JPH0236578B2 - - Google Patents
Info
- Publication number
- JPH0236578B2 JPH0236578B2 JP61070892A JP7089286A JPH0236578B2 JP H0236578 B2 JPH0236578 B2 JP H0236578B2 JP 61070892 A JP61070892 A JP 61070892A JP 7089286 A JP7089286 A JP 7089286A JP H0236578 B2 JPH0236578 B2 JP H0236578B2
- Authority
- JP
- Japan
- Prior art keywords
- fluorene
- hydroxyphenyl
- bis
- solvent
- phenol
- 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 - Lifetime
Links
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 claims description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LNNIPFBETXOKIA-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-9h-fluoren-2-yl]phenol Chemical compound C1=CC(O)=CC=C1C1=CC=C(C=2C(=CC=CC=2)C2)C2=C1C1=CC=C(O)C=C1 LNNIPFBETXOKIA-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RJUUNZBMJIUPQB-UHFFFAOYSA-N 2-sulfanylpropanoic acid;hydrochloride Chemical compound Cl.CC(S)C(O)=O RJUUNZBMJIUPQB-UHFFFAOYSA-N 0.000 description 1
- GIXNHONPKYUROG-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)phenol Chemical compound C1=CC(O)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C12 GIXNHONPKYUROG-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 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
- 238000010438 heat treatment 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
- 239000002184 metal Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、耐熱性ポリエステルなどの原料とし
て利用することのできる９、９−ビス（４−ヒド
ロキシフエニル）フルオレンの合成後の分離、精
製方法に関する。
従来の技術
フエノールとフルオレノンの縮合により、９、
９−ビス（４−ヒドロキシフエニル）フルオレン
を合成する方法は、金属塩化物−塩化水素を触媒
として合成する方法が知られている。
またチエンら（ジヤーナル オブ アプライド
ポリマー サイエンス、J.Appl.Polym.Sci.、
27（９）、3289、1982年）は、金属塩化物に代え、
メルカプトプロピオン酸−塩化水素を触媒として
用いて、９、９−ビス（４−ヒドロキシフエニ
ル）フルオレンを合成したことを報告している。
前述のいずれの合成方法も、反応生成物の分
離、精製段階が、未反応のフエノールの水蒸気蒸
留に始まり、アルカリ溶解、濾過、中和再沈、濾
過、乾燥、再結晶と手順が非常に多く煩雑であ
る。これは工業化を意図した場合には、生産効率
から見て不利な条件である。
本願発明者らが前記のチエンらの方法などによ
り、同様の実験を繰り返し行つたが、手順が多
く、操作上アルカリ塩とするなどのために、目的
物の収率は約50％が限度であり、さらに得られた
９、９−ビス（４−ヒドロキシフエニル）フルオ
レンの純度も低く、着色が認められた。さらに製
品の純度を向上させるために、エーテルで再結晶
を２度行なつても、純度は99.0％であつた。
発明が解決しようとする問題点
本発明の目的は、これまで知られていた方法に
より、フルオレノンとフエノールより、９、９−
ビス（４−ヒドロキシフエニル）フルオレンを合
成し、反応生成物の分離、精製過程を改善し、簡
易な操作で収率向上を計り、高純度の目的物を得
ることにある。
問題を解決するための手段、作用
すなわち、本発明は、既存の方法により、フル
オレノンとフエノールより９、９−ビス（４−ヒ
ドロキシフエニル）フルオレンを合成し、反応後
未反応フエノールを除去した後、生成した９、９
−ビス（４−ヒドロキシフエニル）フルオレンを
一旦は溶解するが、時間の経過により９、９−ビ
ス（４−ヒドロキシフエニル）フルオレンと不溶
性の付加物を形成する溶剤により、９、９−ビス
（４−ヒドロキシフエニル）フルオレンを溶解後、
析出させることを特徴とする９、９−ビス（４−
ヒドロキシフエニル）フルオレンの分離、精製方
法である。前述の溶剤による溶解、析出は室温に
おいて行なうことができる。さらに、溶剤中の析
出物を分離して、再結晶法により精製すること
で、より純度を向上させることも可能である。
従来の方法では、目的物の９、９−ビス（４−
ヒドロキシフエニル）フルオレンと未反応のフエ
ノールおよび触媒との分離を水蒸気蒸留と言う固
定した手段で行なつているが、本発明では、この
目的物の分離、精製の工程を改善し、最も単純化
することを目指して検討を行ない本発明を完成し
た。
本発明を実施するには、まず例えば触媒として
塩化水素およびメルカプトプロピオン酸を用い、
フルオレノンとフエノールより９、９−ビス（４
−ヒドロキシフエニル）フルオレンを合成する。
反応の結果得られた残留物の中には、目的物の
９、９−ビス（４−ヒドロキシフエニル）フルオ
レン、未反応のフエノールおよび触媒の塩化水
素、メルカプトプロピオン酸が存在しているの
で、最初に未反応のフエノールを減圧蒸発等の手
段で除去する。未反応のフエノールが残留する
と、次の工程で溶剤中に溶解し、目的物の回収割
合を低下させるため、予め残留フエノールをでき
るだけ少なくしておくことが望ましい。
その後反応生成物を、特定の溶剤を用いて洗浄
法とも呼べるような手段で精製する。
一般には反応生成物は溶剤等による洗浄のみで
は、その純度が十分向上しないので、再結晶法が
用いられるが、本発明では、フエノールおよび触
媒の塩化水素、メルカプトプロピオン酸を良く溶
解し、目的物の９、９−ビス（４−ヒドロキシフ
エニル）フルオレンとは付加物を形成し、実質的
に溶解しないような溶剤を用いて分離、精製を行
なう。
溶剤としては、ジエチルエーテル、アセトン、
エタノール、プロパノール、ジオキサン、酢酸の
単独もしくは混合したものが使用できる。
未反応のフエノールを除去した後、反応生成物
を前述の溶剤中に入れたり、濾別後濾材上の反応
生成物に前述の溶剤を注ぎかけると、反応生成物
は室温において、加熱をしなくとも一旦溶解した
後、しばらくすると溶液中に結晶が析出する。こ
の析出物は各々の溶剤と９、９−ビス（４−ヒド
ロキシフエニル）フルオレンとが付加物を形成し
ているものと考えられる。この付加物について
は、赤外吸収（IR）スペクトル、核磁気共鳴
（NMR）スペクトルおよび熱重量分析（TGA）
により確認した。
この析出物は濾過等の手段で分離した後、30〜
80℃程度に加熱して乾燥することにより溶剤を除
くと、１回の操作で純度99.0％以上の９、９−ビ
ス（４−ヒドロキシフエニル）フルオレンが得ら
れる。
さらに、得られた９、９−ビス（４−ヒドロキ
シフエニル）フルオレンについて、これまで知ら
れている方法により再結晶を行なえば、容易に
99.6％以上の高純度のものを得ることができる。
本発明の場合には、特定の溶剤を使用して、触
媒の塩化水素、メルカプトプロピオン酸および残
存している極少量の未反応フエノールを溶剤中に
溶解し、目的物の９、９−ビス（４−ヒドロキシ
フエニル）フルオレンを一旦溶解してから、各々
の溶剤と付加物を形成して結晶化し析出するため
に、簡易な操作により容易に目的物の分離、精製
の目的を達するものと考えられる。
特定の溶剤を用いて、９、９−ビス（４−ヒド
ロキシフエニル）フルオレンを析出させ、濾過等
により分離した後は、前述のように分離した固体
を30〜80℃程度で減圧加熱することによつて、溶
剤を除去することができる。
このようにして得られる99.0％以上の純度の
９、９−ビス（４−ヒドロキシフエニル）フルオ
レンの純度をさらに向上させるには、前述の特定
の溶剤のほか、トルエン等の芳香族炭化水素系の
溶剤を使用して、再結晶法により高純度のものを
得ることができる。
以下本発明の内容を実施例により詳細に説明す
る。
実施例
実施例 １
三つ口フラスコに９−フルオレン45ｇ、フエノ
ール180ｇ、メルカプトプロピオン酸１mlを入れ、
40℃に加温し、溶液に塩化水素ガスを15分間吹き
込み、その後、系内の塩化水素ガスが飛散しない
ようにしながら、１時間撹拌した。
反応後、未反応のフエノールを減圧留去し、さ
らに真空ポンプを用いて、できる限りフエノール
を除去した。
その後フラスコ内にN2ガスを吹込みながら、
室温迄冷却した後、ジエチルエーテルを加えた。
さらに、フラスコを冷却しながら、撹拌すると、
一度均一溶液となつた後、結晶が析出した。この
顆粒状固体を濾過し分離してから、さらにトルエ
ンを用いて再結晶を行なつた。トルエンで再結晶
後の収率は75〜85％で、純度は99.6％以上であつ
た。
得られた９、９−ビス（４−ヒドロキシフエニ
ル）フルオレンの融点は223.7〜224.1℃であつ
た。
実施例 ２
三つ口フラスコに９−フルオレン45ｇ、フエノ
ール180ｇ、メルカプトプロピオン酸１mlを入れ、
40℃に加温し、溶液に塩化水素ガスを15分間吹き
込み、その後系内の塩化水素ガスが飛散しないよ
うにしながら、１時間撹拌した。
反応後、未反応のフエノールを減圧留去し、さ
らに真空ポンプを用いて、できる限りフエノール
を除去した。
その後フラスコ内にN2ガスと吹込みながら、
室温迄冷却した後、溶剤を実施例１のジエチルエ
ーテルに代えて、エタノール、アセトン、酢酸、
プロパノールおよびジオキサンとして同様に分
離、精製を行なつた。
結果は実施例１の場合とほゞ同様で、９、９−
ビス（４−ヒドロキシフエニル）フルオレンの収
率は80〜85％、純度99.6％以上であつた。
発明の効果
本発明では、従来の方法に比べ簡易な手段によ
り、９、９−ビス（４−ヒドロキシフエニル）フ
ルオレンの合成後、その分離、精製が容易にでき
ることから、工業化には非常に有利である。
９、９−ビス（４−ヒドロキシフエニル）フル
オレンは、耐熱性を要求される高分子用のモノマ
ーとして巾広く用いられる有用性の高い化合物で
ある。特にポリアリレート、ポリカーボネート、
エポキシ樹脂などの原料として利用され、このよ
うな原料が安価かつ安定して高純度のモノマーが
供給されることは、産業上有意義である。 DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for separating and purifying 9,9-bis(4-hydroxyphenyl)fluorene after synthesis, which can be used as a raw material for heat-resistant polyester and the like. . Conventional technology By condensation of phenol and fluorenone, 9,
A known method for synthesizing 9-bis(4-hydroxyphenyl)fluorene is to synthesize it using a metal chloride-hydrogen chloride as a catalyst. Also, Chien et al. (Journal of Applied Polymer Science, J.Appl.Polym.Sci.,
27(9), 3289, 1982), instead of metal chlorides,
It has been reported that 9,9-bis(4-hydroxyphenyl)fluorene was synthesized using mercaptopropionic acid-hydrogen chloride as a catalyst. In all of the above-mentioned synthesis methods, the reaction product separation and purification steps begin with steam distillation of unreacted phenol, followed by alkali dissolution, filtration, neutralization and reprecipitation, filtration, drying, and recrystallization. It's complicated. This is a disadvantageous condition from the viewpoint of production efficiency when industrialization is intended. The inventors of the present application repeatedly conducted similar experiments using the method of Chien et al., but the yield of the target product was limited to about 50% due to the large number of steps and the use of an alkali salt during the operation. Furthermore, the purity of the obtained 9,9-bis(4-hydroxyphenyl)fluorene was low, and coloration was observed. In order to further improve the purity of the product, recrystallization with ether was performed twice, and the purity remained 99.0%. Problems to be Solved by the Invention The object of the present invention is to produce fluorenone and phenol from 9,9-
The objective is to synthesize bis(4-hydroxyphenyl)fluorene, improve the separation and purification process of the reaction product, and improve the yield with simple operations to obtain a highly pure target product. Means and action for solving the problem That is, the present invention synthesizes 9,9-bis(4-hydroxyphenyl)fluorene from fluorenone and phenol by an existing method, and after removing unreacted phenol after the reaction. , generated 9, 9
- Bis(4-hydroxyphenyl)fluorene is dissolved once, but over time, the solvent forms an insoluble adduct with 9,9-bis(4-hydroxyphenyl)fluorene. After dissolving (4-hydroxyphenyl)fluorene,
9,9-bis(4-
This is a method for separating and purifying fluorene (hydroxyphenyl). Dissolution and precipitation using the above-mentioned solvents can be carried out at room temperature. Furthermore, it is also possible to further improve the purity by separating the precipitate in the solvent and purifying it by a recrystallization method. In the conventional method, 9,9-bis(4-
The separation of hydroxyphenyl)fluorene from unreacted phenol and catalyst is carried out by a fixed means called steam distillation, but in the present invention, the separation and purification process of this target product has been improved and simplified. The present invention was completed after conducting studies aimed at achieving this goal. To carry out the invention, first, for example, using hydrogen chloride and mercaptopropionic acid as catalysts,
9,9-bis(4) from fluorenone and phenol
-Hydroxyphenyl)fluorene is synthesized.
The residue obtained as a result of the reaction contains the target product 9,9-bis(4-hydroxyphenyl)fluorene, unreacted phenol, and the catalyst hydrogen chloride and mercaptopropionic acid. First, unreacted phenol is removed by means such as vacuum evaporation. If unreacted phenol remains, it will be dissolved in the solvent in the next step, reducing the recovery rate of the target product, so it is desirable to reduce the amount of residual phenol as much as possible in advance. Thereafter, the reaction product is purified using a specific solvent by what may be called a washing method. Generally, washing the reaction product with a solvent does not sufficiently improve its purity, so a recrystallization method is used. However, in the present invention, the phenol and the catalyst hydrogen chloride and mercaptopropionic acid are well dissolved and the desired product is obtained. It forms an adduct with 9,9-bis(4-hydroxyphenyl)fluorene, and is separated and purified using a solvent that does not substantially dissolve it. As a solvent, diethyl ether, acetone,
Ethanol, propanol, dioxane, and acetic acid can be used alone or in combination. After removing unreacted phenol, if the reaction product is placed in the above-mentioned solvent or the above-mentioned solvent is poured onto the reaction product on the filter medium after filtration, the reaction product will remain at room temperature without being heated. Once both are dissolved, crystals will precipitate in the solution after a while. This precipitate is considered to be an adduct formed by each solvent and 9,9-bis(4-hydroxyphenyl)fluorene. For this adduct, infrared absorption (IR) spectra, nuclear magnetic resonance (NMR) spectra and thermogravimetric analysis (TGA)
Confirmed by. After separating this precipitate by means such as filtration,
When the solvent is removed by heating to about 80° C. and drying, 9,9-bis(4-hydroxyphenyl)fluorene with a purity of 99.0% or more can be obtained in one operation. Furthermore, the obtained 9,9-bis(4-hydroxyphenyl)fluorene can be easily recrystallized by a known method.
High purity of 99.6% or higher can be obtained. In the case of the present invention, a specific solvent is used to dissolve the catalyst hydrogen chloride, mercaptopropionic acid and a very small amount of unreacted phenol in the solvent, and the desired product 9,9-bis( After 4-hydroxyphenyl)fluorene is dissolved, adducts are formed with each solvent, crystallized, and precipitated, so it is believed that the purpose of separating and purifying the target product can be easily achieved through simple operations. It will be done. After precipitating 9,9-bis(4-hydroxyphenyl)fluorene using a specific solvent and separating it by filtration, etc., heat the separated solid under reduced pressure at about 30 to 80°C as described above. The solvent can be removed by. In order to further improve the purity of 9,9-bis(4-hydroxyphenyl)fluorene, which has a purity of 99.0% or more, it is necessary to use aromatic hydrocarbons such as toluene in addition to the specific solvents mentioned above. High purity can be obtained by recrystallization using a solvent of The content of the present invention will be explained in detail below using examples. Examples Example 1 Put 45 g of 9-fluorene, 180 g of phenol, and 1 ml of mercaptopropionic acid into a three-necked flask.
The solution was heated to 40° C., hydrogen chloride gas was blown into the solution for 15 minutes, and then stirred for 1 hour while preventing the hydrogen chloride gas in the system from scattering. After the reaction, unreacted phenol was distilled off under reduced pressure, and as much phenol as possible was removed using a vacuum pump. Then, while blowing N2 gas into the flask,
After cooling to room temperature, diethyl ether was added.
Furthermore, by stirring while cooling the flask,
Once the solution became homogeneous, crystals precipitated. This granular solid was filtered and separated, and then recrystallized using toluene. The yield after recrystallization with toluene was 75-85%, and the purity was 99.6% or more. The melting point of the obtained 9,9-bis(4-hydroxyphenyl)fluorene was 223.7 to 224.1°C. Example 2 Put 45 g of 9-fluorene, 180 g of phenol, and 1 ml of mercaptopropionic acid into a three-necked flask.
The solution was heated to 40° C., hydrogen chloride gas was blown into the solution for 15 minutes, and then the solution was stirred for 1 hour while keeping the hydrogen chloride gas in the system from scattering. After the reaction, unreacted phenol was distilled off under reduced pressure, and as much phenol as possible was removed using a vacuum pump. Then, while blowing N2 gas into the flask,
After cooling to room temperature, the solvent was replaced with diethyl ether of Example 1, and ethanol, acetone, acetic acid,
Propanol and dioxane were similarly separated and purified. The results are almost the same as in Example 1, 9, 9-
The yield of bis(4-hydroxyphenyl)fluorene was 80-85%, and the purity was 99.6% or more. Effects of the Invention The present invention allows easy separation and purification of 9,9-bis(4-hydroxyphenyl)fluorene after its synthesis by simpler means than conventional methods, which is very advantageous for industrialization. It is. 9,9-bis(4-hydroxyphenyl)fluorene is a highly useful compound that is widely used as a monomer for polymers that require heat resistance. Especially polyarylate, polycarbonate,
It is industrially significant that it is used as a raw material for epoxy resins and the like, and that such a raw material is inexpensive and can stably supply high-purity monomers.
Claims (1)
れた粗製９、９−ビス（４−ヒドロキシフエニ
ル）フルオレンを精製する方法において、未反応
フエノールを除去したのち、９、９−ビス（４−
ヒドロキシフエニル）フルオレンを一旦は溶解す
るが、時間の経過により９、９−ビス（４−ヒド
ロキシフエニル）フルオレンと不溶性の付加物を
形成する溶剤により、９、９−ビス（４−ヒドロ
キシフエニル）フルオレンを溶解後析出させるこ
とを特徴とする９、９−ビス（４−ヒドロキシフ
エニル）フルオレンの分離、精製方法。 ２ 析出した析出物を分離したのち、再結晶精製
する特許請求の範囲第１項記載の分離、精製方
法。 ３ 溶剤が、ジエチルエーテル、アセトン、エタ
ノール、プロパノール、ジオキサン、酢酸の単独
もしくは混合したものである特許請求の範囲第１
項記載の分離、精製方法。[Claims] 1. In a method for purifying crude 9,9-bis(4-hydroxyphenyl)fluorene obtained by reacting fluorenone and phenol, after removing unreacted phenol, 9,9-bis(4-hydroxyphenyl)fluorene is purified. (4-
The solvent dissolves 9,9-bis(4-hydroxyphenyl)fluorene, but over time forms an insoluble adduct with 9,9-bis(4-hydroxyphenyl)fluorene. A method for separating and purifying 9,9-bis(4-hydroxyphenyl)fluorene, which comprises dissolving and then precipitating 9,9-bis(4-hydroxyphenyl)fluorene. 2. The separation and purification method according to claim 1, wherein the precipitate is separated and then purified by recrystallization. 3. Claim 1 in which the solvent is diethyl ether, acetone, ethanol, propanol, dioxane, or acetic acid alone or in combination.
Separation and purification methods described in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7089286A JPS62230741A (en) | 1986-03-31 | 1986-03-31 | Separation and purification of 9,9-bis(4-hydroxyphenyl) fluorene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7089286A JPS62230741A (en) | 1986-03-31 | 1986-03-31 | Separation and purification of 9,9-bis(4-hydroxyphenyl) fluorene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62230741A JPS62230741A (en) | 1987-10-09 |
| JPH0236578B2 true JPH0236578B2 (en) | 1990-08-17 |
Family
ID=13444631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7089286A Granted JPS62230741A (en) | 1986-03-31 | 1986-03-31 | Separation and purification of 9,9-bis(4-hydroxyphenyl) fluorene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62230741A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19638888A1 (en) * | 1996-09-23 | 1998-03-26 | Bayer Ag | Production of cyclic aromatic bis:phenol compounds |
| JP5054299B2 (en) * | 2004-12-14 | 2012-10-24 | 大阪瓦斯株式会社 | Method for producing fluorene derivative |
| JP5572430B2 (en) * | 2009-03-23 | 2014-08-13 | 本州化学工業株式会社 | Process for producing 9,9-bis (4-hydroxyphenyl) fluorenes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4049721A (en) * | 1976-09-07 | 1977-09-20 | General Electric Company | Purification of crude 9,9-bis-(4-hydroxyphenyl)-fluorene |
-
1986
- 1986-03-31 JP JP7089286A patent/JPS62230741A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4049721A (en) * | 1976-09-07 | 1977-09-20 | General Electric Company | Purification of crude 9,9-bis-(4-hydroxyphenyl)-fluorene |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62230741A (en) | 1987-10-09 |
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