JPS63126838A - Recovery of chloromethyl methyl ether in chloromethylation of aromatic compound - Google Patents
Recovery of chloromethyl methyl ether in chloromethylation of aromatic compoundInfo
- Publication number
- JPS63126838A JPS63126838A JP61271097A JP27109786A JPS63126838A JP S63126838 A JPS63126838 A JP S63126838A JP 61271097 A JP61271097 A JP 61271097A JP 27109786 A JP27109786 A JP 27109786A JP S63126838 A JPS63126838 A JP S63126838A
- Authority
- JP
- Japan
- Prior art keywords
- methyl ether
- chloromethyl methyl
- chloromethyl
- aromatic
- unreacted
- 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
- 229940061627 chloromethyl methyl ether Drugs 0.000 title claims abstract description 63
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 20
- 238000007265 chloromethylation reaction Methods 0.000 title claims abstract description 9
- 238000011084 recovery Methods 0.000 title description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 15
- -1 aromatic chloromethyl compound Chemical class 0.000 claims abstract description 15
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 14
- 239000011707 mineral Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000011541 reaction mixture Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 4
- 239000000975 dye Substances 0.000 abstract description 4
- 239000003456 ion exchange resin Substances 0.000 abstract description 4
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 3
- 229920001477 hydrophilic polymer Polymers 0.000 abstract description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XMWGTKZEDLCVIG-UHFFFAOYSA-N 1-(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1 XMWGTKZEDLCVIG-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical group C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229950011008 tetrachloroethylene Drugs 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- CWSAGTDWRVNVLC-UHFFFAOYSA-N 4-chlorobut-2-enylbenzene Chemical compound ClCC=CCC1=CC=CC=C1 CWSAGTDWRVNVLC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000008096 xylene 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
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はフリーデルクラフッ触媒の存在下に芳香族化合
物とクロロメチルメチルエーテルとを反応せしめて芳香
族クロロメチル化合物を得る反応において、未反応のク
ロロメチルメチルエーテルを効率よく回収する方法に関
する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a reaction for obtaining an aromatic chloromethyl compound by reacting an aromatic compound with chloromethyl methyl ether in the presence of a Friedelkraff catalyst. This invention relates to a method for efficiently recovering chloromethyl methyl ether from a reaction.
〔従来の技術及び発明が解決しようとする問題点〕芳香
族クロロメチル化合物は医薬品、染料、イオン交換樹脂
や導電剤、帯電防止剤６間原料として広く利用されてい
る。この種芳香族クロロメチル化合物を得る方法として
は例えばポリスチレン等の芳香族化合物に、フリーデル
クラフッ触媒の存在下にクロロメチルメチルエーテルを
反応せしめる方法が一般に採用されている（例えば米国
特許第２６１４０９９号明細書、高分子化学第２５巻第
２７９号（１９６８年）４１９頁、インダストリアル・
アンド・エンジニアリング・ケミストリー第４４巻第１
１号（１９５２年）２６８６頁）。[Prior art and problems to be solved by the invention] Aromatic chloromethyl compounds are widely used as raw materials for pharmaceuticals, dyes, ion exchange resins, conductive agents, and antistatic agents. As a method for obtaining this type of aromatic chloromethyl compound, a method is generally employed in which an aromatic compound such as polystyrene is reacted with chloromethyl methyl ether in the presence of a Friedel-Kraf catalyst (for example, U.S. Pat. No. 2,614,099). Specification, Kobunshi Kagaku Vol. 25, No. 279 (1968), p. 419, Industrial
and Engineering Chemistry Volume 44 No. 1
No. 1 (1952) p. 2686).
上記反応において、ゲル化等の副反応を抑制し、目的と
するクロロメチル化合物を高純度、高収率で得るために
はクロロメチルメチルエーテルを過剰に用いる必要があ
り、クロロメチルメチルエーテルの使用量が多いほど良
好なりロロメチル化合物を得ることができる。ところが
クロロメチルメチルエーテルを多量に用いて反応を行っ
た後未反応のクロロメチルメチルエーテルを蒸留して回
収しようとすると反応生成物が脱塩酸反応を起してゲル
化するという問題があシ、従来は目的とする反応生成物
を蒸留等によって精製−単離するに際し、反応生成物と
未反応のクロロメチルメチルエーテルを含む反応混合物
に水や水とジオギサンとの混合物等を添加して洗浄し、
未反応のり四ロメチルメチルエーテルを分解除去せざる
を得ず、り目ロメチルメチルエーテルは値段の高い原料
であるために未反応のクロロメチルメチルエーテルを回
収して再使用し得ないことは製造コストの上できわめて
大きな問題であり九。従ってクロロメチルメチルエーテ
ルを大過剰に用いて反応を行うことは、よシ高純度のク
ロロメチル化合物が得られるとしても製造コストの上で
困難であ夛、従来は反応生成物の純度等を多少犠牲にし
て、クロロメチルメチルエーテルの使用量を必要量の３
〜５倍量程度としてクロロメチル化を行っているのが現
状である。In the above reaction, in order to suppress side reactions such as gelation and obtain the desired chloromethyl compound with high purity and high yield, it is necessary to use an excess of chloromethyl methyl ether. The larger the amount, the better the lolomethyl compound can be obtained. However, when attempting to recover unreacted chloromethyl methyl ether by distillation after carrying out a reaction using a large amount of chloromethyl methyl ether, there is a problem in that the reaction product undergoes a dehydrochloric acid reaction and turns into a gel. Conventionally, when purifying and isolating the desired reaction product by distillation, etc., the reaction mixture containing the reaction product and unreacted chloromethyl methyl ether was washed by adding water or a mixture of water and geohysanate, etc. ,
Unreacted chloromethyl methyl ether has to be decomposed and removed, and unreacted chloromethyl methyl ether cannot be recovered and reused because it is an expensive raw material. This is a huge problem in terms of manufacturing costs. Therefore, carrying out the reaction using a large excess of chloromethyl methyl ether is difficult due to production costs, even if a highly pure chloromethyl compound can be obtained. At the cost of reducing the amount of chloromethyl methyl ether used to 3% of the required amount.
Currently, chloromethylation is carried out at about 5 times the amount.
一方、上記の問題を解決するために芳香族化合物にハロ
ゲンを反応させて得た芳香族ハロゲン化物を芳香族クロ
ロメチル化合物のかわりに用いることも提案されている
（特公昭５２−２２９９２号公報）。しかしながら芳香
族化合物をハロゲンと反応させる方法では、ハロゲンの
反応位置に選択性がないため副反応生成物の生成が多く
、そのため多くの精製工程を必要とする等の問題があシ
、芳香族クロロメチル化合物の代替として芳香族ハロゲ
ン化物を精製せずにそのまま用いることは、製造コスト
の上で多少の利点があるものの製品性状の点からは好ま
しいものではなかった。On the other hand, in order to solve the above problem, it has been proposed to use an aromatic halide obtained by reacting an aromatic compound with a halogen instead of an aromatic chloromethyl compound (Japanese Patent Publication No. 52-22992). . However, in the method of reacting aromatic compounds with halogen, there are problems such as the formation of many side reaction products due to lack of selectivity in the reaction position of halogen, which requires many purification steps. Although using aromatic halides as they are without purification as a substitute for methyl compounds has some advantages in terms of manufacturing costs, it is not preferable in terms of product properties.
本発明者らは上記の点に鑑み、芳香族化合物のクロロメ
チル化において未反応のクロロメチルメチルエーテルを
回収する方法を開発すべく鋭意研究した結果、反応生成
物と未反応のクロロメチルメチルエーテルを含む反応混
合物が蒸留によってゲル化するのはフリーデルクラフッ
触媒の存在によるためであることを見出し、更に鋭意研
究した結果、反応生成物と未反応のクロロメチルメチル
・エーテルを含む反応混合物を濃鉱酸で洗浄することに
よシ、未反応のクロロメチルメチルエーテルを分解する
ことなくフリーデルクラフッ触媒を除去でき、蒸留によ
ってゲル化を生じることなく容易にクロロメチルメチル
エーテルを回収することができることを見出し、本発明
を完成するに至った。In view of the above points, the present inventors conducted intensive research to develop a method for recovering unreacted chloromethyl methyl ether during chloromethylation of aromatic compounds, and as a result, the reaction product and unreacted chloromethyl methyl ether were recovered. It was discovered that the reason why a reaction mixture containing the reaction product and unreacted chloromethyl methyl ether gelled by distillation was due to the presence of Friedelkrach's catalyst. By washing with concentrated mineral acid, the Friedelkrach catalyst can be removed without decomposing unreacted chloromethyl methyl ether, and chloromethyl methyl ether can be easily recovered by distillation without gelation. The inventors have discovered that this can be done, and have completed the present invention.
即ち本発明はフリーデルクラフッ触媒の存在下に芳香族
化合物とクロロメチルメチルエーテルを反応せしめた後
、芳香族クロロメチル化合物と未反応のクロロメチルメ
チルエーテルを含有する反応混合物を濃鉱酸で洗浄して
７リーデルク２７ツ触媒を除去し、次いで蒸留して未反
応のクロロメチルメチルエーテルを回収することを特徴
とする芳香族化合物のクロロメチル化におけるクロロメ
チルメチルエーテルの回収方法を要旨とするものである
。That is, in the present invention, an aromatic compound and chloromethyl methyl ether are reacted in the presence of a Friedelkraff catalyst, and then the reaction mixture containing the aromatic chloromethyl compound and unreacted chloromethyl methyl ether is reacted with concentrated mineral acid. Abstract: A method for recovering chloromethyl methyl ether in chloromethylation of aromatic compounds, which is characterized by washing to remove a 7-Riederk catalyst and then distilling to recover unreacted chloromethyl methyl ether. It is something.
本発明においてりｏｔｘメチルメチルエーテルと反応せ
しめる芳香族化合物としては例えばベンゼン、トルエン
、キシレン等のベンゼンｍを１ｍ有する芳香族炭化水素
やナフタレン、アントラセン等の縮合べ／ゼン環を有す
る芳香族炭化水素類、ビフェニル、ジフェニルメタン、
トリフェニ・ルメタン、スチルベン等の独立したベンゼ
ン環を２個以上有する炭化水素類、スチレン、ビニルト
ルエン、メチルスチレン、ジビニルベンゼン等のビニル
芳香族モノマーあるいはこれらビニル芳香族モノマーの
ホモポリマー、コポリマー等が挙げられ、コポリマーと
してはビニル芳香族モノマー同志のコポリマーや、スチ
レン−アクリロニトリル共重合体、スチレン−ブタジェ
ン共重合体、スチレン−アクリロニトリル−ブタジェン
共重合体等のビニル芳香族モノマーと他のモノマーとの
コポリマーが挙げられる。In the present invention, aromatic compounds reacted with otx methyl methyl ether include aromatic hydrocarbons having 1 m of benzene m such as benzene, toluene, and xylene, and aromatic hydrocarbons having fused benzene rings such as naphthalene and anthracene. , biphenyl, diphenylmethane,
Examples include hydrocarbons having two or more independent benzene rings such as triphenylumethane and stilbene, vinyl aromatic monomers such as styrene, vinyltoluene, methylstyrene, and divinylbenzene, and homopolymers and copolymers of these vinyl aromatic monomers. Examples of copolymers include copolymers of vinyl aromatic monomers and copolymers of vinyl aromatic monomers and other monomers such as styrene-acrylonitrile copolymers, styrene-butadiene copolymers, and styrene-acrylonitrile-butadiene copolymers. Can be mentioned.
上記芳香族化合物とクロロメチルメチルエーテルとの反
応にはフリーデルクラフッ触媒が用いられ、本発明方法
では芳香族化合物とクロ薗メチルメチルエーテルを反応
せしめた後に濃鉱酸で洗浄してフリーデルクラフッ触媒
を除去するが、フリーデルクラフッ触媒が通常用いられ
ているものであれば本発明方法を適用することができる
。フリーデルクラフッ触媒としては例えばＡｌＣ１５、
Ｓｂ Ｃｋ、ＦｅＣ１５、ＦｅＣ１ｘ 、 ５ｎＣ１ａ
、Ｔｉ Ｃ１ａ、ＴｅＣ１ａ、ＢＩＣｊｓ 、 ＺｎＣ
Ｊ＊等の塩化物が一般に用いられる。また芳香族化合物
とクロロメチルメチルエーテルとの反応を四塩化炭素、
エチレンジクロリド、テトラクロロエチレン、ジクロロ
ベンゼン等の有機溶媒中で行うこともでキ、更にクロロ
メチルメチルエーテルを溶媒として用いることもできる
が、いずれの場合にも本発明方法を適用可能である。A Friedel-Kraf catalyst is used for the reaction between the aromatic compound and chloromethyl methyl ether, and in the method of the present invention, the aromatic compound and Kuro-zono methyl methyl ether are reacted and then washed with concentrated mineral acid. Although the Krachow catalyst is removed, the method of the present invention can be applied to any Friedel-Crach catalyst that is commonly used. Friedel Krach catalysts include, for example, AlC15,
Sb Ck, FeC15, FeC1x, 5nC1a
, Ti C1a, TeC1a, BICjs, ZnC
Chlorides such as J* are commonly used. In addition, the reaction between aromatic compounds and chloromethyl methyl ether is performed using carbon tetrachloride,
The reaction may be carried out in an organic solvent such as ethylene dichloride, tetrachloroethylene or dichlorobenzene, and furthermore, chloromethyl methyl ether may be used as a solvent, but the method of the present invention is applicable in either case.
上記濃鉱酸としては濃塩酸、濃硫酸、濃硝酸、濃リン酸
、濃ホウ酸等が挙げられるが、フリーデルクラフッ触媒
が前記Ｚｎ Ｃ１＊の如き塩化物の場合には特に濃塩酸
が好ましい。濃鉱酸はフリーデルクラフッ触媒を効果的
に溶解除去するとともにクロロメチルメチルエーテルの
分解を確実に防止する上で通常５Ｎ以上であればよいが
、特に８Ｎ以上が好ましい。目的とする反応生成物と未
反応のクロロメチルメチルエーテルを含む反応混合物の
量に対する濃鉱酸の量は通常０．１〜１０倍程度であ）
、反応混合物中のフリーデルクラフッ触媒を確実に除去
するために反応混合物に濃鉱酸を添加して充分攪拌又は
振とうした後、静置して濃鉱酸の層を完全分離せしめる
ことが好ましい。濃鉱酸による洗浄は必要により数回に
わけて行なってもよい、濃鉱酸によシ洗浄してフリーデ
ルクラフッ触媒を除去した反応混合物中の未反応クロロ
メチルメチルエーテルは蒸留によって容易に回収するこ
とができる。Examples of the above-mentioned concentrated mineral acids include concentrated hydrochloric acid, concentrated sulfuric acid, concentrated nitric acid, concentrated phosphoric acid, concentrated boric acid, etc., but when the Friedel Krach catalyst is a chloride such as the above-mentioned Zn C1*, concentrated hydrochloric acid is particularly preferred. preferable. In order to effectively dissolve and remove the Friedel-Crauch catalyst and reliably prevent the decomposition of chloromethyl methyl ether, the concentrated mineral acid should normally be at least 5N, but preferably at least 8N. The amount of concentrated mineral acid is usually about 0.1 to 10 times the amount of the reaction mixture containing the desired reaction product and unreacted chloromethyl methyl ether.)
In order to reliably remove the Friedel-Craft catalyst in the reaction mixture, it is possible to add concentrated mineral acid to the reaction mixture, stir or shake it thoroughly, and then leave it to stand to completely separate the layer of concentrated mineral acid. preferable. Washing with concentrated mineral acid may be carried out several times if necessary. Unreacted chloromethyl methyl ether in the reaction mixture that has been washed with concentrated mineral acid to remove the Friedel-Crach catalyst can be easily removed by distillation. It can be recovered.
以下実施例を挙げて本発明を更に詳細に説明する。 EXAMPLES The present invention will be explained in more detail with reference to Examples below.
実施例１
ポリスチレン（平均重合度３０００）１０４．９をエチ
レンジクロリド３００−に溶解した後、クロロメチルト
ルエン中＃４００＃とＺｎＣ１５１０ｆｉを添加し、４
０℃で１０時間反応を行なった。次いでＩＯＮ塩酸１０
０１１７を添加して洗浄した後、蒸留して未反応のクロ
ロメチルメチルエーテル３°１０１１を回収し、しかる
後、エチレンジクロリドを留去して塩素含有率ＩＺＯｗ
ｔ％のクロロメチル化ポリマーを得た。このポリマーの
塩素含有率よ）未反応クロロメチルメチルエーテルの理
論量を算出し、実際に回収されたクロロメチルメチルエ
ーテルの回収率を求めたところ、回収率９０．８％であ
った。Example 1 After dissolving 104.9 of polystyrene (average degree of polymerization 3000) in ethylene dichloride 300, #400# and ZnC1510fi in chloromethyltoluene were added,
The reaction was carried out at 0°C for 10 hours. Then ION hydrochloric acid 10
After adding 0117 and washing, distillation is performed to recover unreacted chloromethyl methyl ether 3°1011, and then ethylene dichloride is distilled off to reduce the chlorine content IZOw.
t% of chloromethylated polymer was obtained. The theoretical amount of unreacted chloromethyl methyl ether (based on the chlorine content of this polymer) was calculated, and the recovery rate of the actually recovered chloromethyl methyl ether was determined, and the recovery rate was 90.8%.
実施例２
ビニルトルエン（９０ｖｔ％）、ジビニルベンゼン（６
ｖｔ％）、エチルビニルベンゼン（４ｗｔ％）共重合体
よりなる球状ビーズ（１０〜４８メツシユ）１００．９
をエチレンジク四リド２００１１１７中で膨潤させた後
、クロロメチルメチルエーテル４００ｙとＺｎＣ１雪３
０１を添加し、４５℃で８時間反応を行なった。次いで
１２Ｎ塩酸１００ｄによる洗浄を３回行なった後、蒸留
して未反応のクロロメチルメチルエーテル３００．９を
回収し、更にエチレンジクロリドを留去して塩素含有率
２ Ｌ ５ ｖｔ％のクロロメチル化ポリマーを得た。Example 2 Vinyltoluene (90vt%), divinylbenzene (6
vt%), spherical beads (10 to 48 mesh) made of ethylvinylbenzene (4wt%) copolymer 100.9
After swelling in ethylene ditetralide 2001117, chloromethyl methyl ether 400y and ZnC1 snow 3
01 was added, and the reaction was carried out at 45°C for 8 hours. Next, after washing with 100 d of 12N hydrochloric acid three times, 300.9 g of unreacted chloromethyl methyl ether was recovered by distillation, and ethylene dichloride was further distilled off to obtain chloromethylation with a chlorine content of 2 L 5 vt%. A polymer was obtained.
このポリマーの塩素含有率よシ算出したクロロメチルメ
チルエーテルの回収率は９１８％であった。The recovery rate of chloromethyl methyl ether calculated from the chlorine content of this polymer was 918%.
実施例３
スチレン−アクリロニトリル共重合体（スチレン成分９
５モル％）１０１．５ｇをパークロロエチレン２００１
Ｌｔに溶解した後、クロロメチルメチルエーテル５００
．９を添加し、更にｋｌｃｌｓ １０ ｇを添加して４
５℃で４時間反応を行った。次いで１５Ｎ硫酸２００１
Ｌｔによって洗浄した後、蒸留してクロロメチルメチル
エーテル３９０ｇを回収するとともに、塩素含有率２１
．９ ｖｔ％のクロロメチル化ポリマーを得た。ポリマ
ーの塩素含有率よシ算出したクロロメチルメチルエーテ
ルの回収率は９１．３％であった。Example 3 Styrene-acrylonitrile copolymer (styrene component 9
5 mol%) 101.5g perchlorethylene 2001
After dissolving in Lt, chloromethyl methyl ether 500
．． Add 9 and then add 10 g of klcls to 4
The reaction was carried out at 5°C for 4 hours. Then 15N sulfuric acid 2001
After washing with Lt, 390 g of chloromethyl methyl ether was recovered by distillation, and the chlorine content was 21.
．． A 9 vt% chloromethylated polymer was obtained. The recovery rate of chloromethyl methyl ether calculated from the chlorine content of the polymer was 91.3%.
実施例４
トルエン９２ＩＩｔ−クロロメチルメチルエーテル５０
０．９に溶解し、 ＺｎＣ１＊ １０ Ｊｉ’を添加し
て５０℃で５時間反応を行った後、ＩＯＮ硫酸１００−
による洗浄を３回行い、次いで蒸留して未反応のクロロ
メチルメチルエーテル３５３Ｉを回収し、クロロメチル
トルエン中得り。クロロメチルトルエン中の塩素含有率
は２７．８ ｖｔ％であり、この値よシ算出したクロロ
メチルメチルエーテルの回収率は８４％であった。Example 4 Toluene 92 IIt-Chloromethyl methyl ether 50
After adding ZnC1*10 Ji' and reacting at 50°C for 5 hours, ION sulfuric acid 100-
Washing with 353I was carried out three times, and unreacted chloromethyl methyl ether 353I was recovered by distillation and obtained in chloromethyltoluene. The chlorine content in chloromethyltoluene was 27.8 vt%, and the recovery rate of chloromethyl methyl ether calculated from this value was 84%.
実施例５
す７タレン１２８Ｉをエチレンジクロリド１５０ｄに溶
解した後、 ＳｎＣｊｍ ２０９及びクロロメチルメチ
ルエーテル２５０ＩＩを添加して５０℃で７時間反応を
行った。次いで９Ｎ塩酸３００ｄで２回洗浄した後、蒸
留して１４５＃の未反応クロロメチルメチルエーテルを
回収し、更にエチレンジクロリドを留去してクロロメチ
ルナフタレンを得た。Example 5 After dissolving Su7talene 128I in ethylene dichloride 150d, SnCjm 209 and chloromethyl methyl ether 250II were added and the reaction was carried out at 50°C for 7 hours. After washing twice with 300 d of 9N hydrochloric acid, the mixture was distilled to recover 145# unreacted chloromethyl methyl ether, and ethylene dichloride was further distilled off to obtain chloromethylnaphthalene.
クロロメチルナフタレンの塩素含有率は２０．１ ｗｔ
％であ）、またクロロメチルメチルエーテルの回収率は
８５．３％であっ九。The chlorine content of chloromethylnaphthalene is 20.1 wt.
%), and the recovery rate of chloromethyl methyl ether was 85.3%.
実施例６
ビニルトルエｙ１１ Ｂｉｔエチレンジクロリド１５０
ｄに溶解し、クロロメチルメチルエーテル５ｏｏｙを添
加し更にＺｎＣｊｚ １５ ｇを添加し、４５℃で５時
間反応を行い、反応終了後１１Ｎ塩酸２００１１ｊで洗
浄後、蒸留して未反応のクロロメチルメチルエーテルを
回収し塩素含有率１９．５ｗｔ％のクロロメチルビニル
トルエンを得た。回収したクロロメチルメチルエーテル
のｊＩｋは３９０９であり、回収率は９１゜３％であっ
た。Example 6 Vinyl toluene y11 Bit ethylene dichloride 150
d, added 5ooy of chloromethyl methyl ether, and further added 15 g of ZnCjz, and reacted at 45°C for 5 hours. After the reaction was completed, washed with 20011j of 11N hydrochloric acid, and distilled to remove unreacted chloromethyl methyl ether. was recovered to obtain chloromethylvinyltoluene with a chlorine content of 19.5 wt%. The jIk of the recovered chloromethyl methyl ether was 3909, and the recovery rate was 91.3%.
実施例７
ジフェニルメタン１６８Ｉをエチレンジクロリド１５０
ｄに溶解し、これにＦｅＣ１５１５、！ｉ’及びクロロ
メチルメチルエーテル２５０Ｉを添加して６０℃で３時
間反応を行った。反応終了後、ＩＩＮ硝酸３００ｍで洗
浄し、次いで蒸留して未反応のクロロメチルメチルエー
テル１５５ｇを回収し、更にエチレンジクロリドを留去
して塩素含有率１ｔ８ｖｔ％のクロロメチル化ジフェニ
ルメタンを得九。クロロメチルメチルエーテルの回収率
は８７％であった。Example 7 Diphenylmethane 168I to ethylene dichloride 150
d, and FeC1515,! i' and chloromethyl methyl ether 250I were added and the reaction was carried out at 60°C for 3 hours. After the reaction was completed, the reaction mixture was washed with 300 m of IIN nitric acid, and then distilled to recover 155 g of unreacted chloromethyl methyl ether. Ethylene dichloride was further distilled off to obtain chloromethylated diphenylmethane with a chlorine content of 1t8vt%. The recovery rate of chloromethyl methyl ether was 87%.
以上説明したように本発明方法は、フリーデルクラフッ
触媒の存在下に芳香族化合物とクロロメチルメチルエー
テルとを反応せしめて得られる芳香族クロロメチル化合
物と未反応のクロロメチルメチルエーテルを含む反応混
合物を濃鉱酸で洗浄してフリーデルクラフッ触媒を除去
した後、蒸留する方法を採用したことによって芳香族化
合物のクロロメチル化における未反応のクロロメチルメ
チルエーテルを効率よく回収して再使用することを可能
とし、この結果高価なりロロメチルメチルエーテルを水
等により分解除去する等の製造コスト上の問題を改善で
き、芳香族クロロメチル化合物を安価に製造できる。し
かも未反応のクロロメチルメチルエーテルを回収再使用
できるため、クロロメチルメチルエーテルを芳香族化合
物に対して大過剰に用いても、はとんどコスト上昇がな
く、クロロメチルメチルエーテルを大過剰に用いればよ
υ高純度の芳香族クロロメチル化合物を高収率で得るこ
とができ、医薬品、染料、イオン交換樹脂、親水性高分
子第４級アンモニウム塩等の中間原料として用いた場合
、従来芳香族り党ロメチル化合物の代替として用いられ
ていた芳香族ハロゲン化物のように多くの副反応物の混
ざシ込みによる製品性状の低下をきたす慮れがなく、医
薬品、染料、イオン交換樹脂、親水性高分子第４級アン
モニウム塩等の中間原料として有用な芳香族クロロメチ
ル化合物を安価に提供できる等のきわめて優れた効果を
奏するものである。As explained above, the method of the present invention involves a reaction involving an aromatic chloromethyl compound obtained by reacting an aromatic compound and chloromethyl methyl ether in the presence of a Friedel Krach catalyst and unreacted chloromethyl methyl ether. Unreacted chloromethyl methyl ether in chloromethylation of aromatic compounds can be efficiently recovered and reused by washing the mixture with concentrated mineral acid to remove Friedelkrach's catalyst and then distilling it. As a result, it is possible to solve the production cost problems such as decomposition and removal of expensive lolomethyl methyl ether with water or the like, and it is possible to produce aromatic chloromethyl compounds at low cost. In addition, unreacted chloromethyl methyl ether can be recovered and reused, so even if chloromethyl methyl ether is used in large excess relative to aromatic compounds, there is almost no increase in cost, and chloromethyl methyl ether can be used in large excess. When used as an intermediate raw material for pharmaceuticals, dyes, ion exchange resins, hydrophilic polymer quaternary ammonium salts, etc., aromatic chloromethyl compounds of high purity can be obtained in high yields. There is no possibility of deterioration of product properties due to mixing of many side reactants such as aromatic halides, which were used as substitutes for methyl compounds, and are suitable for pharmaceuticals, dyes, ion exchange resins, and hydrophilic products. This method has extremely excellent effects such as being able to provide an aromatic chloromethyl compound useful as an intermediate raw material for polymeric quaternary ammonium salts and the like at a low cost.
Claims (1)
ロメチルメチルエーテルを反応せしめた後、芳香族クロ
ロメチル化合物と未反応のクロロメチルメチルエーテル
を含有する反応混合物を濃鉱酸で洗浄してフリーデルク
ラフツ触媒を除去し、次いで蒸留して未反応のクロロメ
チルメチルエーテルを回収することを特徴とする芳香族
化合物。 クロロメチル化におけるクロロメチルメチルエーテルの
回収方法。[Claims] After reacting an aromatic compound and chloromethyl methyl ether in the presence of a Friedel-Crafts catalyst, the reaction mixture containing the aromatic chloromethyl compound and unreacted chloromethyl methyl ether is mixed with concentrated mineral acid. An aromatic compound characterized in that the Friedel-Crafts catalyst is removed by washing with water, and then the unreacted chloromethyl methyl ether is recovered by distillation. Method for recovering chloromethyl methyl ether in chloromethylation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61271097A JPH07116069B2 (en) | 1986-11-14 | 1986-11-14 | Method for recovering chloromethyl methyl ether in chloromethylation of aromatic compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61271097A JPH07116069B2 (en) | 1986-11-14 | 1986-11-14 | Method for recovering chloromethyl methyl ether in chloromethylation of aromatic compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63126838A true JPS63126838A (en) | 1988-05-30 |
| JPH07116069B2 JPH07116069B2 (en) | 1995-12-13 |
Family
ID=17495310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61271097A Expired - Fee Related JPH07116069B2 (en) | 1986-11-14 | 1986-11-14 | Method for recovering chloromethyl methyl ether in chloromethylation of aromatic compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07116069B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111530432A (en) * | 2020-05-07 | 2020-08-14 | 西安蓝深环保科技有限公司 | Preparation method of adsorbing material for blood perfusion |
-
1986
- 1986-11-14 JP JP61271097A patent/JPH07116069B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111530432A (en) * | 2020-05-07 | 2020-08-14 | 西安蓝深环保科技有限公司 | Preparation method of adsorbing material for blood perfusion |
| CN111530432B (en) * | 2020-05-07 | 2022-06-14 | 西安蓝深新材料科技有限公司 | Preparation method of adsorbing material for blood perfusion |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07116069B2 (en) | 1995-12-13 |
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