JPH02225433A - Purification of 4,4'-biphenol - Google Patents
Purification of 4,4'-biphenolInfo
- Publication number
- JPH02225433A JPH02225433A JP4833189A JP4833189A JPH02225433A JP H02225433 A JPH02225433 A JP H02225433A JP 4833189 A JP4833189 A JP 4833189A JP 4833189 A JP4833189 A JP 4833189A JP H02225433 A JPH02225433 A JP H02225433A
- Authority
- JP
- Japan
- Prior art keywords
- ketone
- biphenol
- water
- molar ratio
- 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.)
- Pending
Links
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000000746 purification Methods 0.000 title description 3
- 150000002576 ketones Chemical class 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 239000012046 mixed solvent Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 8
- 238000009835 boiling Methods 0.000 abstract description 5
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 abstract description 4
- 229920006351 engineering plastic Polymers 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000012043 crude product Substances 0.000 abstract 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- -1 3,5-dimethylbiphenol Chemical compound 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006210 debutylation Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000007858 starting material Substances 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〕 本発明は４．４′−ビフェノール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 4,4'-biphenol.
４．４′−ビフェノール類は、近年耐熱性エンジニアリ
ングプラスチックスの出発原料として腓光を浴びており
、本発明の方法により、当該ポリマー用原料として供す
るに足る高純度の４．４′ −ビフェノール類を経済的
に製造することが出来る。4.4'-biphenols have recently been in the spotlight as starting materials for heat-resistant engineering plastics, and the method of the present invention produces 4.4'-biphenols of high purity sufficient to serve as raw materials for the polymers. can be produced economically.
ビフェノールは、一般に高融点、高沸点物質であるため
、蒸留操作による精製は困難である。しかしながら、ビ
フェノールは各種有機溶媒に対する溶解性が比較的悪く
、高純度のビフェノールを効率的に回収する為には、溶
媒の選択が難しい。Since biphenol is generally a high melting point and high boiling point substance, it is difficult to purify it by distillation. However, biphenol has relatively poor solubility in various organic solvents, and it is difficult to select a solvent in order to efficiently recover high-purity biphenol.
特公昭６３−１９２８号公報にはケトン、アルコール及
びエーテルの少なくとも一種にビフェノールを溶解復水
を添加し、生成する結晶を分離する方法が報告されてい
る。しかしながらこれらの有機溶媒に対するビフェノー
ルの溶解度は、工業的方法に用いるには十分とはいえな
い。また、ポリマー原料として適する高純度ビフェノー
ルを得る為には、活性炭処理等の操作が必要であるが、
その際にビフェノールの析出を抑える為に過剰の溶媒を
加えておく必要がありバッチ当りのビフェノール収量が
低くなるという欠点がある。Japanese Patent Publication No. 63-1928 reports a method in which biphenol is dissolved in at least one of ketone, alcohol, and ether, condensate is added, and the resulting crystals are separated. However, the solubility of biphenol in these organic solvents is not sufficient for use in industrial methods. In addition, in order to obtain high-purity biphenol suitable as a polymer raw material, operations such as activated carbon treatment are necessary.
At that time, it is necessary to add an excessive amount of solvent to suppress the precipitation of biphenol, which has the disadvantage of lowering the yield of biphenol per batch.
上述した様に、従来の方法ではビフェノールの溶解性が
低く又、多量の溶媒が必要であり非能率的である等の問
題点があり、本発明は、かかる従来技術の難点を著しく
改善４，４′−ビフェノールの精製方法を提供せんとす
るものである。As mentioned above, the conventional method has problems such as the low solubility of biphenol and the need for a large amount of solvent, making it inefficient, and the present invention significantly improves these drawbacks of the prior art4. The object of the present invention is to provide a method for purifying 4'-biphenol.
本発明者らは、上記問題点を解決する為、鋭意検討を行
った結果、驚くべき事に特定割合の水／ケトン混合系溶
媒に於いてビフェノール類の溶解度がケトンのみの場合
に比べ、著しく増大する事を見い出し本発明を完成した
。In order to solve the above problems, the present inventors conducted intensive studies and found that, surprisingly, the solubility of biphenols in a mixed solvent of water/ketone at a specific ratio is significantly higher than that of ketones alone. The present invention was completed based on the discovery that the increase in
即ち、本発明は、粗製４．４’−ビフェノールをモル比
０．１〜１．５の水／ケトン混合溶媒に溶解させ、得ら
れた溶液の水／ケトンモル比を２以上にして析出した結
晶を分離することを特徴とする４、４′−ビフェノール
の精製方法を提供するものである。That is, the present invention involves dissolving crude 4,4'-biphenol in a water/ketone mixed solvent with a molar ratio of 0.1 to 1.5, and making the resulting solution have a water/ketone molar ratio of 2 or more to produce precipitated crystals. The present invention provides a method for purifying 4,4'-biphenol, which is characterized by separating 4,4'-biphenol.
本発明の方法は、４，４′−ビフェノールの精製に必要
な溶媒量を著しく減らす事が可能となり、経済的、効率
的な精製方法である。The method of the present invention makes it possible to significantly reduce the amount of solvent required for purifying 4,4'-biphenol, and is an economical and efficient purification method.
本発明に用いられる粗製４．４′−ビフェノールとして
は例えば２．６−置換アルキルフェノールの酸化２量化
、及び置換ビフェノールの酸触媒等による脱アルキル化
により得られる下記一般弐Ｒ１Ｒ４
（式中、ＲＩ、 Ｒ４は水素又はアルキル基を示す。）
で表されるビフェノールが挙げられる。具体的には４．
４′−ビフェノール、３．５−ジメチルビフェノール、
３．３ ’ 、５．５’ −テトラメチルビフェノール
、３．３’ 、５．５’−テトラブチルビフェノール等
含む純度９０％以上のものが一般的である。The crude 4,4'-biphenol used in the present invention is, for example, the following general 2R1R4 (wherein RI, R4 represents hydrogen or an alkyl group.)
Examples include biphenols represented by Specifically, 4.
4'-biphenol, 3,5-dimethylbiphenol,
Those containing 3.3', 5.5'-tetramethylbiphenol, 3.3', 5.5'-tetrabutylbiphenol, etc. with a purity of 90% or more are generally used.
これらのうちでも４．４′ −ビフェノールが特に好ま
しい。Among these, 4,4'-biphenol is particularly preferred.
溶媒として用いるケトン類としては、低級脂肪族ケトン
が好ましく特に、沸点又は水との共沸点が１００°Ｃ以
下のものが好ましい。具体的には、アセトン、メチルエ
チルケトン、２−ペンタノン等が挙げられる。The ketones used as the solvent are preferably lower aliphatic ketones, particularly those having a boiling point or azeotropic point with water of 100°C or less. Specific examples include acetone, methyl ethyl ketone, and 2-pentanone.
上記ビフェノールを溶解する際の水／ケトンの混合モル
比は０．１〜１．５、より好ましくは０．２〜０．１の
範囲である。この組成範囲に於けるビフェノールの溶解
度はケトンのみの場合に比べ著しく増大する。特にビフ
ェノール類の水に対する溶解度はほとんどなく撥水性を
示す程であることから、この溶解現象は、４．４′ −
ビフェノールと水／ケトン混合溶媒の組合せに於いて特
異的なものである。これら混合溶媒の使用量はビフェノ
ール類が完全に溶解する以上の量を用いれば良いが、具
体的には、ビフェノール類に対し３重量倍以上好ましく
は、３〜１０重量倍程度用いる０が好妻七（転）混合溶
液は、所定量を別々に添加するのが一般的であるが、あ
らかじめ調整したものを用いてもよい。また、溶解温度
は室温以上溶媒の沸点以下より選ばれるが、高温程溶解
度が大きいのでより好ましい。The mixing molar ratio of water/ketone when dissolving the biphenol is in the range of 0.1 to 1.5, more preferably 0.2 to 0.1. The solubility of biphenols in this composition range is significantly increased compared to ketones alone. In particular, since biphenols have almost no solubility in water and only exhibit water repellency, this dissolution phenomenon is 4.4'-
This is a unique combination of biphenol and water/ketone mixed solvent. The amount of these mixed solvents should be at least enough to completely dissolve the biphenols, but specifically, 3 to 10 times the weight of the biphenols, preferably 3 to 10 times the weight of the biphenols. Although it is common to separately add a predetermined amount of the seven-fold mixed solution, a solution prepared in advance may also be used. The dissolution temperature is selected from room temperature or higher and lower than the boiling point of the solvent, but higher temperatures are more preferable because the solubility is higher.
次に、得られた混合溶媒のビフェノール溶液の水／ケト
ンのモル比を２以上好ましくは３以上にして結晶の析出
を行う、水／ケトンモル比を太きくするには、得られた
溶液に水を添加するか、又はケトンを留去する事により
行うことができる。Next, crystals are precipitated by setting the water/ketone molar ratio of the obtained mixed solvent biphenol solution to 2 or more, preferably 3 or more. This can be done by adding or distilling off the ketone.
水の添加は、析出する結晶の粒径を出来るだけ大きくす
る為、ゆっくり滴下する方法で添加するのが好ましい。In order to increase the particle size of the precipitated crystals as much as possible, it is preferable to add water slowly and dropwise.
また。ケトンを留去する方法では、溶液をケトンの沸点
まで加温するか系内をケトンの蒸気圧まで減圧にするか
の方法により行う。この様にして析出したビフェノール
の結晶を、濾過により分離するが、その際の温度として
は、回収率を上げる為に出来るだけ低温で行うことが好
ましい。−船釣には、５０″Ｃ以下、好ましくは３０″
Ｃ〜１０℃の範囲で行われる。Also. The method of distilling off the ketone is carried out by heating the solution to the boiling point of the ketone or reducing the pressure in the system to the vapor pressure of the ketone. The biphenol crystals thus precipitated are separated by filtration, and the temperature at that time is preferably as low as possible in order to increase the recovery rate. - For boat fishing, below 50″C, preferably 30″
It is carried out in the range of 10°C to 10°C.
本発明の方法では無機不純物は容易に炉液側へ移行する
のでポリマー原料として供するに足りる高純度ビフェノ
ールを得ることが出来る。また着色成分についても容易
に炉液側へ溶は込むので、色相の良好なビフェノール類
を得ることが出来る。In the method of the present invention, inorganic impurities are easily transferred to the furnace liquid side, so that high purity biphenol that can be used as a polymer raw material can be obtained. Furthermore, since the coloring components are easily dissolved into the furnace liquid, biphenols with good hue can be obtained.
〔実施例〕 つぎに実験例により本発明を具体的に説明する。〔Example〕 Next, the present invention will be specifically explained using experimental examples.
参考例
温度、溶媒組成をかえて、４．４′−とフェノールの溶
解度を測定した結果を以下に示す。尚、溶解度の測定は
公知の方法（例えば、「物理化学実験法」東京化学同人
出版１１９頁等参照）によった。Reference Example The solubility of 4.4'- and phenol was measured by changing the temperature and solvent composition, and the results are shown below. The solubility was measured by a known method (for example, see "Physical Chemistry Experimental Method", Tokyo Kagaku Dojin Publishing, p. 119).
実施例１
２６−ジーｔｅｒｔ−ブチルフェノールの酸化・脱ブチ
ル化によって得られた淡紫色の粗製４，４′−ビフエノ
ール（ビフェノール１度９８．０％、Ｓ含有量３７５
ｐｐｍ ） ｌ Ｏｇにアセトン３２ ｇ （０，５５
ｍｏｆ）と水８ ｇ （０，４４ｍｏｆ ）を加えて５
０″Ｃにて攪拌し、４．４′−ビフェノールを完全に溶
解した。次に水３２ ｇ （１，７８ｔｓｏｌ ）を滴
下し、室温まで冷却した。得られた結晶をか別、乾燥し
て８．０ｇの白色のビフェノールを得た（回収率８０％
） ＨＰＬＣにて分析した結果、純度９９．５％、また
イオンクロマトにて分析の結果Ｓ含有量は２２ｐｐｍで
あった。Example 1 Light purple crude 4,4'-biphenol obtained by oxidation and debutylation of 26-di-tert-butylphenol (biphenol 1 degree 98.0%, S content 375
ppm ) 32 g of acetone (0,55
mof) and 8 g (0.44 mof) of water.
The mixture was stirred at 0"C to completely dissolve 4,4'-biphenol. Next, 32 g (1,78 tsol) of water was added dropwise and cooled to room temperature. The resulting crystals were separated and dried. 8.0 g of white biphenol was obtained (recovery rate 80%).
) As a result of HPLC analysis, the purity was 99.5%, and as a result of ion chromatography analysis, the S content was 22 ppm.
実施例２
実施例１に於いて、アセトンの代りにメチルエチルケト
ン４０ ｇ （０，５５モル）を用いた以外は実施例１
と同様に精製を行った結果７．７ｇの白色のビフェノー
ルを得た（回収率＝７７％）、分析の結果、純度９９．
６％、Ｓ含有量は２０ｐｐｍであった。Example 2 Example 1 except that 40 g (0.55 mol) of methyl ethyl ketone was used instead of acetone.
As a result of purification in the same manner as above, 7.7 g of white biphenol was obtained (recovery rate = 77%), and as a result of analysis, the purity was 99.
6%, and the S content was 20 ppm.
Claims (1)
水／ケトン混合溶媒に溶解させ、得られた溶液の水／ケ
トンモル比を２以上にして析出した結晶を分離すること
を特徴とする４，４′−ビフェノールの精製方法。Crude 4,4'-biphenol is dissolved in a water/ketone mixed solvent with a molar ratio of 0.1 to 1.5, and the resulting solution has a water/ketone molar ratio of 2 or more to separate the precipitated crystals. A method for purifying 4,4'-biphenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4833189A JPH02225433A (en) | 1989-02-28 | 1989-02-28 | Purification of 4,4'-biphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4833189A JPH02225433A (en) | 1989-02-28 | 1989-02-28 | Purification of 4,4'-biphenol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02225433A true JPH02225433A (en) | 1990-09-07 |
Family
ID=12800434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4833189A Pending JPH02225433A (en) | 1989-02-28 | 1989-02-28 | Purification of 4,4'-biphenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02225433A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008050669A1 (en) * | 2006-10-18 | 2008-05-02 | Idemitsu Kosan Co., Ltd. | Polycarbonate copolymer, method for producing the same, molded body, optical material, and electrophotographic photosensitive body |
-
1989
- 1989-02-28 JP JP4833189A patent/JPH02225433A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008050669A1 (en) * | 2006-10-18 | 2008-05-02 | Idemitsu Kosan Co., Ltd. | Polycarbonate copolymer, method for producing the same, molded body, optical material, and electrophotographic photosensitive body |
| US7888455B2 (en) | 2006-10-18 | 2011-02-15 | Idemitsu Kosan Co., Ltd. | Polycarbonate copolymer, method for producing the same, molded body, optical material, and electrophotographic photosensitive body |
| US7893185B2 (en) | 2006-10-18 | 2011-02-22 | Idemitsu Kosan Co., Ltd. | Polycarbonate copolymer, method for producing the same, molded body, optical material, and electrophotographic photosensitive body |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4162270A (en) | Process for producing 4,4'-dihydroxydiphenylsulfone of high purity | |
| JPH06287161A (en) | Preparation of oxyphthalic dianhydride and purified oxyphthalic dianhydride from crude oxyphthalic dianhydride | |
| JP2515765B2 (en) | Method for separating o, p ''-isomer of bisphenol A | |
| EP0220855B1 (en) | Process for recovering 4,4' dihydroxydiphenyl sulfone from an isomer mixture | |
| CA2053604C (en) | Improved method for the purification of acetaminophen | |
| JPH02225433A (en) | Purification of 4,4'-biphenol | |
| JPH01226842A (en) | Isolation of dihydroxydiphenylmethane | |
| JPH10218798A (en) | Purification of organic solvent | |
| JPH04145061A (en) | Production of highly pure 4,4'-dihydroxydiphenyl sulfone | |
| JPS582236B2 (en) | Method for isolating 4,4'-dihydroxydiphenylsulfone from a mixture of dihydroxydiphenylsulfone isomers | |
| CN108863862B (en) | Method for refining crude bisphenol S by using pseudocumene mixed solvent | |
| US5001270A (en) | Process for recovering 4,4' dihydroxydiphenyl sulfone from an isomer mixture | |
| JPH0248543A (en) | Purification of p,p'-biphenol | |
| JPS62138443A (en) | Production of biscresol | |
| US4021495A (en) | Purification of β-naphthol | |
| EP1199298A1 (en) | Process for producing refined pyromellitic acid and refined pyromellitic anhydride | |
| JP3001097B1 (en) | Method for producing sorbic acid | |
| WO2008060107A1 (en) | Method for purifying terephthalaldehyde | |
| JP2874281B2 (en) | Method for separating and purifying biphenyl-4,4'-diol | |
| JPS6261955A (en) | Purification of n,n-diethylaminophenol | |
| JP2503153B2 (en) | Method for producing neutral salt of naphthalenesulfonic acid formalin cocondensate | |
| JPH0512344B2 (en) | ||
| JPS62255445A (en) | Method for purifying 2,4,6-trimethylphenol | |
| JP2641022B2 (en) | Purification method of 4,4'-dihydroxydiphenyl sulfone | |
| JPS5896035A (en) | Purification of phloroglucin |