JPH045251A - Purification of 4,4'-dihydroxybiphenyl - Google Patents
Purification of 4,4'-dihydroxybiphenylInfo
- Publication number
- JPH045251A JPH045251A JP10528490A JP10528490A JPH045251A JP H045251 A JPH045251 A JP H045251A JP 10528490 A JP10528490 A JP 10528490A JP 10528490 A JP10528490 A JP 10528490A JP H045251 A JPH045251 A JP H045251A
- Authority
- JP
- Japan
- Prior art keywords
- bpl
- crude
- dihydroxybiphenyl
- phenols
- purified
- 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 group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 238000000746 purification Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 150000002989 phenols Chemical class 0.000 claims abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 150000001298 alcohols Chemical class 0.000 claims abstract description 6
- 238000001953 recrystallisation Methods 0.000 claims abstract description 6
- 150000002576 ketones Chemical class 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- -1 phenol) Chemical class 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 abstract description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 abstract description 2
- 229920006015 heat resistant resin Polymers 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 241001550224 Apha Species 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- NUEUMFZLNOCRCQ-UHFFFAOYSA-N 1-propan-2-yl-4-(4-propan-2-ylphenyl)benzene Chemical group C1=CC(C(C)C)=CC=C1C1=CC=C(C(C)C)C=C1 NUEUMFZLNOCRCQ-UHFFFAOYSA-N 0.000 description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- WMVJWKURWRGJCI-UHFFFAOYSA-N 2,4-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC=C(O)C(C(C)(C)CC)=C1 WMVJWKURWRGJCI-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- HOLHYSJJBXSLMV-UHFFFAOYSA-N 2,6-dichlorophenol Chemical compound OC1=C(Cl)C=CC=C1Cl HOLHYSJJBXSLMV-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- RJEUFLRBVCILIH-UHFFFAOYSA-N 3-butyl-2-(2-hydroxyphenyl)phenol Chemical compound CCCCC1=CC=CC(O)=C1C1=CC=CC=C1O RJEUFLRBVCILIH-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
- JTHGIRIGZAGNOX-UHFFFAOYSA-N 4-pentan-2-ylphenol Chemical compound CCCC(C)C1=CC=C(O)C=C1 JTHGIRIGZAGNOX-UHFFFAOYSA-N 0.000 description 1
- ZYZWCJWINLGQRL-UHFFFAOYSA-N 4-phenylcyclohexa-2,4-diene-1,1-diol Chemical group C1=CC(O)(O)CC=C1C1=CC=CC=C1 ZYZWCJWINLGQRL-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000006210 debutylation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000008096 xylene 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’−ジヒドロキシビフェニル（以下、
ＢＰＬと略記する）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 relates to 4,4'-dihydroxybiphenyl (hereinafter referred to as
This paper relates to a method for purifying BPL (abbreviated as BPL).
本発明の目的物であるＢＰＬは、液晶性ポリマーや耐熱
性樹脂等の原料として有用な化合物てあ［従来の技術］
ＢＰＬは各種樹脂原料として使用されるが、これらの用
途に使用するためには高純度で色相の良好なものてなけ
れはならない。しかし、ＢＰＬは融点、沸点とも高く、
蒸留操作による精製が困難であり、空気中の酸素により
酸化され着色しヤすい。BPL, which is the object of the present invention, is a compound useful as a raw material for liquid crystal polymers, heat-resistant resins, etc. [Prior art] BPL is used as a raw material for various resins, but in order to use it for these purposes, must be of high purity and good hue. However, BPL has a high melting point and boiling point,
It is difficult to purify by distillation and is easily oxidized and colored by oxygen in the air.
ＢＰＬの製造方法として、これまでにいくつかの方法が
提案されている。例えば、
■ ビフェニルをスルホン化してアルカリ溶融する方法
、
■ ビフェニルをハロゲン化して加水分解する方法、
■ ２，６−ジー第三−ブチルフェノールを酸化カップ
リング後、還元して得られるテトラ−第三−ブチルビフ
ェノールを酸触媒の存在下で脱ブチル化する方法、
■ ４，４′−ジイソプロピルビフェニルを酸化してジ
ヒドロペルオキシドとし、酸分解する方法、■ ｐ−ク
ロロフェノールを脱ハロゲンニ量化する方法
等が知られている。Several methods have been proposed so far for manufacturing BPL. For example, ■ a method of sulfonating biphenyl and melting it with alkali, ■ a method of halogenating biphenyl and hydrolyzing it, and ■ a method of reducing 2,6-di-tert-butylphenol after oxidative coupling. A method of debutylating butylbiphenol in the presence of an acid catalyst, a method of oxidizing 4,4'-diisopropylbiphenyl to dihydroperoxide and decomposing it with an acid, and a method of dehalogenizing p-chlorophenol are known. It is being
これらの各種製造方法から得られる粗製ＢＰＬ中には、
単官能性フェノールなどの副生物が含まれており、さら
に、いずれの場合においても、ＢＰＬの酸化によって生
成するジフェノキノンが含まれるため、褐色ないしは黄
土色に着色している。In the crude BPL obtained from these various manufacturing methods,
It contains by-products such as monofunctional phenol, and in any case also contains diphenoquinone produced by oxidation of BPL, so it is colored brown or ocher.
このような背景から、粗製ＢＰＬの精製方法がいくつか
提案されている。Against this background, several methods for purifying crude BPL have been proposed.
例えは特開昭５６−３９０３０号公報には、粗製ＢＰＬ
を沸点１００℃以下の有機溶剤に溶解し、同有機溶剤の
沸点以下で活性炭処理した後、水を添加して晶析を行い
、生成する結晶を分離する方法が開示されている。また
、特開昭５９−９８０２７号公報には、粗製ＢＰＬを脂
肪族低級アルコール、ケトン類または環状エーテルに溶
解し、この溶液に芳香族炭化水素を加え、得られた溶液
を蒸留して上記アルコール、ケトン類または環状エーテ
ル類の大部分を留去してＢＰＬを析出させ、これを分離
する方法か開示されている。特開平１−２２６８４１号
公報および特開平２−４８５４３号公報には、粗製ＢＰ
Ｌを脂肪族低級ケトン類及びアルコール類と水との混合
溶媒に加熱溶解し、活性炭処理を行なった後、冷却晶析
し、析出した結晶を分離する方法が開示されている。For example, in Japanese Patent Application Laid-Open No. 56-39030, crude BPL
Disclosed is a method in which the compound is dissolved in an organic solvent having a boiling point of 100° C. or less, treated with activated carbon at a temperature below the boiling point of the organic solvent, water is added to perform crystallization, and the resulting crystals are separated. Furthermore, JP-A No. 59-98027 discloses that crude BPL is dissolved in an aliphatic lower alcohol, ketones, or cyclic ether, aromatic hydrocarbons are added to this solution, and the resulting solution is distilled to dissolve the above-mentioned alcohol. , a method is disclosed in which most of the ketones or cyclic ethers are distilled off to precipitate BPL and this is separated. In JP-A-1-226841 and JP-A-2-48543, crude BP
A method is disclosed in which L is heated and dissolved in a mixed solvent of aliphatic lower ketones and alcohols and water, treated with activated carbon, cooled and crystallized, and the precipitated crystals are separated.
これらの方法は、いずれも色相を向上させるために活性
炭処理を行なわなけれはならないという問題点があった
。All of these methods have the problem of requiring activated carbon treatment to improve the hue.
［発明が解決しようとする課題］
本発明の目的は、高純度かつ色相のすぐれたＢＰＬを簡
便に得ることができるＢＰＬの精製方法を提案すること
である。[Problems to be Solved by the Invention] An object of the present invention is to propose a method for purifying BPL that can easily obtain BPL with high purity and excellent hue.
［課題を解決するための手段］
本発明は、粗製ＢＰＬを再結晶により精製する方法にお
いて、 「フェノール類」ならびに「脂肪族低級アルコ
ール類およびケトン類から選ばれる一種以上の含水又は
無水有機溶剤」の混合液を再結晶溶剤として用いること
を特徴とする、４，４−ジヒドロキシビフェニルの精製
方法である。[Means for Solving the Problems] The present invention provides a method for purifying crude BPL by recrystallization, in which one or more hydrous or anhydrous organic solvents selected from "phenols", "aliphatic lower alcohols, and ketones" This is a method for purifying 4,4-dihydroxybiphenyl, which is characterized by using a mixed solution of as a recrystallization solvent.
本発明の方法を用いれは、活性炭素処理する事なく、高
純度で色相の改善されたＢＰＬを得る事が出来る。By using the method of the present invention, BPL with high purity and improved hue can be obtained without any activated carbon treatment.
本発明の方法で精製されうる粗製ＢＰＬは、いかなる方
法で製造された物でもよいが、ＢＰＬ １重量部に対し
て、反応副生物や未反応原料なとの有機不純物の量が１
重量部以下、一般には０．１重量部以下のものが用いら
れる。粗製ＢＰＬは、一般に固形状であるが、ＢＰＬが
溶媒中で生成され、溶解している場合にはその溶媒を留
去する必要はなく、溶液中ヘフェノール類を加えて晶析
することができる。例えは、４，４゛−ジイソプロピル
ビフェニルを酸化し、生成したジヒドロペルオキシド類
を酸分解することによりＢＰＬを製造する方法では、酸
分解後のＢＰＬはアセトン等の有機溶媒に溶解している
が、この場合は他の有機溶媒を加える事なくフェノール
類を加え晶析してもよい。The crude BPL that can be purified by the method of the present invention may be produced by any method, but the amount of organic impurities such as reaction by-products and unreacted raw materials is 1 part by weight of BPL.
Parts by weight or less, generally 0.1 parts by weight or less, are used. Crude BPL is generally in solid form, but if BPL is produced in a solvent and is dissolved, there is no need to distill off the solvent, and it can be crystallized by adding hephenols to the solution. . For example, in a method of producing BPL by oxidizing 4,4'-diisopropylbiphenyl and acid decomposing the generated dihydroperoxides, the BPL after acid decomposition is dissolved in an organic solvent such as acetone. In this case, phenols may be added and crystallized without adding any other organic solvent.
本発明の方法で粗製ＢＰＬを有機溶媒に溶解する際に添
加されうるフェノール類としては、例えは、フェノール
、０−クレゾール、ｐ−クレゾール、ｍ−クレゾール、
■）−第三−ブチルフェノール、ｐ−第二一アミルフェ
ノール、０−クロロフェノールおよびｐ−クロロフェノ
ールなとのモノ置換フェノール類、２，４−キシレノー
ル、２゜６−キシレノール、２，４−ジー第三−フチル
フェノール、２，４−ジー第三−アミルフェノール、２
．４−ジクロロフェノールおよび２，６−ジクロロフェ
ノールなどの二置換フェノール、２，４゜６−ドリメチ
ルフエノールなとの三置換フェノールなとがある。これ
らは単独でも、二種類以上を任意の割合で混合した物で
も、どちらでも使用することができ、この中では、フェ
ノールが最も好ましい。Examples of phenols that can be added when dissolving crude BPL in an organic solvent in the method of the present invention include phenol, 0-cresol, p-cresol, m-cresol,
■) - Monosubstituted phenols such as tert-butylphenol, p-sec-amylphenol, 0-chlorophenol and p-chlorophenol, 2,4-xylenol, 2゜6-xylenol, 2,4-di- Tertiary-phthylphenol, 2,4-di-tertiary-amylphenol, 2
．． There are disubstituted phenols such as 4-dichlorophenol and 2,6-dichlorophenol, and trisubstituted phenols such as 2,4°6-dolimethylphenol. These can be used alone or in a mixture of two or more in any proportion, and among these, phenol is the most preferred.
フェノール類の使用量は、粗製ＢＰＬ １重量部に対し
０． ２〜２０重量部、好ましくは０． ４〜１５重量
部、特に好ましくは０．６〜１０重量部である。フェノ
ールの使用量が０．２重量部未満だと、十分な精製効果
が得られず、また２０重量部以上使用してもその効果に
変わりはなく、ＢＰＬの回収率が低下するため好ましく
ない。The amount of phenols to be used is 0.00 parts by weight of crude BPL. 2 to 20 parts by weight, preferably 0. It is 4 to 15 parts by weight, particularly preferably 0.6 to 10 parts by weight. If the amount of phenol used is less than 0.2 parts by weight, a sufficient purification effect cannot be obtained, and even if 20 parts by weight or more is used, the effect remains unchanged and the recovery rate of BPL decreases, which is not preferable.
粗製ＢＰＬの上記フェノール類に対する溶解度が低いた
め、本発明の方法では、溶解性を向上するために、ＢＰ
Ｌの溶解性が比較的高い有機溶媒として、炭素数１〜６
の脂肪族低級ケトン類および／又はアルコール類を用い
る。これらの例としては、アセトン、メチルエチルケト
ン、メチルイソブチルケトン、ジエチルケトンなとの脂
肪族低級ケトン類、メタノール、エタノール、 １−プ
ロパツール、２−プロパツール、１−フタノール、２−
ブタノール、５ｅＣ−ブタノールなどの脂肪族低級アル
コール類などがある。これらは単独でも、２種類以上を
任意の割合で混合した物でも、どちらでも使用すること
ができる。Since the solubility of crude BPL in the above-mentioned phenols is low, in the method of the present invention, in order to improve the solubility, BP
Organic solvents with relatively high solubility for L include carbon atoms of 1 to 6.
aliphatic lower ketones and/or alcohols are used. Examples of these include acetone, aliphatic lower ketones such as methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methanol, ethanol, 1-propanol, 2-propanol, 1-phthanol, 2-
Examples include aliphatic lower alcohols such as butanol and 5eC-butanol. These can be used alone or in a mixture of two or more in any proportion.
ある種の有機溶媒では、水を添加することにより粗製Ｂ
ＰＬの溶解度が向上することが知られており・ 本発明
の方法でも水を含有する有機溶媒を用いることがてきる
。含水有機溶媒を用いる場合、水の割合は、有機溶媒１
重量部に対し０．０３〜１重量部使用するのが好ましい
。In some organic solvents, the crude B
It is known that the solubility of PL is improved. An organic solvent containing water can also be used in the method of the present invention. When using a water-containing organic solvent, the proportion of water is 1 part organic solvent
It is preferable to use 0.03 to 1 part by weight based on the weight part.
有機溶媒あるいは含水有機溶媒の使用量は、フェノール
類の存在下で粗製ＢＰＬが完全に溶解するのに十分な量
であれはよく、溶媒の種類や含水量、溶解温度、フェノ
ール類の添加量、圧力によってＢＰＬの溶解度が異なる
ため一律には規定てきないか、一般に常圧で溶媒の沸点
近くて溶解を行なう場合、ＢＰＬ １重量部に対し０．
５〜２０重量部が好ましい。The amount of organic solvent or water-containing organic solvent used should be sufficient to completely dissolve the crude BPL in the presence of phenols, and the amount of organic solvent or water-containing organic solvent used should be sufficient to completely dissolve the crude BPL in the presence of phenols. Since the solubility of BPL varies depending on the pressure, it cannot be specified uniformly, or generally when dissolving at normal pressure near the boiling point of the solvent, the solubility of BPL is 0.0% per 1 part by weight of BPL.
5 to 20 parts by weight is preferred.
本発明では、上記のようにして得られた溶液から、ＢＰ
Ｌを溶解するのに使用した有機溶媒の６割以上、好まし
くは８割以上を留去した後、冷却することによって晶析
を行なう。In the present invention, from the solution obtained as described above, BP
After 60% or more, preferably 80% or more of the organic solvent used to dissolve L is distilled off, crystallization is performed by cooling.
有機溶媒を留去していくと、ＢＰＬが徐々に析出してく
るため、晶析の温度に特に制限はないが、ＢＰＬの回収
率を高くするため、０〜６０℃で行うのが好ましい。As the organic solvent is distilled off, BPL gradually precipitates out, so there is no particular restriction on the crystallization temperature, but in order to increase the recovery rate of BPL, it is preferable to perform the crystallization at a temperature of 0 to 60°C.
冷却により析出したＢＰＬは、そのままフェノール類の
母液から分離することにより、回収できるが、低温てＢ
ＰＬを回収する場合には、炭化水素類を添加し、母液の
粘度を下げて分離操作を行なっでもよい。添加される炭
化水素類としては、常温で液体で存在し、粘度が低くか
つＢＰＬの溶解度が小さいものが好ましく、例えは、ペ
ンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサ
ンなとの脂肪族炭化水素類、ベンゼン、トルエン、キシ
レン、エチルヘンゼン、キュメンなとの芳香族炭化水素
類なとがあり、これらは単独でも、２種以上を混合した
物でもどちらでも使用することができる。BPL precipitated by cooling can be recovered by separating it from the mother liquor of phenols, but BPL can be recovered at low temperatures.
When recovering PL, hydrocarbons may be added to lower the viscosity of the mother liquor and a separation operation may be performed. The hydrocarbons to be added are preferably those that exist in liquid form at room temperature, have low viscosity, and have low solubility in BPL, such as aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane; There are aromatic hydrocarbons such as benzene, toluene, xylene, ethylhenzene, and cumene, and these can be used alone or in a mixture of two or more.
炭化水素類の添加量は、粗製ＢＰＬ １重量部に対し、
０．０５〜１０重量部が好ましい。The amount of hydrocarbons added is 1 part by weight of crude BPL,
0.05 to 10 parts by weight is preferred.
こうして得られたＢＰＬは、高純度で色相の良好な白色
の結晶である。The BPL thus obtained is a white crystal with high purity and good hue.
［実施例コ 以下実施例により、本発明の詳細な説明する。[Example code] The present invention will be described in detail below with reference to Examples.
なお、ＢＰＬの純度は高速液体クロマトグラフィーで測
定し、ＵＶ２５７ｎｍの面積％で表わした・ ＡＰＨＡ
の測定は以下の方法で行った。In addition, the purity of BPL was measured by high performance liquid chromatography and expressed as area % of UV 257 nm.
The measurement was performed using the following method.
′「１Ｓ
ＢＰＬｌ、００ｇをメタノール２０．０ｇに溶解し、予
め調製したＡＰＨＡ標準溶液と比較し測定した。'1S BPLl, 00g was dissolved in 20.0g of methanol and compared with a pre-prepared APHA standard solution for measurement.
実施例１
２．６−ジー第三フチルフエノールを酸化カップリング
し、還元後脱ブチル化反応を行なって得られた粗製ＢＰ
Ｌ５ｏｇ （純度９９，０％、ＡＰＨＡ＞５００） を
２０％含水アセトン２５０ｇ、フェノール１００ｇの混
合溶液に加え加熱溶解し、アセトンの留去を行ない、室
温まで冷却し、ＢＰＬを晶析させた。この際に回収され
たアセトンは２１６．４ｇで、加えた２０％含水アセト
ンの８６．６％が回収された。結晶が析出した溶液に、
トルエン１０ｇを加えて吸引濾過を行ない、結晶を回収
した。トルエン１０ｇで結晶をリンスし乾燥することに
より１．！ｉ！ＢＰＬ４７．８ｇを得た。Example 1 Crude BP obtained by oxidative coupling of 2.6-di-tertiary phthylphenol and debutylation reaction after reduction
L5og (purity 99.0%, APHA>500) was added to a mixed solution of 250 g of 20% aqueous acetone and 100 g of phenol and dissolved by heating, the acetone was distilled off, and the mixture was cooled to room temperature to crystallize BPL. At this time, 216.4 g of acetone was recovered, which was 86.6% of the 20% aqueous acetone added. In the solution where the crystals have precipitated,
10 g of toluene was added and suction filtration was performed to collect crystals. 1. By rinsing the crystals with 10 g of toluene and drying them. ! i! 47.8 g of BPL was obtained.
この精製ＢＰＬの純度は９９．９％で、ＡＰＨＡは１５
てあり、回収率は９５．６％であった。The purity of this purified BPL is 99.9%, and the APHA content is 15
The recovery rate was 95.6%.
実施例２
４．４′−ジイソプロピルビフェニルを酸素酸化して得
られた、ジヒドロペルオキシドを含有する反応混合物を
、過酸化水素の存在下で酸分解して得られた粗製ＢＰＬ
５０ｇ （純度９７．２％、ＡＰＨＡ＞５００）を用い
た以外は、実施例１と全く同じ操作を行なった。回収さ
れたアセトンは２１８．５ｇで、加えた２０％含水アセ
トンの８７．４％が回収された。得られた精製ＢＰＬは
４８．２ｇで、純度９９．８％、ＡＰＨＡ４０、回収率
は９６．４％であった。Example 2 Crude BPL obtained by acid decomposition of a reaction mixture containing dihydroperoxide obtained by oxygen oxidation of 4.4'-diisopropylbiphenyl in the presence of hydrogen peroxide
Exactly the same operation as in Example 1 was performed except that 50 g (purity 97.2%, APHA>500) was used. The amount of acetone recovered was 218.5 g, which was 87.4% of the added 20% aqueous acetone. The obtained purified BPL weighed 48.2 g, had a purity of 99.8%, an APHA of 40, and a recovery rate of 96.4%.
比較例１と全く同し操作を行なった。得られた精製ＢＰ
Ｌは３８．１ｇで、純度９９．６％、ＡＰＨＡ２００、
回収率は７６．２％であった・［発明の効果コ
本発明の方法によれば、活性炭処理する事なく、高純度
かつ色相の優れたＢＰＬを工業的に有利な方法で回収率
よく精製することができる。The same operation as in Comparative Example 1 was performed. Obtained purified BP
L is 38.1g, purity 99.6%, APHA200,
The recovery rate was 76.2%. [Effects of the invention] According to the method of the present invention, BPL with high purity and excellent color can be purified with a high recovery rate by an industrially advantageous method without using activated carbon treatment. can do.
比較例１
実施例１で用いたのと同じ粗ｉ！ＢＰＬ５０ｇを２０％
含水アセトン２５０ｇで加熱溶解し、アセトン１００ｇ
を留去し１５℃まで冷却し、結晶を析出させた。得られ
た結晶を濾過し、乾燥して精製ＢＰＬ３８．９ｇを得た
。この精製ＢＰＬの純度は９９．８％て、ＡＰ ＨＡ４
００、回収率は７７．８％であ）た。Comparative Example 1 Same coarse i! as used in Example 1! 20% of BPL50g
Heat and dissolve with 250g of hydrous acetone, then add 100g of acetone.
was distilled off and cooled to 15°C to precipitate crystals. The obtained crystals were filtered and dried to obtain 38.9 g of purified BPL. The purity of this purified BPL was 99.8%, and AP HA4
00, the recovery rate was 77.8%).
比較例２Comparative example 2
Claims (1)
により精製する方法において、 ［１］「フェノール類」ならびに ［２］「脂肪族低級アルコール類およびケトン類から選
ばれる一種以上の含水又は無水の有機溶剤」の混合液を
再結晶用溶剤として、 用いることを特徴とする４，４′−ジヒドロキシビフェ
ニルの精製方法。(1) In a method for purifying crude 4,4'-dihydroxybiphenyl by recrystallization, one or more hydrous or anhydrous substances selected from [1] "phenols" and [2] "aliphatic lower alcohols and ketones" 1. A method for purifying 4,4'-dihydroxybiphenyl, which comprises using a mixture of "organic solvent" as a recrystallization solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10528490A JPH045251A (en) | 1990-04-23 | 1990-04-23 | Purification of 4,4'-dihydroxybiphenyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10528490A JPH045251A (en) | 1990-04-23 | 1990-04-23 | Purification of 4,4'-dihydroxybiphenyl |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH045251A true JPH045251A (en) | 1992-01-09 |
Family
ID=14403380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10528490A Pending JPH045251A (en) | 1990-04-23 | 1990-04-23 | Purification of 4,4'-dihydroxybiphenyl |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH045251A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002060847A1 (en) * | 2001-01-31 | 2002-08-08 | Sumitomo Chemical Company, Limited | Process for production of 4,4'-biphenol |
| WO2002072517A1 (en) * | 2001-03-09 | 2002-09-19 | Bayer Aktiengesellschaft | Purification of dihydroxydiphenyl |
-
1990
- 1990-04-23 JP JP10528490A patent/JPH045251A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002060847A1 (en) * | 2001-01-31 | 2002-08-08 | Sumitomo Chemical Company, Limited | Process for production of 4,4'-biphenol |
| WO2002072517A1 (en) * | 2001-03-09 | 2002-09-19 | Bayer Aktiengesellschaft | Purification of dihydroxydiphenyl |
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