JPH0248543A - Purification of p,p'-biphenol - Google Patents
Purification of p,p'-biphenolInfo
- Publication number
- JPH0248543A JPH0248543A JP19724088A JP19724088A JPH0248543A JP H0248543 A JPH0248543 A JP H0248543A JP 19724088 A JP19724088 A JP 19724088A JP 19724088 A JP19724088 A JP 19724088A JP H0248543 A JPH0248543 A JP H0248543A
- Authority
- JP
- Japan
- Prior art keywords
- biphenol
- recrystallization
- solvent
- crude
- water
- 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 34
- 238000000746 purification Methods 0.000 title description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001953 recrystallisation Methods 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004927 clay Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 18
- 239000013078 crystal Substances 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000012046 mixed solvent Substances 0.000 abstract description 5
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 abstract 1
- 238000001914 filtration Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000006210 debutylation Effects 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- KDTZBYPBMTXCSO-UHFFFAOYSA-N 2-phenoxyphenol Chemical class OC1=CC=CC=C1OC1=CC=CC=C1 KDTZBYPBMTXCSO-UHFFFAOYSA-N 0.000 description 1
- DDTHMESPCBONDT-UHFFFAOYSA-N 4-(4-oxocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-one Chemical compound C1=CC(=O)C=CC1=C1C=CC(=O)C=C1 DDTHMESPCBONDT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は芳香族性ポリエステル、ポリカーボネート、エ
ポキシ樹脂等の各種重合体の製造原料として有用なｐ、
ｐ’−ビフェノールの精製方法に関するものである。Detailed Description of the Invention [Industrial Field of Application] The present invention provides p,
The present invention relates to a method for purifying p'-biphenol.
［従来の技術とその課題］
ｐ、ｐ’−ビフェノールは各種樹脂原料として近年注目
を集めている化合物でおるが、これらの用途のためには
、特に高純度でおり、また着色していないことが求めら
れる。しかし、ｐ、ｐ−ビフエノルは、常温で固体であ
り、融点・沸点とも高く、蒸溜操作によって精製するこ
とは不可能であるうえに、空気中の酸素によって酸化を
うけて着色しやすい化合物であり、精製のむずかしい物
質である。[Prior art and its problems] p, p'-biphenol is a compound that has recently attracted attention as a raw material for various resins, but for these uses, it must be of particularly high purity and not colored. is required. However, p,p-biphenol is a solid at room temperature, has a high melting point and high boiling point, and is impossible to purify by distillation. In addition, it is a compound that is easily oxidized and colored by oxygen in the air. , is a substance that is difficult to purify.
ｐ、ｐ’−ビフェノールは、■ジフェニルジスルホン酸
のアルカリ溶融、あるいは■テトラーｔ−ブチルビフェ
ノールの脱ブチル化反応によって製造されるのが一般的
であり、■の方法によってはｐ−フ工二ルフェノールに
代表される単官能性フ■ノルが、■の方法によっては完
全には［−ブチル基の除去の完了していないモノ−も一
ブチル体あるいはジーも一ブチル体が、また■、■いず
れの方法においてもｐ、ｐ−ビフェノールの酸化によっ
て生成するジフェノキノンが不純物として混入するもの
である。ざらに、いずれの場合においても、触媒または
原料としてＮａ、に等のアルカリ金属塩を使用するが、
その存在は、望ましくない場合が多い。p, p'-biphenol is generally produced by (1) alkaline melting of diphenyldisulfonic acid or (2) debutylation reaction of tetra-t-butylbiphenol. Monofunctional phenol represented by phenol may be completely converted into mono- or di-butyl form depending on the method of ①, in which the removal of the -butyl group is not completed, or ①, ■ In either method, diphenoquinone produced by oxidation of p,p-biphenol is mixed as an impurity. Generally speaking, in either case, an alkali metal salt such as Na, etc. is used as a catalyst or raw material, but
Its presence is often undesirable.
このような背景から、粗製ｐ、ｐ’−ビフェノールの精
製り法については、多くの１ｉＪＩ究者によって検δ・
１されており、今日までに次のような方法が公知となっ
ている。Against this background, many 1iJI researchers have investigated the purification method of crude p,p'-biphenol by
1, and the following methods are known to date.
例えば特開昭５９−９８．０２７Ｑ公報に示されるよう
に、アル：１−ル、ケトン、環状エーテル等の可溶性有
機溶媒に、粗製のｐ、ｐ’−ビフェノールを溶解し、不
純物を濾過で除いたのらに、貧溶媒である芳香族炭化水
素（例えばトルエン、キシレン等）を加え、ざらに可溶
性溶媒の大部分を溜去してｐ、ｐ’−ビフェノールを析
出させる方法や、特開昭６０−２３．３３８号公報に示
されるように、前駆体であるテトラ−ｔ−ブチルビフェ
ノールを、酸触媒を用いて、ジフェニルエーテル中で、
脱ブチル化反応を行い、そのままｐ、ｐ−ビフェノール
を晶析させる方法、さらに米国特許第３．６３１ 、２
０８＠に示されるように、脱ブチル化反応を行った粗製
のｐ、ｐ’〜ビフェノールを塩酸−エタノール中で洗浄
後、７〜１０重量倍のエタノールから再結晶する方法等
が挙げられる。For example, as shown in JP-A-59-98.027Q, crude p,p'-biphenol is dissolved in a soluble organic solvent such as al, ketone, or cyclic ether, and impurities are removed by filtration. There is a method in which p,p'-biphenol is precipitated by adding aromatic hydrocarbons (e.g. toluene, xylene, etc.), which are poor solvents, to tanora and distilling off most of the soluble solvent in the colander. As shown in Japanese Patent No. 60-23.338, tetra-t-butylbiphenol, which is a precursor, is prepared in diphenyl ether using an acid catalyst.
A method of performing a debutylation reaction and crystallizing p, p-biphenol as it is, and further US Patent No. 3.631, 2
As shown in 08@, the crude p, p'-biphenol subjected to the debutylation reaction is washed in hydrochloric acid-ethanol, and then recrystallized from 7 to 10 times the weight of ethanol.
しかし、これらの方法のうり、例えば第１の方法では、
ｐ、ｐ’−ビフェノールに対して１５〜２０倍の溶媒が
必要とされるうえに、多硫の溶媒を蒸溜により除去プる
必要もあり、工業的に有利な方法とはいいがたい。第２
の方法では脱ブチル化反応にジフェニルエーテルのよう
な高沸点で特殊な溶媒を用いることから、結晶からのシ
フ１ニルエーテルの洗浄・除去が面倒であり、かつ経済
的にも有利とは言えないことが指摘できる。さらに第３
の方法では、ｔ−ブチル基の残存する中間体が製品であ
るｐ、ｐ−ビフェノールに混入しやすく、純度か上から
ない欠点を有している。However, among these methods, for example, the first method,
This method requires 15 to 20 times as much solvent as p,p'-biphenol and also requires distillation to remove the polysulfuric solvent, so it cannot be said that this is an industrially advantageous method. Second
Since the method uses a special solvent with a high boiling point such as diphenyl ether for the debutylation reaction, it is troublesome to wash and remove Schiff 1 nyl ether from the crystals, and it cannot be said to be economically advantageous. I can point it out. Furthermore, the third
This method has the disadvantage that the intermediate containing the t-butyl group is likely to be mixed into the p,p-biphenol product, and the purity cannot be improved.
このように、粗製１）、Ｄ’−ビフェノールの精製には
未だ技術的に改善すべき点が多く残されている。As described above, there are still many technical points to be improved in the purification of crude 1) and D'-biphenol.
［課題を解決するための手段］
本発明者らは、以上の従来技術の問題点を解決すべく、
鋭意検討を行った結果、上記の不純物類を効率よ＜ ｐ
、ｐ’−ビフェノールから除去して、高純度・無着色の
ｐ、 ｐ’−ビフェノールを得る方法を見出すに至った
。[Means for Solving the Problems] In order to solve the problems of the above-mentioned prior art, the present inventors have
As a result of intensive studies, we have found that the above impurities can be efficiently
, p'-biphenol to obtain highly pure and uncolored p,p'-biphenol.
すなわち本発明は、粗製ｐ、ｐ−ビフェノールを、親水
性有機溶媒と水との混合液を再結晶溶媒として用いて再
結晶操作を行うことを特徴とするｐ、ｐ’−ビフェノー
ルの精製方法、ｄ３よび、粗製ｐ、ｏ’−ビフェノール
を、親水性有機溶媒と水との混合液を再結晶溶媒として
用いて再結晶操作を行い、次いで回収された再結晶濾液
を再結晶溶媒として循環使用してなることを特徴とする
ｐ、 ｐ’−ビフェノールの精製方法である。That is, the present invention provides a method for purifying p, p'-biphenol, which comprises recrystallizing crude p, p-biphenol using a mixture of a hydrophilic organic solvent and water as a recrystallization solvent; d3 and crude p,o'-biphenol are recrystallized using a mixture of a hydrophilic organic solvent and water as a recrystallization solvent, and then the collected recrystallization filtrate is recycled and used as a recrystallization solvent. This is a method for purifying p, p'-biphenol.
また上記の再結晶操作においては、活性炭および／また
は活性白土を用いることを好適とするしのである。Furthermore, in the above recrystallization operation, it is preferable to use activated carbon and/or activated clay.
本発明では、ｐ、ｐ’−ビフェノールに対して良溶媒で
ある親水性有機溶媒と、貧溶媒である水との混合溶媒を
粗製ｐ、ｐ−ビフェノールの再結晶溶媒に使用すること
を特徴とする。親水性有機溶媒単独による再結晶法、あ
るいはこの親水性有機溶媒に試料を溶解させた後、水の
後添加による再結晶・再沈澱法では良好な精製物が１ｑ
られない。これは、後述づるように、水との混合溶媒系
とづることで大きな溶解度差が確保され、このことによ
って再結晶効率の向上が図られると共に、活性炭・活性
白土を用いた場合には、再結晶時に水が存在覆ることに
よって活性炭・活性白土の脱色・精製効率の向上が図ら
れるためである。The present invention is characterized in that a mixed solvent of a hydrophilic organic solvent, which is a good solvent for p, p'-biphenol, and water, which is a poor solvent, is used as the recrystallization solvent for crude p, p'-biphenol. do. A good purified product can be obtained by recrystallization using a hydrophilic organic solvent alone, or recrystallization/reprecipitation using a hydrophilic organic solvent and subsequent addition of water.
I can't. As will be explained later, by using a mixed solvent system with water, a large difference in solubility is ensured, which improves the recrystallization efficiency, and when activated carbon/activated clay is used, it is possible to This is because the presence of water during crystallization improves the decolorization and purification efficiency of activated carbon and activated clay.
また本発明においては、−度回収した再結晶濾液をざら
に再結晶溶媒として循環使用することができる。この場
合、再結晶媒質中のｐ、ｐ−ビフェノールはすでに飽和
状態になっているので、ざらにｐ、ｐ−ビフェノールが
溶は込むことがほとんどなく、再結晶効率の一層の向上
を図ることができる。Furthermore, in the present invention, the recrystallized filtrate recovered can be recycled as a recrystallization solvent. In this case, since the p, p-biphenol in the recrystallization medium is already saturated, p, p-biphenol hardly dissolves into the recrystallization medium, making it possible to further improve the recrystallization efficiency. can.
本発明において使用される粗’Ｎｐ、ｐ’−ビフエノル
としては、例えばシフＴニルスルホン酸のアルカリ溶融
法によって１７られるもの、あるいはテトラ−１−ブチ
ルビフェノールの脱ブチル化反応によって得られるもの
等があり、ここで含まれる不純物としては、叶フェノキ
シ７１ノール、叶フ■ニルフェノール、ビフェノールの
−しノー、ジ−トリー、テトラ−１−ブヂル体等のビフ
ェノールと類似構造を１４′ｔＪるフェノール誘導体類
、およびジフェノキノン類等の酸化生成物、さらに、Ｎ
ａ。Examples of the crude 'Np, p'-biphenol used in the present invention include those obtained by the alkaline melting method of Schiff T-nylsulfonic acid, or those obtained by the debutylation reaction of tetra-1-butylbiphenol. The impurities contained here include phenol derivatives with a similar structure to biphenol, such as phenoxy-71nol, phenylphenol, biphenol, di-trily, and tetra-1-butyl. , and oxidation products such as diphenoquinones, as well as N
a.
Ｋ、 Ｆｅ等の金属イオンを含有する無機塩類が挙げら
れ、一般にこのような粗￥Ｕｒ）、Ｄ’〜ビフエノルは
、程度に違いはあっても、淡褐色ないしは褐色に着色し
ているものである。Examples include inorganic salts containing metal ions such as K and Fe, and generally, such crude ions, D'~biphenols, are colored light brown or brown, although there are differences in degree. be.
ここで使用される親水・［１１有機溶媒とは、自由な割
合で水と混相しうる溶媒であり、例示すれば、メタノー
ル、エタノール、イソ１０ピルアルコル等の低級アルコ
ール類；アセトン、メチルエチルケトン等のケ１〜ン類
；テトラヒドロフラン、ジオキサン等の環状エーテル類
：メチルｃロソルブ、エチルセロソルブ等のセロソルブ
類等が挙げられ、なかで：ｂ低級アルコール類およびア
セトンが好ましい。The hydrophilic/[11 organic solvents used here are solvents that can be mixed with water in any proportion; examples include lower alcohols such as methanol, ethanol, and iso-10-pyl alcohol; Examples include cyclic ethers such as tetrahydrofuran and dioxane; cellosolves such as methyl cellosolve and ethyl cellosolve; among these, lower alcohols and acetone are preferred.
これらの溶媒１００重量部に対して混和させる水の使用
量は、使用する溶媒種によって異なってくるが、ｐ、ｐ
’−ビフェノールの溶解性を大きく損わない程度の含水
量、すなわら１００重品部以下、好ましくは３５中量部
以下、０．５重量部以上で用いられる。The amount of water to be mixed with 100 parts by weight of these solvents varies depending on the type of solvent used, but p, p
The water content is used at a level that does not significantly impair the solubility of '-biphenol, that is, 100 parts by weight or less, preferably 35 parts by weight or less, and 0.5 parts by weight or more.
ｐ、 ｐ’−ビフェノールの溶解性は、良溶媒単独で用
いられる場合よりも水の存在により溶解性が低下してい
ることから、比較的多量の溶媒が必要であるが、含水溶
媒を用いることは次の二つの利点がある。The solubility of p, p'-biphenol is lowered by the presence of water than when a good solvent is used alone, so a relatively large amount of solvent is required, but it is possible to use a water-containing solvent. has the following two advantages.
すなわら第１は、精製り、ｌ）’−ヒフエノールの前置
の向上である。ｐ、ｐ−ビフェノールの１７弓は再結晶
溶媒中の溶解度差によって決定づけられ、相対的に水で
希釈された溶媒は、良溶媒（１１独の場合よりもはるか
に大きな溶解度差を持つものであり、溶媒の使用績の多
さにもかかわらす、むしろ結晶の前置は増大する。第２
の利点はｐ、ｐ−ビフェノールの精製脱色を行うにあた
り、活性炭および／または活性白土を使用すると、活性
炭および／または活性白土が有する脱色および不純物吸
着の効果か水の共存によってより高められることにある
。The first is purification and improvement of the preposition of l)'-hyphenol. The 17-bow of p,p-biphenol is determined by the solubility difference in the recrystallization solvent, and a solvent relatively diluted with water is a good solvent (one with a much larger solubility difference than the 11-sol). , Despite the extensive use of solvents, the preposition of crystals increases.Second
The advantage of using activated carbon and/or activated clay when purifying and decolorizing p, p-biphenol is that the decolorizing and impurity adsorption effects of activated carbon and/or activated clay are enhanced by the coexistence of water. .
再結晶操作にあたっては、Ｌ記の如き混合溶媒中で粗製
ｐ、ｐ−ビフェノールを加熱・溶解さけ、次いで冷却し
てその溶解度差により精製１）、［）’−ビフェノール
を得る。この際、ざらに結晶の冑÷間の増大を求めるな
らば、再結晶の濾液に水を添加することもよく、これは
結晶の晶析速度を向１−ざぜることにも有効である。ま
た、−度回収しｌこ再結晶濾液をざらに再結晶溶媒とし
て循環使用フることも、結晶の１ｑ禰を増大さける上で
有効である。In the recrystallization operation, crude p,p-biphenol is heated and dissolved in a mixed solvent as described in L, and then cooled to obtain purified 1), [)'-biphenol based on the difference in solubility. At this time, if a rough increase in crystal size/dimension is desired, water may be added to the recrystallization filtrate, and this is also effective in reducing the crystallization rate. Furthermore, recycling the recrystallized filtrate that has been collected twice as a recrystallization solvent is also effective in avoiding an increase in the number of crystals.
活性炭および／または活性白土を使用する場合、その形
状は粒状、粉末、破砕状のいずれも使用が可能であるが
、バッチ式でｌｉ！Ｉ製を行う場合には粉末状か、流通
式で使用される場合には粒状や多孔質の形状が右利であ
る。バッチ式で使用される場合には、粗Ｆ！Ａｐ、ｐ−
ビフェノール１部に対して０、０００５〜０．１５中ω
部、好ましくはｏ、ｏｏｉ〜０．０５巾呈部が使用され
る。活性白土も活性炭と全く同様に使用されるか、これ
らの併用も差支えない。When using activated carbon and/or activated clay, it can be in the form of granules, powder, or crushed, but it can be used in batch-type li! In case of I-manufacturing, it is preferable to use powder form, or in case of using in a flow type, granular or porous form is preferable. When used in batch mode, coarse F! Ap, p-
0.0005 to 0.15 ω per part of biphenol
parts, preferably o, ooi to 0.05 parts are used. Activated clay may be used in exactly the same way as activated carbon, or a combination of these may be used.
このようにして、親水性有機溶媒と水の併用により精製
されたｐ、ｐ’−ヒフエノールは、例えばｐ、ｐ−シフ
１ニルジスルホン酸のアルカリ溶融によって’＋’ｆＪ
られた粗製物に由来するものであれば、スルホン１＞１
を残した中間体あるいは−［）じド［１キシビフエニル
、ｐ、ｐ−ジフェノキノンといった不純物を実質的に含
有せず、またテトラブチルじフェノールの脱ブチル化反
応によって得られた粗製物に由来するものであれば、七
ノー、シー、トリー、テトラ−といったｔ−ブブル基を
残置したビフェノール類あるいはフェノキシフェノール
類、ｐ、ｐ−ジフェノキノン類等の不純物を実質的に含
有しない純白の結晶として取得づ゛ることかできる。In this way, p,p'-hyphenol purified using a combination of a hydrophilic organic solvent and water can be purified by, for example, '+'fJ
Sulfone 1>1 if it is derived from a crude product
It does not substantially contain impurities such as the intermediate remaining or -[)dido[1-xybiphenyl, p, p-diphenoquinone, and is derived from the crude product obtained by the debutylation reaction of tetrabutyl diphenol. If available, it can be obtained as pure white crystals that do not substantially contain impurities such as biphenols with residual t-buble groups such as 7-no, C, tri-, and tetra-, phenoxyphenols, p, p-diphenoquinones, etc. I can do it.
［発明の効果］
以上説明したように、本発明の方法によって１ｑられる
精製ｐ、ｐ’−ビフェノールは、他の不純物を実質的に
含有しない純度の高いものである。特に、再結晶媒質が
水を含有することから、金属イオンの除去効率も高く、
ここで得られた精製ｐ、ｐ’−ビフェノールは、例えば
、縮合系高分子の合成原料などの用途には最適のもので
ある。[Effects of the Invention] As explained above, the purified p,p'-biphenol produced by 1q by the method of the present invention has high purity and does not substantially contain other impurities. In particular, since the recrystallization medium contains water, the removal efficiency of metal ions is also high.
The purified p,p'-biphenol obtained here is optimal for use as a raw material for the synthesis of condensation polymers, for example.
［実施例］ 以下、本発明の実施例について説明する。[Example] Examples of the present invention will be described below.
実施例１
テトラ−（−ブチルピッＴ）・−ルを酸触媒の存在下、
脱ブチル化反応させることによって得られた粗製ｐ、ｐ
’−ヒフエノール（純度９７．６％、淡黄色）１３０９
を８０％メタノール１０００ｇに加熱溶解し、続いて粉
末状活性炭４．０ｇを加え、３０分間攪拌する。Example 1 Tetra-(-butylpit-T)-ol in the presence of an acid catalyst,
Crude p, p obtained by debutylation reaction
'-Hiphenol (purity 97.6%, pale yellow) 1309
was heated and dissolved in 1000 g of 80% methanol, then 4.0 g of powdered activated carbon was added and stirred for 30 minutes.
熱部濾過により活性炭を除去した後、攪拌をしながら、
室温まで冷却し、ｐ、ｐ’−ビフェノールを晶析させる
。析出した結晶を濾過により回収し、真空乾燥すること
により、白色のｐｉｆ！Ａｐ、ｐ’−ヒフエノール１０
５Ｊを得た。この精製ｐ、ｐ−ビフェノールの分析値は
、純度９９．９ ｗｔ％、回収率は粗製ｐ、ｐ−ビフェ
ノール中のビフェノール含有量を基準として８２．８％
であった。After removing activated carbon by hot section filtration, while stirring,
Cool to room temperature and crystallize p,p'-biphenol. The precipitated crystals are collected by filtration and vacuum dried to produce white pif! Ap, p'-hyphenol 10
I got 5J. The analytical value of this purified p, p-biphenol is that the purity is 99.9 wt%, and the recovery rate is 82.8% based on the biphenol content in the crude p, p-biphenol.
Met.
実施例２
実施例１で得られたｐ、ｐ’−ビフェノールの再結晶濾
液を、８０％メタノール１０００ ｇのかわりに用いる
他は、実施例１と同様にして、粗製ｐ、ｐ−ビフェノー
ル１３０ｇの再結晶を行い、白色の精製ｐ、ｐ’−ビフ
ェノール１２３ｇを得た。この精製ｐ、ｐ’−ビフェノ
ールの分析値は、ＭＡ度９９．９ ｗｔ％てあった。Example 2 130 g of crude p, p'-biphenol was prepared in the same manner as in Example 1, except that the recrystallized filtrate of p, p'-biphenol obtained in Example 1 was used instead of 1000 g of 80% methanol. Recrystallization was performed to obtain 123 g of white purified p,p'-biphenol. The analytical value of this purified p,p'-biphenol was that the MA degree was 99.9 wt%.
実施例３
テトラ−１−ブチルビフェノールを酸触媒の存在下、脱
ブチル化反応させることによって得られた粗製ｐ、ｐ−
ビフェノール（純度９７．６％、淡黄色）２００９を９
５％メタノール１３５０ＳＪに加熱溶解し、内容物が完
全に溶解した後、活性炭６．０ｇを加え、３０分間攪拌
する。熱部濾過により活性炭を除去した後、７０℃の温
水２５０ｇを濾液に加えて攪拌しなからｐ、ｐ’−ビフ
ェノールを晶析させる。析出した結晶を濾過により回収
し、真空乾燥することにより、白色の精製ｐ、ｐ−ビフ
ェノール１８５．４ｇを得る。この精製ｐ、ｐ’−ビフ
ェノールの分析値は、純度９９．９ｗｔ％、回収率は粗
製ｐ、ｐ−ビフェノール中のビフェノール含有量を阜ｊ
％として９５．０％であり、金属イオンは検出されなか
った。Example 3 Crude p, p- obtained by debutylating tetra-1-butylbiphenol in the presence of an acid catalyst
Biphenol (purity 97.6%, pale yellow) 2009 9
Heat and dissolve in 5% methanol 1350SJ, and after the contents are completely dissolved, 6.0 g of activated carbon is added and stirred for 30 minutes. After removing activated carbon by hot section filtration, 250 g of 70°C warm water is added to the filtrate and stirred to crystallize p,p'-biphenol. The precipitated crystals are collected by filtration and vacuum dried to obtain 185.4 g of white purified p,p-biphenol. The analytical value of this purified p, p'-biphenol is that the purity is 99.9 wt%, and the recovery rate is the same as the biphenol content in the crude p, p-biphenol.
% was 95.0%, and no metal ions were detected.
実施例４
実施例３に記載の粗製ヒフ１ノールと同じ試料２０（１
７を７５％アセトン１１００５７に加熱溶解し、内容物
が完全に溶解した後、活↑４炭５．２ｇと活性白土３．
１ｇを加え、３０分間攪拌覆る。熱部濾過により活性炭
・活性白土を除去した後、５０℃の温水７００９を加え
て、攪拌しなからり、ｌ）’−ヒフエノールを析出させ
る。結晶を濾過により回収し、真空乾燥することにより
、白色の＃！ｌ製ビノビフェノール１９２．９９る。こ
の精製ビフェノールの分析値は純度９９．９ｗｔ％、回
収率は９８．８％であり、含有する金属イオンはＫが１
０ｐｐｍであった。Example 4 Sample 20 (1
7 in 75% acetone 110057, and after the contents were completely dissolved, 5.2 g of activated ↑4 charcoal and activated clay 3.
Add 1 g, stir and cover for 30 minutes. After removing activated carbon and activated clay by hot section filtration, 50° C. warm water 7009 is added and without stirring, l)′-hyphenol is precipitated. By collecting the crystals by filtration and drying them under vacuum, white #! Binobiphenol manufactured by L 192.99. The analytical value of this purified biphenol is 99.9 wt% purity, 98.8% recovery rate, and the metal ion contained is 1 K.
It was 0 ppm.
実施例５
シフＩニルジスルホン酸をアルカリ溶融することによっ
て得られる、粗製のｐ、 ｐ’−ビフェノール（純度９
２．３％、淡紅色） １３０ｇを８０％メタノール１
０００ｇに加熱溶解し、続いて粉末状活性炭５゜０９と
活性白土１．Ｏｇを加え、３０分間おだやかに加熱・攪
拌する。熱部濾過（７０°Ｃ）で活性炭と活性白土を除
去した後、攪拌しながら、室温まで冷却し、ｐ、ｐ−ヒ
フエノールを晶析させる。析出した結晶を濾過により回
収し、真空乾燥づることにより、白色の精製ｐ、ｐ’−
ビフェノール１００ゾを１７た。Example 5 Crude p, p'-biphenol (purity 9
2.3%, light pink) 130g to 80% methanol 1
000g and then add 5.09g of powdered activated carbon and 1.0g of activated clay. Add Og and gently heat and stir for 30 minutes. After removing activated carbon and activated clay by hot section filtration (70°C), the mixture is cooled to room temperature while stirring, and p,p-hyphenol is crystallized. The precipitated crystals were collected by filtration and vacuum dried to give white purified p,p'-
Biphenol 100 zo was 17.
このｖ５製ｐ、ｐ’−ビフェノールの分析値は、純度９
９．８ｗｔ％、回収率は粗製ｐ、ｐ”−ヒフエノール中
のビフェノール含有量を基準として８３．３％であった
。また精製ビフェノール中に含有する金属イオンは、Ｎ
ａ ： ４１）Ｉ）ｍ 、 Ｋ ：１０ ｐＩ）ｍ、
Ｆｅ ： ８１）１１１１１であった。The analysis value of this v5 p,p'-biphenol is purity 9.
9.8 wt%, and the recovery rate was 83.3% based on the biphenol content in crude p,p''-hyphenol.Also, the metal ions contained in purified biphenol were
a: 41) I) m, K: 10 pI) m,
Fe: 81)11111.
Claims (4)
と水との混合液を再結晶溶媒として用いて再結晶操作を
行うことを特徴とするｐ，ｐ’−ビフェノールの精製方
法。(1) A method for purifying p,p'-biphenol, which comprises recrystallizing crude p,p'-biphenol using a mixture of a hydrophilic organic solvent and water as a recrystallization solvent.
白土を用いる請求項（１）記載のｐ，ｐ’−ビフェノー
ルの精製方法。(2) The method for purifying p,p'-biphenol according to claim (1), wherein activated carbon and/or activated clay is used in the recrystallization operation.
と水との混合液を再結晶溶媒として用いて再結晶操作を
行い、次いで回収された再結晶濾液を再結晶溶媒として
循環使用してなることを特徴とするｐ，ｐ’−ビフェノ
ールの精製方法。(3) Recrystallize crude p,p'-biphenol using a mixture of a hydrophilic organic solvent and water as a recrystallization solvent, and then recycle and use the recovered recrystallization filtrate as a recrystallization solvent. A method for purifying p,p'-biphenol, characterized by:
白土を用いる請求項（３）記載のｐ，ｐ’−ビフェノー
ルの精製方法。(4) The method for purifying p,p'-biphenol according to claim (3), wherein activated carbon and/or activated clay is used in the recrystallization operation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19724088A JPH0248543A (en) | 1988-08-09 | 1988-08-09 | Purification of p,p'-biphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19724088A JPH0248543A (en) | 1988-08-09 | 1988-08-09 | Purification of p,p'-biphenol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0248543A true JPH0248543A (en) | 1990-02-19 |
Family
ID=16371180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19724088A Pending JPH0248543A (en) | 1988-08-09 | 1988-08-09 | Purification of p,p'-biphenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0248543A (en) |
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-
1988
- 1988-08-09 JP JP19724088A patent/JPH0248543A/en active Pending
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| JP2008121009A (en) * | 2006-10-18 | 2008-05-29 | Idemitsu Kosan Co Ltd | Polycarbonate copolymer, method for producing the same and electrophotographic photoreceptor |
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| JP2010013656A (en) * | 2006-10-18 | 2010-01-21 | Idemitsu Kosan Co Ltd | Polycarbonate copolymer, molding, optical material, electrophotographic material, and electrophotographic photoreceptor |
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