JPH045252A - Production of 4,4'-dihydroxy-3,3',5,5'-tetramethyl-diphenylmethane - Google Patents
Production of 4,4'-dihydroxy-3,3',5,5'-tetramethyl-diphenylmethaneInfo
- Publication number
- JPH045252A JPH045252A JP2105304A JP10530490A JPH045252A JP H045252 A JPH045252 A JP H045252A JP 2105304 A JP2105304 A JP 2105304A JP 10530490 A JP10530490 A JP 10530490A JP H045252 A JPH045252 A JP H045252A
- Authority
- JP
- Japan
- Prior art keywords
- dimethylphenol
- formaldehyde
- dihydroxy
- tetramethyldiphenylmethane
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- AZZWZMUXHALBCQ-UHFFFAOYSA-N 4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(CC=2C=C(C)C(O)=C(C)C=2)=C1 AZZWZMUXHALBCQ-UHFFFAOYSA-N 0.000 title claims 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 67
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000007514 bases Chemical class 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 8
- 150000001298 alcohols Chemical class 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 5
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims abstract description 5
- 150000002576 ketones Chemical class 0.000 claims abstract description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000008096 xylene Substances 0.000 claims abstract description 4
- 238000000746 purification Methods 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- FYOZTECTYSJBFT-UHFFFAOYSA-N 1-benzyl-2,3,4,5-tetramethylbenzene Chemical compound CC1=C(C)C(C)=CC(CC=2C=CC=CC=2)=C1C FYOZTECTYSJBFT-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 4
- 238000004821 distillation Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000001953 recrystallisation Methods 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000012043 crude product Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は２，６〜ジメチルフエノールとホルムアルデヒ
ドを塩基性化合物触媒存在下に縮合させることにより４
，４゛−ジヒドロキシ−３，３°、５．５’−テトラメ
チルジフェニルメタンを容易に、且つ高収率、高純度で
製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides 4-dimethylphenol by condensing 2,6-dimethylphenol and formaldehyde in the presence of a basic compound catalyst.
, 4'-dihydroxy-3,3', 5,5'-tetramethyldiphenylmethane easily, in high yield, and with high purity.
本発明の方法で得られる４、４゛−ジヒドロキシ−３゜
３′，５．５’−テトラメチルジフェニルメタンはポリ
カーボッイト、ポリエステル、トリアジン樹脂等の重合
原料として有用な化合物である。4,4'-dihydroxy-3'3',5.5'-tetramethyldiphenylmethane obtained by the method of the present invention is a compound useful as a polymerization raw material for polycarboit, polyester, triazine resin, etc.
２．６−ジメチルフェノールとホルムアルデヒドを酸性
触媒存在下で縮合させ４，４′−ジヒドロキシ−３３″
、５．５’−テトラメチルジフェニルメタンを生成し得
ることは知られている（特開昭５２−９１８４８号公報
及び特開昭５８−６９８２７号公報）。しかしこれら製
造方法は反応時間が長り、蒸留工程が必要で操作が繁雑
であり、且つ副生物も多く着色しており、精製方法も開
示されておらず、高収率で、且つ高純度品を得るのは困
難であった。2.6-dimethylphenol and formaldehyde are condensed in the presence of an acidic catalyst to produce 4,4'-dihydroxy-33''
, it is known that 5,5'-tetramethyldiphenylmethane can be produced (JP-A-52-91848 and JP-A-58-69827). However, these production methods require long reaction times, require a distillation process, are complicated to operate, produce many colored by-products, and do not disclose purification methods. was difficult to obtain.
本発明の目的は、上記従来技術では満足されなかった、
高収率、高純度で、且つ生産性の優れた４、４“−ジヒ
ドロキシ−３，３′，５．５’−テトラメチルジフェニ
ルメタンの製造方法を提供するものである。The object of the present invention was not satisfied by the above-mentioned prior art.
The present invention provides a method for producing 4,4"-dihydroxy-3,3',5.5'-tetramethyldiphenylmethane with high yield, high purity, and excellent productivity.
〔課題を解決するための手段］
本発明者らは上記目的を達成するため鋭意検討１、に結
果、２．６−ジメチルフェノールとホルムアルデヒドを
水溶媒中で塩基性化合物触媒存在Ｔｃこ縮合する二とに
より、装置の腐食が少なく、反応時間が短縮され、副生
物が少なく、高収率で高純度品が得られることを見出し
本発明に到った。[Means for Solving the Problems] In order to achieve the above object, the present inventors conducted intensive studies and found that 2,6-dimethylphenol and formaldehyde were condensed in an aqueous solvent in the presence of a basic compound catalyst. The present invention was achieved by discovering that a high purity product can be obtained with less corrosion of the equipment, shorter reaction time, fewer by-products, and a higher yield.
即ち本発明は２，６−ジメチルフェノールとホルムアル
デヒドを縮合させるに際し、触媒としてアルカリ金属或
いはアルカリ土類金属を含有する塩基性化合物を存在さ
せ、且つ水溶媒中で縮合させることを特徴とする４、４
°−ジヒドロキン−３，３′，５５゛−テトラメチルジ
フェニルメタンの製造方法である。That is, the present invention is characterized in that when condensing 2,6-dimethylphenol and formaldehyde, a basic compound containing an alkali metal or alkaline earth metal is present as a catalyst, and the condensation is carried out in an aqueous solvent. 4
This is a method for producing °-dihydroquine-3,3',55'-tetramethyldiphenylmethane.
又２，６−ジメチルフェノールとホルムアルデヒドを触
媒の存在下に縮合させて得られる相４，４°−ジヒドロ
キシ−３，３′，５．５’−テトラメチルジフェニルメ
タンを、アルコール類、ケトン類、エステル類、ベンゼ
ン、キシレン、トルエンの群から選ばれる単独、或いは
２種以上混合、又は該物質と水との混合物により洗浄す
ること特徴とする４、４°−ジヒドロキシ−３，３′，
５．５’−テトラメチルジフェニルメタンの精製方法で
ある。In addition, the phase 4,4°-dihydroxy-3,3',5.5'-tetramethyldiphenylmethane obtained by condensing 2,6-dimethylphenol and formaldehyde in the presence of a catalyst is combined with alcohols, ketones, and esters. 4,4°-dihydroxy-3,3′, which is characterized by being washed with a single substance, a mixture of two or more selected from the group consisting of benzene, xylene, and toluene, or a mixture of the substance and water.
This is a method for purifying 5.5'-tetramethyldiphenylmethane.
本発明に用いるホルムアルデヒドとしてはパラホルムア
ルデヒド、水性ホルムアルデヒＦが挙げられるが、水性
ホルムアルデヒドを使用する方が操作が簡単であり、且
つ反応の進行に対しても有利である。水性ホルムアルデ
ヒド溶液は３０〜５０重量％の濃度が好ましい。The formaldehyde used in the present invention includes paraformaldehyde and aqueous formaldehyde F, but the use of aqueous formaldehyde is easier to operate and is also advantageous for the progress of the reaction. The aqueous formaldehyde solution preferably has a concentration of 30 to 50% by weight.
ホルムアルデヒドを２．６−ジメチルフェノールに対す
るモル比としては、０．５〜０３９が好ましく、更に好
ましくは０．５５〜０．７５の範囲である。モル比が０
．５未満の場合は２，６−ジメチルフェノールが全部反
応せず残留するため除去しなくてはならず、０．９を超
える場合はホルムアルデヒドが無駄になるだけで経済的
でない。The molar ratio of formaldehyde to 2.6-dimethylphenol is preferably from 0.5 to 0.039, more preferably from 0.55 to 0.75. molar ratio is 0
．． If it is less than 5, all of the 2,6-dimethylphenol remains unreacted and must be removed, while if it exceeds 0.9, formaldehyde is wasted and is not economical.
本発明に用いる触媒としては、アルカリ金属或いはアル
カリ土類金属を含有する塩基性化合物であり、例えば水
酸化リチウム、水酸化ナトリウム、水酸化カリウム、酸
化リチウム、酸化ナトリウム、酸化カリウム、水酸化マ
グネシウム、水酸化カルシウム、水酸化バリウム、酸化
マグネシウム、酸化カルシウム、酸化バリウム等が挙げ
られる。この中でも水酸化リチウム、水酸化ナトリウム
、水酸化カリウムが好ましい。The catalyst used in the present invention is a basic compound containing an alkali metal or alkaline earth metal, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium oxide, sodium oxide, potassium oxide, magnesium hydroxide, Examples include calcium hydroxide, barium hydroxide, magnesium oxide, calcium oxide, barium oxide, and the like. Among these, lithium hydroxide, sodium hydroxide, and potassium hydroxide are preferred.
塩基性化合物の使用量は、２．６−シメチルフエノルに
対するモル比０．０２〜０２が好ましく 、０．０５〜
０．１２の範囲で使用するのが特に好ましい。使用量の
モル比が０．０２未満の場合は反応時間が長くなり、０
．２を超えると不純物の生成が多くなり色相も悪くなる
。The amount of the basic compound used is preferably a molar ratio of 0.02 to 0.02, and 0.05 to 0.02 to 2.6-dimethylphenol.
It is particularly preferable to use it in the range of 0.12. If the molar ratio of the amount used is less than 0.02, the reaction time will be longer and the
．． When it exceeds 2, more impurities are produced and the hue becomes worse.
本発明の製造方法において、２，６−ジメチルフェノー
ルとホルムアルデヒドが縮合して生成する４４”−ジヒ
ドロキシ−３，３′，５．５’−テトラメチルジフェニ
ルメタンは、反応溶液に晶出するので、反応混合物は攪
拌可能な状態に保つため水で希釈することが好ましい。In the production method of the present invention, 44"-dihydroxy-3,3',5.5'-tetramethyldiphenylmethane, which is produced by the condensation of 2,6-dimethylphenol and formaldehyde, crystallizes in the reaction solution, so Preferably, the mixture is diluted with water to keep it stirrable.
反応系への水の装入は反応初期に一括に装入してもよく
、或いは反応中連続、又は間歇的に装入してもよい。Water may be introduced into the reaction system all at once at the beginning of the reaction, or may be introduced continuously or intermittently during the reaction.
又、反応温度としては６０〜１００’Ｃが好ましく、更
に好ましくは７０〜９０°Ｃである。温度が６０°Ｃ未
満の場合は反応時間が長くなり、１００°Ｃを超えると
不純物の生成が多くなる。白色の生成物を得るためには
窒素雰囲気下が好ましい。Further, the reaction temperature is preferably 60 to 100'C, more preferably 70 to 90'C. If the temperature is less than 60°C, the reaction time will be long, and if it exceeds 100°C, more impurities will be produced. A nitrogen atmosphere is preferred in order to obtain a white product.
本発明の製造方法としては、反応機に■２，６−ジメチ
ルフェノール、ホルムアルデヒド、塩基性化合物及び希
釈水からなる混合物を、６０〜１００°Ｃの温度で攪拌
する方法。■２，６−ジメチルフェノール、塩基性化合
物及び希釈水からなる混合物の攪拌下にホルムアルデヒ
ドを連続的、又は間歇的に供給する方法。■２，６〜ジ
メチルフェノール、塩基性化合物からなる混合物の攪拌
下に、ホルムアルデヒドを供給した後、希釈水を攪拌可
能な状態に保つため連続的、又は間歇的に供給する方法
等いずれの方法も採用できる。反応終了後の反応混合物
中には４，４”−ジヒドロキシ−３，３′，５．５’−
テトラメチルジフェニルメタンが結晶として析出してお
り、該混合物を濾過、水洗することにより高純度の４゜
４”−ジヒドロキジー３．３′，５．５’−テトラメチ
ルジフェニルメタンを得ることができる。The manufacturing method of the present invention is as follows: (1) A mixture of 2,6-dimethylphenol, formaldehyde, a basic compound, and dilution water is stirred in a reactor at a temperature of 60 to 100°C. (2) A method of continuously or intermittently supplying formaldehyde to a stirred mixture of 2,6-dimethylphenol, a basic compound, and dilution water. ■A method in which formaldehyde is supplied while stirring a mixture consisting of 2,6-dimethylphenol and a basic compound, and then the dilution water is supplied continuously or intermittently to keep it in a stirrable state. Can be adopted. After the reaction is complete, the reaction mixture contains 4,4''-dihydroxy-3,3',5.5'-
Tetramethyldiphenylmethane is precipitated as crystals, and by filtering the mixture and washing with water, highly pure 4°4''-dihydroxydi3.3',5.5'-tetramethyldiphenylmethane can be obtained.
更に高純度の４，４゛−ジヒドロキシ−３，３’ 、
５．５’テトラメチルジフエニルメタンを必要とする場
合の精製方法としては、アルコール類、ケトン類、エス
テル類、ヘンゼン、トルエン、キシレンの群から選ばれ
る単独、或いは２種以上混合、又は該物質と水との混合
物により洗浄することにより微量の不純物の除去と色相
の改善を図ることができる。又、水と混合するアルコー
ル類、ケトン類、エステル類は含水率５０％未満で使用
するのが好ましい。含水率５０％を超える場合は洗浄効
果が低下し該物質を得るには困難である。Furthermore, highly purified 4,4'-dihydroxy-3,3',
When 5.5'tetramethyldiphenylmethane is required, the purification method may be one selected from the group of alcohols, ketones, esters, henzhen, toluene, xylene, or a mixture of two or more of these substances. By washing with a mixture of and water, trace impurities can be removed and the hue can be improved. Furthermore, alcohols, ketones, and esters that are mixed with water are preferably used at a water content of less than 50%. When the water content exceeds 50%, the cleaning effect decreases and it is difficult to obtain the substance.
上記精製方法は、２．６−ジメチルフェノールとホルム
アルデヒドを縮合させるに際し、用いる触媒が、塩基性
化合物のみならず酸性触媒等を用いた場合、或いは水溶
媒に限らず有ｌａ溶媒等を用いた場合に得られる粗４，
４゛−ジヒドロキシ−３，３′，５゜５′−テトラメチ
ルジフェニルメタンについても本発明に含まれる。The above purification method is applicable when 2,6-dimethylphenol and formaldehyde are condensed, and when the catalyst used is not only a basic compound but also an acidic catalyst, or when not only an aqueous solvent but also an la solvent, etc. is used. 4,
4'-dihydroxy-3,3',5'5'-tetramethyldiphenylmethane is also included in the present invention.
以下本発明を実施例により説明する。 The present invention will be explained below with reference to Examples.
実施例１
コンデンサー、攪拌機及び滴下ロートを備えた内容積１
．Ｏｐのセパラブルフラスコに２８６−ジメチルフェノ
ール２９２．８ ｇ （２，４モル）と２帽１％ＮａＯ
Ｈ３６ｇ （ＮａＯＨ０，１８モル）及び水４７５．７
ｇを入れ、窒素雰囲気下で６０°Ｃに保って、攪拌しな
がら滴下ロートから３７重量％ホルマリン１２６．５ｇ
（ホルムアルデヒド１．５６モル）を１０分間を要
し滴下させた。Example 1 Internal volume 1 with condenser, stirrer and dropping funnel
．． 292.8 g (2.4 mol) of 286-dimethylphenol and 2 caps of 1% NaO were placed in a separable flask.
36 g of H (0.18 mol of NaOH) and 475.7 g of water
126.5 g of 37 wt% formalin was added from the dropping funnel while stirring at 60°C under a nitrogen atmosphere.
(formaldehyde 1.56 mol) was added dropwise over a period of 10 minutes.
滴下後３０分間を要して８０°Ｃに昇温しその温度で５
時間攪拌した。次いで反応物である結晶性スラリを吸引
下に濾別し水で中性になるまで洗浄し、真空乾燥機で１
２０’Ｃ１３時間乾燥させ白色の結晶３０３ｇを得た。It took 30 minutes after dropping to raise the temperature to 80°C, and at that temperature
Stir for hours. Next, the crystalline slurry as a reaction product was filtered under suction, washed with water until neutral, and dried in a vacuum dryer for 1 hour.
It was dried for 13 hours at 20'C to obtain 303 g of white crystals.
この結晶の融点は１７５〜１７６°Ｃ（文献値１７５°
Ｃ）であった。これは２．６−ジメチルフェノールを基
準として９８．５％の収率に相当する。The melting point of this crystal is 175-176°C (literature value: 175°
C). This corresponds to a yield of 98.5% based on 2,6-dimethylphenol.
得られた結晶の純度と色相の値を第１表に示す。The purity and hue values of the obtained crystals are shown in Table 1.
実施例２
実施例１と同一の装置に、２，６−ジメチルフェノール
２９２．８ｇ （２，４モル）と２０重量％ＫＯＨ６７
ｇ（ＫＯ８０，２４モル）を入れ、窒素雰囲気下で６０
°Ｃに保って、撹拌しながら滴下ロートから３７重量％
ホルマリン１３６．２ ｇ （ホルムアルデヒド１．６
８モル）を３０分間を要し滴下させた。滴下後３０分間
を要し９０°Ｃに昇温しその温度で２時間撹拌した。反
応混合物を攪拌可能な状態に保つため３００ ｍｌの水
を反応期間中休々に加えた。実施例１と同様に処理して
白色の結晶３０１ ｇを得た。これは２，６−ジメチル
フェノールを基準とそで９８％の収率に相当する。得ら
れた結晶の純度と色相の値を第１表に示す。Example 2 In the same apparatus as in Example 1, 292.8 g (2.4 mol) of 2,6-dimethylphenol and 20% by weight KOH67 were added.
g (KO80, 24 mol) and heated under nitrogen atmosphere.
37% by weight from the dropping funnel while stirring at °C.
Formalin 136.2 g (formaldehyde 1.6
8 mol) was added dropwise over a period of 30 minutes. It took 30 minutes after the dropwise addition to raise the temperature to 90°C, and stirred at that temperature for 2 hours. 300 ml of water was added at intervals during the reaction to keep the reaction mixture stirrable. It was treated in the same manner as in Example 1 to obtain 301 g of white crystals. This corresponds to a yield of 98% based on 2,6-dimethylphenol. The purity and hue values of the obtained crystals are shown in Table 1.
比較例Ｉ
２．６−ジメチルフェノール４３４ ｇ （３，５６モ
ル）と３７重量％ホルマリン１４６ｇ（ホルムアルデヒ
ド１゜８モル）及びシュウ酸１４．２ ｇを、窒素雰囲
気下で攪拌しながら沸騰温度に加熱し１８時間その温度
に保った。反応混合物を攪拌可能な状態に保つため３０
０ ｄの水を反応期間中休々に加えた。反応後未反応の
２，６−ジメチルフェノールを水蒸気蒸留により結晶性
スラリーから除去した。次いで結晶性スラリーを吸引下
に濾別し、水で中性になるまで洗浄した後乾燥させて黄
色の結晶４３０ｇを得た。この結晶の融点は１７２〜１
７５°Ｃであった。これは２６−ジメチルフェノールを
基準として９４．４％の収率に相当する。得られた結晶
の純度と色相の値を第１表に示す。Comparative Example I 434 g (3.56 mol) of 2,6-dimethylphenol, 146 g of 37% by weight formalin (1.8 mol of formaldehyde) and 14.2 g of oxalic acid are heated to boiling temperature with stirring under a nitrogen atmosphere. It was kept at that temperature for 18 hours. 30 to keep the reaction mixture stirrable.
0 d of water was added at intervals during the reaction period. After the reaction, unreacted 2,6-dimethylphenol was removed from the crystalline slurry by steam distillation. The crystalline slurry was then filtered off under suction, washed with water until neutral and dried to obtain 430 g of yellow crystals. The melting point of this crystal is 172-1
The temperature was 75°C. This corresponds to a yield of 94.4% based on 26-dimethylphenol. The purity and hue values of the obtained crystals are shown in Table 1.
実施例３
実施例１で得られた結晶１００ｇを水／メタノール容量
比で２／８の混合溶媒２００ｄで洗浄した後乾燥して９
５ｇの精結晶を得た。得られた精結晶の純度と色相の値
を第１表に示す。Example 3 100 g of the crystals obtained in Example 1 were washed with 200 d of a mixed solvent with a water/methanol volume ratio of 2/8, and then dried.
5 g of fine crystals were obtained. Table 1 shows the purity and hue values of the obtained fine crystals.
実施例４
実施例２で得られた結晶１００ｇを水／アセトン容量比
で４／６の混合溶媒２００ｄで洗浄した後乾燥して９７
ｇの精結晶を得た。得られた精結晶の純度と色相の値を
第１表に示す。Example 4 100 g of the crystals obtained in Example 2 were washed with 200 d of a mixed solvent with a water/acetone volume ratio of 4/6, and then dried to give 97.
A fine crystal of g was obtained. Table 1 shows the purity and hue values of the obtained fine crystals.
実施例５
比較例１で得られた結晶１００ｇをベンゼン３０〇−で
洗浄した後乾燥して９６ｇの精結晶を得た。得られた精
結晶の純度と色相の値を第１表に示す。Example 5 100 g of the crystals obtained in Comparative Example 1 were washed with 300 g of benzene and then dried to obtain 96 g of fine crystals. Table 1 shows the purity and hue values of the obtained fine crystals.
比較例２
比較例１で得られた結晶１００ ｇをヘンゼン９００社
で再結晶した後乾燥して９０ｇの精結晶を得た。Comparative Example 2 100 g of the crystals obtained in Comparative Example 1 were recrystallized at Henzen 900 and dried to obtain 90 g of fine crystals.
得られた精結晶の純度と色相の値を第１表に示す。Table 1 shows the purity and hue values of the obtained fine crystals.
第１表
注１ ） ＮａＯＨ：水酸化ナトリウム ＫＯＨ：水酸
化カリウム注２）純度の測定は液体クロマトグラフィー
による。Table 1 Note 1) NaOH: Sodium hydroxide KOH: Potassium hydroxide Note 2) Purity is measured by liquid chromatography.
注３）色相は４．４゛−ジヒドロキシ−３，３′，５．
５’−テトラメチルジフェニルメタン１．０ｇをメタノ
ール１０−に溶解し波長４２０ｎｍ 、セル１０關で測
定した吸光度で表す。Note 3) Hue is 4.4'-dihydroxy-3,3',5.
It is expressed as the absorbance measured by dissolving 1.0 g of 5'-tetramethyldiphenylmethane in 10-methanol and using a cell 10 at a wavelength of 420 nm.
本発明の製造方法は上記実施例からも明らかの如く反応
時間が短く蒸留工程、再結晶工程がなく省工フルギープ
ロセスで生産性が良く、且っ高収率で無色の高純度品を
得ることができる。又、精製方法は従来の再結晶法より
色相の良い高純度品を得ることができる。As is clear from the above examples, the production method of the present invention has a short reaction time, no distillation step, no recrystallization step, labor-saving flugy process, good productivity, and produces a colorless, high-purity product in high yield. be able to. In addition, the purification method can provide a highly purified product with a better color than the conventional recrystallization method.
本発明により得られる４、４゛−ジヒドロキシ３，３５
．５−テトラメチルジフェニルメタンを重合原料として
用いた樹脂は高品質の樹脂が得られる。4,4′-dihydroxy 3,35 obtained by the present invention
．． A high-quality resin can be obtained using 5-tetramethyldiphenylmethane as a polymerization raw material.
特許出願人 三井東圧化学株式会社Patent applicant Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
縮合させるに際し、触媒としてアルカリ金属或いはアル
カリ土類金属を含有する塩基性化合物を存在させ、且つ
水溶媒中で縮合させることを特徴とする４，４′−ジヒ
ドロキシ−３，３′，５，５′−テトラメチルジフェニ
ルメタンの製造方法。 ２、アルカリ金属あるいはアルカリ土類金属を含有する
塩基性化合物を２，６−ジメチルフェノールに対するモ
ル比として０．０２〜０．２の範囲で使用する請求項１
記載の４，４′−ジヒドロキシ−３，３′，５，５′−
テトラメチルジフェニルメタンの製造方法。 ３、ホルムアルデヒドを２，６−ジメチルフェノールに
対するモル比として０．５〜０．９の範囲で使用する請
求項１記載の４，４′−ジヒドロキシ−３，３′，５，
５′−テトラメチルジフェニルメタンの製造方法。 ４、２，６−ジメチルフェノールとホルムアルデヒドを
触媒の存在下に縮合させて得られる粗４，４′−ジヒド
ロキシ−３，３′，５，５′−テトラメチルジフェニル
メタンを、アルコール類、ケトン類、エステル類、ベン
ゼン、キシレン、トルエンの群から選ばれる単独、或い
は２種以上混合、又は該物質と水との混合物により洗浄
すること特徴とする４，４′−ジヒドロキシ−３，３′
，５，５′−テトラメチルジフェニルメタンの精製方法
。[Scope of Claims] When 1,2,6-dimethylphenol and formaldehyde are condensed, a basic compound containing an alkali metal or alkaline earth metal is present as a catalyst, and the condensation is carried out in an aqueous solvent. A method for producing 4,4'-dihydroxy-3,3',5,5'-tetramethyldiphenylmethane. 2. Claim 1, wherein the basic compound containing an alkali metal or alkaline earth metal is used in a molar ratio of 0.02 to 0.2 to 2,6-dimethylphenol.
4,4'-dihydroxy-3,3',5,5'-
A method for producing tetramethyldiphenylmethane. 3. 4,4'-dihydroxy-3,3',5, according to claim 1, wherein formaldehyde is used in a molar ratio of 0.5 to 0.9 with respect to 2,6-dimethylphenol.
A method for producing 5'-tetramethyldiphenylmethane. Crude 4,4'-dihydroxy-3,3',5,5'-tetramethyldiphenylmethane obtained by condensing 4,2,6-dimethylphenol and formaldehyde in the presence of a catalyst is mixed with alcohols, ketones, 4,4'-dihydroxy-3,3', which is characterized by being washed with a single substance selected from the group of esters, benzene, xylene, and toluene, or a mixture of two or more thereof, or a mixture of the substance and water.
, 5,5'-Tetramethyldiphenylmethane purification method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2105304A JP2927880B2 (en) | 1990-04-23 | 1990-04-23 | Method for producing 4,4'-dihydroxy-3,3 ', 5,5'-tetramethyldiphenylmethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2105304A JP2927880B2 (en) | 1990-04-23 | 1990-04-23 | Method for producing 4,4'-dihydroxy-3,3 ', 5,5'-tetramethyldiphenylmethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH045252A true JPH045252A (en) | 1992-01-09 |
| JP2927880B2 JP2927880B2 (en) | 1999-07-28 |
Family
ID=14403963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2105304A Expired - Lifetime JP2927880B2 (en) | 1990-04-23 | 1990-04-23 | Method for producing 4,4'-dihydroxy-3,3 ', 5,5'-tetramethyldiphenylmethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2927880B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6273805B1 (en) * | 1997-01-23 | 2001-08-14 | Showa Kenma Kogyo Co., Ltd. | Grindstone and method of manufacturing the same |
| CN114671740A (en) * | 2022-01-27 | 2022-06-28 | 濮阳市恩赢高分子材料有限公司 | Synthesis method of bisphenol F |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10308579B2 (en) | 2015-12-11 | 2019-06-04 | Sabic Global Technologies B.V. | Method of bisphenol manufacture |
-
1990
- 1990-04-23 JP JP2105304A patent/JP2927880B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6273805B1 (en) * | 1997-01-23 | 2001-08-14 | Showa Kenma Kogyo Co., Ltd. | Grindstone and method of manufacturing the same |
| CN114671740A (en) * | 2022-01-27 | 2022-06-28 | 濮阳市恩赢高分子材料有限公司 | Synthesis method of bisphenol F |
| CN114671740B (en) * | 2022-01-27 | 2024-03-12 | 濮阳市恩赢高分子材料有限公司 | Bisphenol F synthesis method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2927880B2 (en) | 1999-07-28 |
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