JPH013136A - Method for purifying 2,4-xylenol - Google Patents
Method for purifying 2,4-xylenolInfo
- Publication number
- JPH013136A JPH013136A JP62-156640A JP15664087A JPH013136A JP H013136 A JPH013136 A JP H013136A JP 15664087 A JP15664087 A JP 15664087A JP H013136 A JPH013136 A JP H013136A
- Authority
- JP
- Japan
- Prior art keywords
- xylenol
- reaction
- aldehyde
- purifying
- purity
- 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
- 238000000034 method Methods 0.000 title claims description 25
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 title claims description 23
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 16
- 150000003739 xylenols Chemical class 0.000 claims description 15
- 239000002841 Lewis acid Substances 0.000 claims description 8
- 150000007517 lewis acids Chemical class 0.000 claims description 8
- -1 xylenol aldehyde Chemical class 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 229910001510 metal chloride Inorganic materials 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 17
- 150000001299 aldehydes Chemical class 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- QPVRKFOKCKORDP-UHFFFAOYSA-N 1,3-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC(C)(O)CC=C1 QPVRKFOKCKORDP-UHFFFAOYSA-N 0.000 description 5
- PCNMALATRPXTKX-UHFFFAOYSA-N 1,4-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CCC(C)(O)C=C1 PCNMALATRPXTKX-UHFFFAOYSA-N 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000003842 bromide salts Chemical class 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
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、２．４−キシレノールの精製方法に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a method for purifying 2,4-xylenol.
さらに詳しくは、２，５−キシレノールを含む粗２．４
−キシレノール異性体混合物からルイス酸の存在下、ア
ルデヒドと反応させ、２，５−キシレノールを、キシレ
ノール−アルデヒド縮合物として分離除去することを特
徴とする高純度２，４−キシレノールの精製方法に関す
る。More specifically, crude 2.4 containing 2,5-xylenol
- A method for purifying high-purity 2,4-xylenol, which comprises reacting a xylenol isomer mixture with an aldehyde in the presence of a Lewis acid to separate and remove 2,5-xylenol as a xylenol-aldehyde condensate.
２．４−キシレノールは、合成樹脂、接着剤、殺虫剤、
抗酸化剤、除草剤、色素等の原料として極めて有用な化
合物であり、大量に生産、使用されており、用途によっ
ては高純度品が要求される。2.4-xylenol is used in synthetic resins, adhesives, insecticides,
It is an extremely useful compound as a raw material for antioxidants, herbicides, pigments, etc. It is produced and used in large quantities, and high purity products are required depending on the application.
一方、キシレノール−アルデヒド縮合物は抗酸化剤、顕
色剤として有用な化合物である。On the other hand, xylenol-aldehyde condensates are useful compounds as antioxidants and color developers.
（従来の技術）
キシレノールには、２，３−キシレノール、２．４−キ
シレノール、２．５−キシレノール、２．６−キシレノ
ール、３，４−キシレノールおよび３．５−キシレノー
ルの６種の異性体が存在する。(Prior art) There are six isomers of xylenol: 2,3-xylenol, 2.4-xylenol, 2.5-xylenol, 2.6-xylenol, 3,4-xylenol, and 3.5-xylenol. exists.
これらのそれぞれの異性体の沸点は近接しているために
、キシレノール異性体混合物を蒸留法ではそれぞれの異
性体成分に効率よく分離することは極めて難しい。Since the boiling points of each of these isomers are close to each other, it is extremely difficult to efficiently separate a xylenol isomer mixture into each isomer component by distillation.
特に、２．４−キシレノールと２，５−キシレノールは
沸点がほぼ同一であり、単なる精留によって分離するこ
とはできない。In particular, 2,4-xylenol and 2,5-xylenol have almost the same boiling point and cannot be separated by simple rectification.
２．４−キシレノールと２，５−キシレノールを分離す
る方法については、さまざまな提案がされている。Various proposals have been made regarding methods for separating 2,4-xylenol and 2,5-xylenol.
たとえば、２，４−キシレノールがメチルキノリン、ア
ニリン、トルイジンなどと分子化合物を形成する性質を
利用して分離精製する方法（米国特許２５２６８０７号
）、イソブチレンでアルキル化してｔｅｒｔ−ブチル化
物とし、これの分留によって分離した後、酸の存在下に
脱アルキル化することにより分離精製する方法（英国特
許５８２０５７号等）、スルホン化した後、通熱水蒸気
によって部分加水分解することによって分離する方法（
米国特許２３２７３１２号等）、またモレキュラーシー
ブス、酸化カルシウム、ゼオライト等の吸着剤を用いる
方法（特開昭５６−６８６２８号等）などが提案されて
いる。For example, there is a method of separating and purifying 2,4-xylenol by utilizing its property of forming molecular compounds with methylquinoline, aniline, toluidine, etc. (US Pat. No. 2,526,807), and alkylating it with isobutylene to form a tert-butylated product. A method of separation by fractional distillation followed by dealkylation in the presence of an acid (such as British Patent No. 582057), a method of separation by sulfonation and then partial hydrolysis with heated steam (
U.S. Pat. No. 2,327,312, etc.), and methods using adsorbents such as molecular sieves, calcium oxide, zeolite, etc. (Japanese Patent Laid-Open No. 56-68628, etc.) have been proposed.
また、本発明と類似の方法、即ち、キシレノールを塩酸
、あるいは強塩基の存在下でホルマリンと反応させ、２
，５−キシレノールをキシレノール−ホルマリン樹脂と
して分離除去する方法も提案されている（米国特許２９
１７４８７号）。In addition, a method similar to the present invention, that is, reacting xylenol with formalin in the presence of hydrochloric acid or a strong base,
, a method of separating and removing 5-xylenol as a xylenol-formalin resin has also been proposed (U.S. Pat.
No. 17487).
（発明が解決しようとする問題点）
しかしながら、分子化合物を形成する性質を利用した精
製法においては得られる精２，４−キシレノールの純度
、収率を共に満足する様な化合物は見つかっておらず、
前述の従来法に見られるように高価なアミン類を使用す
る方法ではそのアミン類の損失も無視できない。(Problems to be Solved by the Invention) However, no compound has been found that satisfies both the purity and yield of refined 2,4-xylenol obtained using a purification method that utilizes the property of forming molecular compounds. ,
In methods that use expensive amines, as seen in the conventional methods described above, the loss of the amines cannot be ignored.
また、アルキル化して分離する方法、スルホン化して分
離する方法は煩雑な操作を必要とし、高価な原料、ある
いは多量の酸や塩基を必要とする。Furthermore, the methods of alkylation and separation and sulfonation and separation require complicated operations and require expensive raw materials or large amounts of acids and bases.
モレキユラーシーブス等への吸着法は、効率的に異性体
混合物を分離する吸着剤が見つかっておらず、工業的な
実用化は難しい。As for the adsorption method using molecular sieves, etc., no adsorbent that efficiently separates isomer mixtures has been found, making it difficult to put it into practical use industrially.
米国特許２９１７４８７号は本発明と類似の方法である
が、得られる２、４−キシレノールの純度、収率と共に
満足させることはできていない。US Pat. No. 2,917,487 is a method similar to the present invention, but the purity and yield of the obtained 2,4-xylenol cannot be satisfied.
従って、高純度の２，４−キシレノールを工業的規模で
得ることは非常に困難であった。Therefore, it has been very difficult to obtain highly pure 2,4-xylenol on an industrial scale.
（問題を解決するための手段）
本発明者らは、２，４−キシレノール及び２．５−キシ
レノールを含むキシレノール異性体混合物により、純度
及び収率ともに満足できる２、４−キシレノールの精製
方法につき検討を行い、ある特定の条件下にアルデヒド
と反応させると優先的に２，５−キシレノールが反応す
る事を見出し、本発明に到達した。(Means for Solving the Problem) The present inventors have developed a method for purifying 2,4-xylenol that can satisfy both purity and yield using a xylenol isomer mixture containing 2,4-xylenol and 2,5-xylenol. After conducting a study, it was discovered that 2,5-xylenol reacts preferentially when reacted with an aldehyde under certain specific conditions, and the present invention was achieved.
即ち、本発明は２，４−キシレノールおよび２．５−キ
シレノールを含むキシレノール異性体混合物を、ルイス
酸の存在下、アルデヒドと反応させ、２，５−キシレノ
ールをキシレノールアルデヒド縮金物として分離、除去
することを特徴とする２、４−キシレノールの精製方法
である。That is, in the present invention, a xylenol isomer mixture containing 2,4-xylenol and 2,5-xylenol is reacted with an aldehyde in the presence of a Lewis acid, and 2,5-xylenol is separated and removed as a xylenol aldehyde condensate. This is a method for purifying 2,4-xylenol.
本発明方法に供されるキシレノール異性体混合物には、
特に組成比の制限はないが特に純度８５〜９５％の２，
４−キシレノールを純度９５％以上にするような精製に
効果が大きい。また２、３−キシレノール等の他のキシ
レノール異性体も、２，５−キシレノールと同様にアル
デヒドと縮合反応して分離できるが、２．４．６−ドリ
メチルフエノールの如き、アルデヒドと反応しがたいア
ルキルフェノールは本発明方法によっては除去できない
。そこで、この様なアルキルフェノールを多量に含む場
合は他の分離法、例えば、蒸留あるいは再結晶で除去し
たのちに本発明方法を使用するとよい。The xylenol isomer mixture subjected to the method of the invention includes:
There is no particular restriction on the composition ratio, but in particular 2, with a purity of 85 to 95%,
It is highly effective in purifying 4-xylenol to a purity of 95% or higher. In addition, other xylenol isomers such as 2,3-xylenol can be separated by condensation reaction with aldehydes in the same way as 2,5-xylenol, but they do not react with aldehydes such as 2,4,6-dolimethylphenol. Alkylphenols cannot be removed by the method of the present invention. Therefore, when a large amount of such alkylphenol is contained, it is preferable to use the method of the present invention after removing it by another separation method, such as distillation or recrystallization.
本発明によるアルデヒド化合物としては、ホルムアルデ
ヒド、アセトアルデヒド、プロピオンアルデヒド、ブチ
ルアルデヒドの如き脂肪族低分子アルデヒド、ベンズア
ルデヒドの如き芳香族アルデヒド等が挙げられる。これ
らのアルデヒドのうちでは、反応性、選択性、価格、収
率、縮合物の用途等を考慮した場合、ホルムアルデヒド
、アセトアルデヒドが好ましい。この際、アルデヒドは
水溶液、アルコール溶液、三重体、ポリマー、あるいは
アセクールの形で使用してもよい。アルデヒドの使用量
は、除去すべき２．５−キシレノールの量や、反応条件
等により異なり、少量のアルデヒドの使用で高純度の２
，４−キシレノールを得るべく反応条件を選択すること
になる。この際、通常、２．５−キシレノールの０．５
〜３倍モル、好まし−くは０．５〜１．５倍モルのアル
デヒドを使用する。Examples of the aldehyde compound according to the present invention include aliphatic low-molecular-weight aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde, and aromatic aldehydes such as benzaldehyde. Among these aldehydes, formaldehyde and acetaldehyde are preferred in consideration of reactivity, selectivity, price, yield, use of the condensate, and the like. In this case, the aldehyde may be used in the form of an aqueous solution, alcoholic solution, triplex, polymer, or acecool. The amount of aldehyde used varies depending on the amount of 2.5-xylenol to be removed and the reaction conditions.
, 4-xylenol. At this time, usually 0.5 of 2.5-xylenol
~3 times the mole, preferably 0.5 to 1.5 times the mole of aldehyde is used.
本発明においては、触媒としてルイス酸が使用され、こ
れはたとえば、亜鉛、鉄、アルミニウム、アンチモン、
ニラケラ、銅、スズ、コバルト、クロム、鉛等の塩素化
物、臭素化物、フッ素化物および沃素化物が挙げられる
。その使用量は、触媒の種別あるいは反応条件等により
異なるがキシレノール１００重量部に対し通常０．０１
〜２０重量部、好ましくは０．１〜５重量部の範囲であ
る。触媒にルイス酸を用いることにより、従来の塩酸触
媒法に比べ、飛躍的に高純度の２．４−キシレノールを
得ることができる。In the present invention, Lewis acids are used as catalysts, such as zinc, iron, aluminum, antimony,
Examples include chlorides, bromides, fluorides, and iodides of copper, copper, tin, cobalt, chromium, lead, and the like. The amount used varies depending on the type of catalyst and reaction conditions, but it is usually 0.01 parts by weight per 100 parts by weight of xylenol.
-20 parts by weight, preferably 0.1-5 parts by weight. By using a Lewis acid as a catalyst, 2,4-xylenol can be obtained with significantly higher purity than the conventional hydrochloric acid catalyst method.
本発明の反応温度は通常０〜２１０°Ｃの範囲、好まし
くは０〜１５０°Ｃの広い範囲で実施できる。The reaction temperature of the present invention can generally be carried out within a wide range of 0 to 210°C, preferably 0 to 150°C.
本発明方法に供されるキシレノール異性体混合物は、組
成によりさまざまな凝固点をとる。したがって、原料の
キシレノール異性体混合物が、実施される反応温度で固
体の場合は反応に悪影響を与えないような溶媒を使用す
ればよい。例えば、ベンゼン、トルエン、キシレン、ク
メン、メシチレン等の芳香族炭化水素、ヘキサン、ヘプ
タン、オクタン等の脂肪族炭化水素、クロルベンゼン、
オルソジクロルベンゼン、クロロホルム、四塩化炭素、
ジクロルエタン等のハロゲン化炭化水素、メタノール、
エタノール、イソプロピルアルコール、ｎ−プロピルア
ルコール等のアルコール、アセトニトリル、プロピオニ
トリル等のニトリルなどが使用できる。精２，４−キシ
レノールの純度、収率、溶剤の回収率、価格、操作性を
考慮した場合、トルエンは最も好ましい溶媒の一つであ
る。また、原料のキシレノール異性体混合物が反応温度
で液状の場合は、上記の様な溶媒を使用してもよいし、
また無溶媒で実施してもよい。The xylenol isomer mixture subjected to the method of the present invention has various freezing points depending on its composition. Therefore, if the raw material xylenol isomer mixture is solid at the reaction temperature, a solvent that does not adversely affect the reaction may be used. For example, aromatic hydrocarbons such as benzene, toluene, xylene, cumene, mesitylene, aliphatic hydrocarbons such as hexane, heptane, octane, chlorobenzene,
Orthodichlorobenzene, chloroform, carbon tetrachloride,
Halogenated hydrocarbons such as dichloroethane, methanol,
Alcohols such as ethanol, isopropyl alcohol, and n-propyl alcohol, and nitriles such as acetonitrile and propionitrile can be used. Toluene is one of the most preferred solvents when considering the purity, yield, solvent recovery rate, price, and operability of purified 2,4-xylenol. In addition, if the raw material xylenol isomer mixture is liquid at the reaction temperature, the above-mentioned solvents may be used,
It may also be carried out without a solvent.
溶媒を使用する場合、その使用量は粗２，４−キシレノ
ール１００重量部あたり、通常５００重量部以下、好ま
しくは２００重量部以下である。When a solvent is used, the amount used is usually 500 parts by weight or less, preferably 200 parts by weight or less, per 100 parts by weight of crude 2,4-xylenol.
キシレノールとアルデヒド類との脱水縮合反応は、平衡
反応であるため、反応マスを直接蒸留に供すると、反応
工程で生成した２、５−キシレノール−アルデヒド縮合
物が蒸留中に加水分解を受けて２，５−キシレノールと
なり、留出液中に混入する為、２，４−キシレノールの
純度が低下する。このため、触媒として使用したルイス
酸を除去したのちに蒸留する。ルイス酸は、水洗分液、
あるいはアンモニア水、苛性ソーダ等の中和操作で容易
に除去できる。The dehydration condensation reaction between xylenol and aldehydes is an equilibrium reaction, so when the reaction mass is directly subjected to distillation, the 2,5-xylenol-aldehyde condensate produced in the reaction process undergoes hydrolysis during distillation, resulting in 2 , 5-xylenol, which is mixed into the distillate, reducing the purity of 2,4-xylenol. For this reason, distillation is performed after removing the Lewis acid used as a catalyst. Lewis acid is washed with water and separated.
Alternatively, it can be easily removed by neutralizing with aqueous ammonia, caustic soda, etc.
このようにして酸を除去した反応マスを蒸留することに
より、留出液として精２，４−キシレノールを得ること
ができる。釜にはキシレノール−アルデヒド縮合物が残
るが、このものはスラッシング、あるいは再結晶等の操
作で精製することができる。By distilling the reaction mass from which the acid has been removed in this way, purified 2,4-xylenol can be obtained as a distillate. A xylenol-aldehyde condensate remains in the pot, but this can be purified by operations such as slushing or recrystallization.
以下、実施例および比較例により本発明を具体的に説明
す。The present invention will be specifically explained below using Examples and Comparative Examples.
（実施例−１）
５００ｍＮガラス製４ツロフラスコに第１表に示す組成
の粗２，４−キシレノール２４４．４ｇ、９０％パラホ
ルムアルデヒド６．６ｇ、無水塩化アルミニウム２．０
ｇを仕込、２０°Ｃで６時間撹拌して反応させた。反応
終了後、トルエン２００ ｍｌ、水２００雁に反応マス
を排出し充分撹拌したのち分液した。トルエン層を脱ト
ルエンしたのち蒸留して、沸点１０４ ／２１ｍｍＨｇ
の留分１９０．Ｏｇを得た。その組成を第１表に示す。(Example-1) 244.4 g of crude 2,4-xylenol having the composition shown in Table 1, 6.6 g of 90% paraformaldehyde, and 2.0 g of anhydrous aluminum chloride were placed in a 500 mN glass 4-tube flask.
g was charged and stirred at 20°C for 6 hours to react. After the reaction was completed, the reaction mass was poured into 200 ml of toluene and 200 ml of water, thoroughly stirred, and then separated. After removing toluene from the toluene layer, it was distilled to a boiling point of 104/21 mmHg.
fraction of 190. Obtained Og. Its composition is shown in Table 1.
−１コｆ
（実施例−２）
無水塩化アルミニウム２．０ｇを塩化第１亜鉛２．０ｇ
に、反応温度を５０°Ｃに反応時間を１０時間に替えた
以外は実施例−１と同様に反応・処理をして精２゜４−
キシレノール１８９．６ｇを得た。純度９７．２％、２
，５体２．２％であった。-1 cof (Example-2) 2.0 g of anhydrous aluminum chloride and 2.0 g of zinc chloride
Next, the reaction and treatment were carried out in the same manner as in Example 1, except that the reaction temperature was changed to 50°C and the reaction time was changed to 10 hours.
189.6 g of xylenol was obtained. Purity 97.2%, 2
, 5 bodies, 2.2%.
（比較例）
米国特許２９１７４８７号に従って反応した。即ち、５
００ ｍガラス製４ツロフラスコに第２表に示す実施例
−１と全く同し組成の粗２，４−キシレノール２４４．
４ｇ、９０％パラホルムアルデヒド６．６ｇを仕込１０
０°Ｃに保った。ついで３６％塩酸３０ｍ１を装入し、
１００°Ｃで３０分保った。反応終了後、水２００ｄ）
ルエン２００ｄに反応マスを排出して充分撹拌したのち
分液した。トルエン層を脱トルエンしたのち減圧蒸留し
て沸点１０４°Ｃ／２１ｍｍＨｇの留分（精２．４−キ
シレノール） １８８．９ｇを得た。その組成を第２表
に示す。(Comparative Example) A reaction was carried out according to US Pat. No. 2,917,487. That is, 5
244.0 m of crude 2,4-xylenol having exactly the same composition as Example-1 shown in Table 2 was placed in a 4-meter glass flask.
4g, 90% paraformaldehyde 6.6g 10
It was kept at 0°C. Then, 30ml of 36% hydrochloric acid was charged,
It was kept at 100°C for 30 minutes. After the reaction is completed, 200 d of water)
The reaction mass was discharged into 200 d of toluene, stirred thoroughly, and then separated. After removing toluene from the toluene layer, it was distilled under reduced pressure to obtain 188.9 g of a fraction (purified 2.4-xylenol) with a boiling point of 104°C/21 mmHg. Its composition is shown in Table 2.
第２表
（発明の効果）
実施例及び比較例に示させるように本発明方法は公知の
方法に比べ、精製によるロスも少なくして、特に分離困
難な２．５−キシレノールの含有量を大幅に除去して、
高純度の精２．４−キシレノールを得ることができる。Table 2 (Effects of the Invention) As shown in the Examples and Comparative Examples, the method of the present invention reduces loss due to purification and significantly reduces the content of 2,5-xylenol, which is particularly difficult to separate. and remove it to
High purity purified 2,4-xylenol can be obtained.
特許出願人 三井東圧化学株式会社Patent applicant: Mitsui Toatsu Chemical Co., Ltd.
Claims (2)
ルを含むキシレノール異性体混合物を、ルイス酸の存在
下、アルデヒドと反応させ、２，５−キシレノールをキ
シレノールアルデヒド縮合物として分離、除去すること
を特徴とする２，４−キシレノールの精製方法。(1) A xylenol isomer mixture containing 2,4-xylenol and 2,5-xylenol is reacted with an aldehyde in the presence of a Lewis acid, and 2,5-xylenol is separated and removed as a xylenol aldehyde condensate. A characterized method for purifying 2,4-xylenol.
１）項記載の方法。(2) Claim No. 1 in which the Lewis acid is a metal chloride (
The method described in section 1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-156640A JPH013136A (en) | 1987-06-25 | Method for purifying 2,4-xylenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-156640A JPH013136A (en) | 1987-06-25 | Method for purifying 2,4-xylenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS643136A JPS643136A (en) | 1989-01-06 |
| JPH013136A true JPH013136A (en) | 1989-01-06 |
Family
ID=
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