しながら共沸還
流脱水下で処理した後、中和、水洗、冷却して析出させ
ることを特徴とすと接触させることにより、力ロ水分解
性臭素及び臭素イオンを脱離させることにある。すなわ
ち、遊離ノ臭素イオン及び主としてビスフェノールＡの
メチル基に付加した臭素をアルカリ金属水酸化物と反応
させ、臭化ナトリウムとして除去するものである。本発
明で使用式九る芳香族炭化水素としては適尚な沸点をも
つトルエンまたはキシレンがよく、使用量はＴＥＡの重
量に対して０．５〜３倍量、好ましくは１〜２倍量がよ
い。本発明で使用されるアルカリ金属水酸化物としては
水酸化リチウム、水酸化カリウム、水酸化ナトリウム及
び水酸化カルシウムが該当し、これらは５〜５０ｆ（量
チ、好ましくＶｉｌ Ｏ〜３０重ｉ％なる水溶液として
使用するのがよい。また、アルカリ金属水酸化物の使用
量はＴＥＡの重量に対して１〜１０重量％、好１しくけ
３〜６重量％がよい。アルカリ金属水酸化物の使用量が
１重量％以下では所望する加水分解性臭素含ｉ′を得る
ことが困難であり、１０重童チ以上ではこれ以上加水分
解性臭素含量を減する効果がうすく、アルカリ金属水酸
化物の浪費となるばかりである。"Means for Solving the Problem" As a result of our efforts to industrially produce LATBAK with a low content of hydrolyzable bromine and bromide ions, we found that TBA
is heated and dissolved in an aromatic hydrocarbon solvent, ]00-150
It is characterized in that it is treated under azeotropic reflux dehydration while dropping an aqueous alkali metal hydroxide solution at ℃, and then neutralized, washed with water, and cooled to precipitate. The purpose is to eliminate bromide ions. That is, free bromine ions and mainly bromine added to the methyl group of bisphenol A are reacted with an alkali metal hydroxide and removed as sodium bromide. The aromatic hydrocarbon used in the present invention is preferably toluene or xylene having an appropriate boiling point, and the amount used is 0.5 to 3 times, preferably 1 to 2 times the weight of TEA. good. The alkali metal hydroxides used in the present invention include lithium hydroxide, potassium hydroxide, sodium hydroxide, and calcium hydroxide, which have a content of 5 to 50 f (by weight, preferably Vil O to 30 weight i%). It is preferable to use it as an aqueous solution.Also, the amount of alkali metal hydroxide used is 1 to 10% by weight, preferably 3 to 6% by weight, based on the weight of TEA.Use of alkali metal hydroxide If the amount is less than 1% by weight, it is difficult to obtain the desired hydrolyzable bromine content, and if the amount is more than 10% by weight, the effect of further reducing the hydrolyzable bromine content is weak, and the amount of alkali metal hydroxide is It's just a waste of money.
本発明における処理温度１１ｔ１００〜１５０℃であり
、芳香族炭化水素の沸点付近で脱水しながら行うのであ
る。例えばトルエンを使用した場合の処理温度Ｉ／′ｉ
］】０℃となる。また処理時間＃−ｉ０．５〜５時間、
好ましくは１〜３時間がよい。アル方り金属水酸化物処
理後、酸を加えて中和し、水洗したのち常温まで冷却し
てＴＥＡの結晶を析ｄさせ２濾過、乾燥して製品とする
。The treatment temperature in the present invention is 11t, 100 to 150°C, and is carried out while dehydrating near the boiling point of aromatic hydrocarbons. For example, the processing temperature I/'i when using toluene
]】0℃. In addition, processing time #-i0.5 to 5 hours,
Preferably, the time is 1 to 3 hours. After the alkali metal hydroxide treatment, acid is added to neutralize, washed with water, and then cooled to room temperature to precipitate TEA crystals, filtered, and dried to obtain a product.
「作用」
ＴＢＡを精製する方法にお論て、アルカリ金属水酸化物
で処理することにより、加水分解性臭素及び臭素イオン
を低減することが可能となる。"Effect" Regarding the method for purifying TBA, by treating it with an alkali metal hydroxide, it becomes possible to reduce hydrolyzable bromine and bromine ions.
これは通常の精製方法（例えば晶析法）では加水分解性
臭素を減じるととけ困難であり、苛酷な条件下すなわち
アルカリ金属水酸化物を作用させ臭化ナトリウムとして
脱離させる方法によらなければ達成できないものである
。This is difficult to eliminate by reducing hydrolyzable bromine using normal purification methods (e.g. crystallization), and must be removed under harsh conditions, i.e. by using an alkali metal hydroxide to eliminate it as sodium bromide. It is unattainable.
芳香族炭化水素を使用することは、芳香族炭化水素の沸
点領域で＃−ｔＴＢＡを溶解し、低温領域ではほとんど
溶解しないとｂう効果を利用したものであり、これによ
り製品収車を向上させることになる。The use of aromatic hydrocarbons utilizes the effect that #-tTBA dissolves in the boiling point region of aromatic hydrocarbons, but hardly dissolves in the low temperature region, thereby improving product collection. It turns out.
また、基本的に非水状態下で処理することは、加水分解
性臭素の脱離を促進するものであり、アルカリ金属水酸
化物水溶液として添加することは分散をよくする効果が
ある。本発明により精製したＴＥＡは加水分解性臭素含
量５０〜】ｏｏｐｐｍ、臭素イオンθ〜２ｐｐｍであり
、精製前のＴＥＡの加水分解性臭素１，０００〜ｚ、ｏ
ｏｏｐｐｍ、臭素イオン１０〜］００ｐｐｍに比較して
大幅に低減しているのが分る。以下に本発明の実施例に
より具体的に説明するが、木登（７）はこれら実施例の
みに限定でれるものではな堕
「実施例及び比較例」
実施例１
温度計、撹拌翼−加熱装置、アルカリ金属水酸化物水溶
液の滴下装置及びトルエン−水共沸混合物より連続的に
水を除去する還流コンデンザー付きの分離装置を有する
容量】ｌのセパラブルフラスコに、刃口水分解性臭素１
，２５０ｐｐｍ、臭素イオン４０ｐｐｍを含有するＴＢ
Ａ ２５０ｙｅとり、これにトルエン３７５９を加えて
、撹拌下１１０℃に昇温しでＴＥＡをトルエンに溶解し
た。これに２０重量％の苛性ソーダ６２．５ｙを３０分
間で滴下し、この間温度を】】０℃に保ってトルエン−
水共沸組成から順次水を系外へ除去した。苛性ソーダ滴
下終了後］］０〜】】２℃なる温度にて２時間反応させ
た。３５重ｉ：％の塩酸３１．７９全加えて中和したの
ち、熱水２００ｙを加えて水洗限装置して分離した水を
分液除去した。さらにもう−度目様に水洗したのち、１
５℃に冷却して結晶を析出きせた。これを許過し、窒素
気流下１００℃にて１時間乾燥して精製ＴＢＡ ２４２
ｙを得た。Furthermore, basically, treating under non-aqueous conditions promotes the elimination of hydrolyzable bromine, and adding it as an aqueous alkali metal hydroxide solution has the effect of improving dispersion. The TEA purified according to the present invention has a hydrolyzable bromine content of 50~]ooppm, bromide ion θ~2ppm, and the hydrolyzable bromine content of TEA before purification is 1,000~z, oppm.
It can be seen that the bromide ion content is significantly reduced compared to 10 to 00 ppm. The present invention will be specifically explained below using Examples, but Kinoto (7) is not limited to these Examples.Example 1 Thermometer, stirring blade - heating In a separable flask with a capacity of 1 liter, water-decomposable bromine with a cutting edge of 1 liter was added.
, 250 ppm, TB containing 40 ppm of bromide ions
250 ye of A was taken, 3,759 yen of toluene was added thereto, and the temperature was raised to 110° C. while stirring to dissolve TEA in toluene. To this, 62.5y of 20% by weight caustic soda was added dropwise over 30 minutes, and during this time the temperature was maintained at 】】0℃ and toluene
Water was sequentially removed from the system from the water azeotrope composition. After the completion of dropping the caustic soda, the mixture was reacted for 2 hours at a temperature of 0 to 2°C. After neutralizing by adding 31.79 ml of 35% hydrochloric acid, 200 y of hot water was added and the water was removed using a water washing device. After rinsing with water again, 1
It was cooled to 5°C to precipitate crystals. This was allowed to pass, and purified TBA 242 was dried for 1 hour at 100°C under a nitrogen stream.
I got y.
この精製ＴＥＡの加水分解性臭素は６２ｐｐｍ。The hydrolyzable bromine content of this purified TEA was 62 ppm.
臭素イオンは１ ｐｐｍであつｆｃ。Bromine ion is 1 ppm and fc.
実施例２
実施例１と同様の装置に、加水分解性臭素１．２５０ｐ
ｐｍ、臭素イオン４０ｐｐｍを含有するＴＥＡ２５０９
をとり、これにキシレン４００ｙを訓えて、撹拌下］４
５℃に昇温してＴＢＡをキシレンに溶解した。これに３
０重量％の苛性ソーダ４１．７ｙを１時間で滴下し、こ
の間温度を１４５℃に保ってキシレン−水共沸組成から
順次水を系外へ除去した。苛性ソーダ滴下終了後１４Ｆ
ｉ〜］４６℃なる温度にて２時間反応させたのち、３５
重量−の塩酸３１．７ｙ金川えて中オロした。以下実施
例１と同様の処理を行い、精製ＴＥＡ ２４０９を得
た。この精製ＴＥＡの加水分解性臭素は５５ｐｐｙｌ、
臭素イオンは］ ｐｐｍ以下であった。Example 2 In an apparatus similar to Example 1, 1.250 p of hydrolyzable bromine was added.
TEA2509 containing pm, bromine ion 40ppm
Add 400y of xylene to it and stir]4
The temperature was raised to 5°C to dissolve TBA in xylene. 3 to this
0% by weight of caustic soda (41.7y) was added dropwise over 1 hour, and during this time the temperature was maintained at 145°C to sequentially remove water from the xylene-water azeotrope composition. 14F after finishing caustic soda dripping
i~] After reacting at a temperature of 46°C for 2 hours, 35
31.7 y of hydrochloric acid by weight was added to Kanagawa and the mixture was washed out. Thereafter, the same treatment as in Example 1 was performed to obtain purified TEA 2409. The hydrolyzable bromine of this purified TEA is 55 ppyl,
Bromine ions were below ppm.
比較例】
温度計、撹拌翼及び力０熱装置を有する容量］ｌのセパ
ラブルフラスコに、加水分解性臭素１，２５９ｐｐｍ、
臭素イオン４ｏｐｐｍを含有するＴＢＡ２５０ｊ７をと
り、これにトルエン３７５ｙを刀ａえて、撹拌下１１０
℃に昇温してＴＢＡをトルエンに溶解した。これに熱水
２００ｙを加えて水洗し静置して分離した水を分液除去
した。１５℃に冷却して結晶を析出させ、許過したのち
、窒才気流下］００℃にて１時間乾燥して精製ＴＢＡ
２４１ｙを得た。この精製ＴＢＡの刃口水分解性臭素は
１．０４０Ｊ）Ｊ）１１１．臭素イオンは５ｐｐｍであ
った。Comparative Example: 1,259 ppm of hydrolyzable bromine,
Take TBA250j7 containing 4 oppm of bromide ions, add 375y of toluene to it, and boil for 110 minutes with stirring.
The temperature was raised to .degree. C. and TBA was dissolved in toluene. This was washed with 200 y of hot water, left to stand, and the separated water was separated and removed. After cooling to 15°C to precipitate crystals and allowing it to pass, drying at 00°C for 1 hour to obtain purified TBA.
241y was obtained. The water-decomposable bromine at the edge of this purified TBA is 1.040J)J)111. Bromine ion was 5 ppm.
比較例２
２０１量チの苛性ソーダ６、：（ｇｔ、３５重量％の塩
酸３．２ｙとした以外は全て実施ｆＡｌ ］と同様の操
作で行−５精製ＴＢＡ２４２ｐを得た。この精製ＴＥＡ
の刃口水分解性臭素は１８０ｐｐｍ、臭素イオンは：ｌ
ｐｐｍであった。Comparative Example 2 201 quantities of caustic soda 6: (gt, except that 35% by weight hydrochloric acid 3.2y) was used in the same manner as in Row 5 to obtain purified TBA242p.This purified TEA
The water decomposable bromine at the cutting edge is 180 ppm, and the bromine ion is: l
It was ppm.
「発りＪの効果」
本発明の精製方法は芳香族炭化水素ＶｃＴＢＡを物
溶解し、所定量のアルカリ金属水酸化水溶液を加△
えて、本質的に非水の状態で処理することにより加水分
解性臭素及び臭素イオンの極端に少ないＴＥＡを高収率
に得ると−う効果を示すものである。"Effect of starting J" The purification method of the present invention dissolves the aromatic hydrocarbon VcTBA, adds a predetermined amount of aqueous alkali metal hydroxide solution, and treats it in an essentially non-aqueous state to hydrolyze it. This shows the effect of obtaining TEA with extremely low amounts of bromine and bromine ions in high yield.
Claims (1)
に加熱溶解させ、１００〜１５０℃でアルカリ金属水酸
化物水溶液を滴下しながら共沸還流脱水下で処理した後
、中和、水洗、冷却して析出させることを特徴とするテ
トラブロムビスフェノールＡの精製方法。Tetrabromobisphenol A is heated and dissolved in an aromatic hydrocarbon solvent, treated under azeotropic reflux dehydration while dropping an aqueous alkali metal hydroxide solution at 100 to 150°C, and then neutralized, washed with water, cooled, and precipitated. A method for purifying tetrabromobisphenol A, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15737187A JPH07107007B2 (en) | 1987-06-24 | 1987-06-24 | Method for purifying tetrabromobisphenol A |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15737187A JPH07107007B2 (en) | 1987-06-24 | 1987-06-24 | Method for purifying tetrabromobisphenol A |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JPH013139A true JPH013139A (en) | 1989-01-06 |
| JPS643139A JPS643139A (en) | 1989-01-06 |
| JPH07107007B2 JPH07107007B2 (en) | 1995-11-15 |
Family
ID=15648194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15737187A Expired - Lifetime JPH07107007B2 (en) | 1987-06-24 | 1987-06-24 | Method for purifying tetrabromobisphenol A |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07107007B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL93176A0 (en) | 1989-01-26 | 1990-11-05 | Tosoh Corp | Process for producing tetra-bromobisphenol a |
| US7929498B2 (en) | 1995-06-30 | 2011-04-19 | Interdigital Technology Corporation | Adaptive forward power control and adaptive reverse power control for spread-spectrum communications |
| ZA965340B (en) | 1995-06-30 | 1997-01-27 | Interdigital Tech Corp | Code division multiple access (cdma) communication system |
| US6885652B1 (en) | 1995-06-30 | 2005-04-26 | Interdigital Technology Corporation | Code division multiple access (CDMA) communication system |
| US7020111B2 (en) | 1996-06-27 | 2006-03-28 | Interdigital Technology Corporation | System for using rapid acquisition spreading codes for spread-spectrum communications |
| JP2013253062A (en) * | 2012-06-08 | 2013-12-19 | Jfe Chemical Corp | Method for reducing halogen content in aromatic compound |
-
1987
- 1987-06-24 JP JP15737187A patent/JPH07107007B2/en not_active Expired - Lifetime
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