JP2968625B2 - Method for producing olefin oxide - Google Patents
Method for producing olefin oxideInfo
- Publication number
- JP2968625B2 JP2968625B2 JP3266898A JP26689891A JP2968625B2 JP 2968625 B2 JP2968625 B2 JP 2968625B2 JP 3266898 A JP3266898 A JP 3266898A JP 26689891 A JP26689891 A JP 26689891A JP 2968625 B2 JP2968625 B2 JP 2968625B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- reaction
- olefin
- olefin oxide
- sodium
- 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.)
- Expired - Fee Related
Links
- 150000001336 alkenes Chemical class 0.000 title claims description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 150000004965 peroxy acids Chemical class 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 235000002639 sodium chloride Nutrition 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006735 epoxidation reaction Methods 0.000 description 8
- 235000011054 acetic acid Nutrition 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 150000002118 epoxides Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000004967 organic peroxy acids Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000003385 ring cleavage reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- -1 tartaric acid Organic acid salts Chemical class 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GLVYLTSKTCWWJR-UHFFFAOYSA-N 2-carbonoperoxoylbenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1C(O)=O GLVYLTSKTCWWJR-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 206010000369 Accident Diseases 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- NCIDKUDOSHBPMB-UHFFFAOYSA-N n-methylmethanamine;sulfuric acid Chemical compound CNC.OS(O)(=O)=O NCIDKUDOSHBPMB-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、オレフィンオキサイ
ド、特には、α−オレフィンのエポキシドの製造方法に
関する。α−オレフィンオキサイドは、各種界面活性剤
原料、ポリマー改質剤等の用途を持ち、工業的に極めて
重要な物質である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing olefin oxides, especially epoxides of .alpha.-olefins. α-Olefin oxide is an industrially extremely important substance having various uses such as a surfactant raw material and a polymer modifier.
【0002】[0002]
【従来の技術】オレフィン類を有機過酸によって相当す
るエポキシドに変える事は、かなり以前から知られてい
る。有機過酸としては、古くは、過安息香酸や、過フタ
ール酸等が使用されていたが、これらの方法で工業的に
オレフィンオキサイドを得るには、これらの過酸を合成
する工程が必要であり、また、これらの母体酸を回収す
るには、多大な経費が必要とされた。The conversion of olefins to the corresponding epoxides by organic peracids has long been known. As the organic peracid, perbenzoic acid, perphthalic acid and the like have been used in the past, but in order to industrially obtain olefin oxide by these methods, a step of synthesizing these peracids is necessary. Yes, and significant expense was required to recover these mother acids.
【0003】また、D.Swernらは、過酢酸の酢酸
溶液を用いてα−オレフィンオキサイドの合成を行って
いるが、(J.Am.Chem.Soc.68,150
4,(1964))この方法は、過酢酸溶液を調整する
ために、高濃度(90%)の過酸化水素を必要とするこ
と、および反応系が均一となるため、反応後多量の水を
加え、エポキシドを抽出する必要があること等、工業的
に実施するには、大きな問題があった。これらの問題を
解決するために、近年においては、鉱酸等の触媒酸の存
在下、過酸化水素と酢酸とで、反応中に、その場で過酢
酸を発生させながらエポキシ化する、いわゆる“in-sit
u法”がエポキシ化の主流となって採用されている。[0003] D. Swern et al. Have synthesized α-olefin oxides using an acetic acid solution of peracetic acid, (J. Am. Chem. Soc. 68 , 150).
4, (1964)) This method requires a high concentration (90%) of hydrogen peroxide in order to prepare a peracetic acid solution, and since the reaction system becomes uniform, a large amount of water is required after the reaction. In addition, there is a big problem in industrial implementation, such as the need to extract epoxide. In order to solve these problems, in recent years, in the presence of a catalytic acid such as a mineral acid, epoxidation is performed while generating peracetic acid in situ with hydrogen peroxide and acetic acid during the reaction. in-sit
The “u method” has been adopted as the mainstream of epoxidation.
【0004】このin-situ法は、酢酸等のカルボン酸の
使用量が原料オレフィンに対して、50モル%程度の少
量で十分反応させる事が出来る点や、簡易な装置で対応
出来る点等、様々な利点を持ち、工業的に極めて意義の
あるプロセスである。しかしながら、in-situ法の欠点
としては、エポキシ環の開裂反応等の副反応が起こりや
すいことである。これを防ぐために、反応時には、有機
溶剤を使用するのが一般的である。The in-situ method is characterized in that a sufficient amount of a carboxylic acid such as acetic acid can be reacted with a starting olefin with a small amount of about 50 mol%, and that a simple apparatus can be used. It is an industrially significant process with various advantages. However, a disadvantage of the in-situ method is that side reactions such as an epoxy ring cleavage reaction are likely to occur. In order to prevent this, an organic solvent is generally used during the reaction.
【0005】例えば、特開昭57−145866号公報
では、ベンゼンを使用し、ドイツ特許1568016号
公報では、ベンゼンあるいはトルエンを使用し、また、
特開昭51−36448号公報においては、クロロホル
ム等の塩素系溶剤の使用を提唱している。For example, Japanese Patent Application Laid-Open No. 57-145866 uses benzene, and German Patent No. 1568016 uses benzene or toluene.
JP-A-51-36448 proposes the use of a chlorine-based solvent such as chloroform.
【0006】[0006]
【発明が解決しようとする課題】しかしながら、ベンゼ
ンは、労働安全衛生法で定める特定化学物質であり、そ
の毒性上、取扱には、特別な注意が必要である。トルエ
ンも毒性を有し、また静電気を帯びやすく、トルエンに
よる火災事故例は、数多く報告されている。特に過酸化
水素酸化反応においては、反応によって発生する熱量も
多く、かつ酸素ガスが発生する系であるため、火災危険
性は高い。However, benzene is a specific chemical substance specified by the Industrial Safety and Health Act, and its handling requires special attention due to its toxicity. Toluene is also toxic and easily charged with static electricity, and numerous fire accidents due to toluene have been reported. In particular, in the hydrogen peroxide oxidation reaction, since there is a large amount of heat generated by the reaction and an oxygen gas is generated, there is a high risk of fire.
【0007】また、塩素系溶剤は、それ自体有毒であ
り、火災の際には、ホスゲン、塩化水素等の毒性ガスを
発生する危険性があり、また近年においては、オゾン層
破壊の原因として地球環境問題上の汚染物質の中に挙げ
られるようになっている。従来、生産性を重視する立場
から、これら危険性のある有機溶剤が使用されることが
一般的であるが、近年は、労働環境の質的向上や本質的
安全性が追求されている。[0007] Chlorinated solvents are toxic in themselves, and there is a danger of generating toxic gases such as phosgene and hydrogen chloride in the event of fire. It is one of the environmental pollutants. Conventionally, from the standpoint of emphasizing productivity, these dangerous organic solvents are generally used. However, in recent years, quality improvement of the working environment and intrinsic safety have been pursued.
【0008】また、用途によっては、溶剤の微量残渣が
製品の品質上大きな問題となる事があり、この面からも
有機溶剤を全く使用しないエポキシ化方法が望まれてい
る。すなわち、本発明が解決しようとする課題は、有機
溶剤の使用なしに、in-situ法エポキシ化反応を選択的
に起こす方法を見出すことにある。[0008] Further, depending on the application, a trace amount of a solvent may cause a serious problem in the quality of a product. From this viewpoint, an epoxidation method using no organic solvent is desired. That is, an object of the present invention is to find a method for selectively causing an in-situ epoxidation reaction without using an organic solvent.
【0009】[0009]
【課題を解決するための手段】本発明者らは、特に無溶
媒条件下において、酸触媒の他に、塩類を添加しておく
と、副反応が抑えられ反応の選択性を向上させることが
出来る事を見出し、本発明を完成した。Means for Solving the Problems The present inventors have found that the addition of salts, in addition to an acid catalyst, under solvent-free conditions can suppress side reactions and improve the selectivity of the reaction. We found what we could do and completed the present invention.
【0010】すなわち、本発明は、分子内に炭素原子を
6〜30個有するオレフィン類を、酸性触媒の存在下、
カルボン酸及び過酸化水素より成る酸化剤混合物によっ
てエポキシ化する工程において、塩類を添加して反応さ
せる事を特徴とする、オレフィンオキサイドの製造方法
である。上記の如く、本発明は、有機溶剤を使用せず
に、オレフィンのエポキシ化を行うものであるが、必要
がある場合は、適当な溶媒を使用することは、全く支障
ない。That is, the present invention provides an olefin having 6 to 30 carbon atoms in a molecule in the presence of an acidic catalyst.
A process for producing an olefin oxide, characterized in that salts are added and reacted in the step of epoxidation with an oxidizing agent mixture comprising a carboxylic acid and hydrogen peroxide. As described above, in the present invention, the olefin is epoxidized without using an organic solvent. However, if necessary, the use of an appropriate solvent does not cause any problem.
【0011】本発明の対象とするオレフィンは、C6 〜
C30のオレフィンであり、特には、直鎖の末端に二重結
合を有するα−オレフィンである。本発明の方法で用い
る酸触媒は、in-situ法で一般的に使用されるものが適
用されるが、特には、硫酸が良い。The olefins to be used in the present invention are C 6 to C 6 .
It is a C 30 olefin, particularly an α-olefin having a double bond at a linear terminal. As the acid catalyst used in the method of the present invention, those generally used in an in-situ method are applied, and sulfuric acid is particularly preferable.
【0012】カルボン酸としては、ギ酸、酢酸、プロピ
オン酸が使用可能であるが、特に酢酸が良い。過酸化水
素としては、25〜75%濃度のものが使用可能である
が、特には、50〜70%のものを使用するのが良い。As the carboxylic acid, formic acid, acetic acid and propionic acid can be used, and acetic acid is particularly preferable. As the hydrogen peroxide, one having a concentration of 25 to 75% can be used, and particularly, one having a concentration of 50 to 70% is preferably used.
【0013】本発明で使用する塩類の酸成分としては、
硫酸、炭酸、硝酸、過塩素酸、塩酸等の無機酸類、酢
酸、プロピオン酸、酒石酸等の有機酸が挙げられる。The acid components of the salts used in the present invention include:
Inorganic acids such as sulfuric acid, carbonic acid, nitric acid, perchloric acid and hydrochloric acid; and organic acids such as acetic acid, propionic acid and tartaric acid.
【0014】また、塩基成分としては、ナトリウム、カ
リウム、アンモニウム等の無機塩基成分、アミン類等の
有機塩基類が使用できる。As the base component, inorganic base components such as sodium, potassium and ammonium, and organic bases such as amines can be used.
【0015】具体的には、硫酸ナトリウム、硫酸カリウ
ム、硫酸水素ナトリウム、硫酸水素カリウム、硫酸アン
モニウム、炭酸ナトリウム、炭酸水素ナトリウム、硝酸
ナトリウム、過塩素酸ナトリウム、塩化ナトリウム等の
無機塩類、酢酸ナトリウム、酒石酸ナトリウム等の、有
機酸塩類、ジメチルアミン硫酸等の有機アミン塩等が有
効であるが、特には、硫酸ナトリウムが良い。More specifically, inorganic salts such as sodium sulfate, potassium sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, ammonium sulfate, sodium carbonate, sodium hydrogen carbonate, sodium nitrate, sodium perchlorate, sodium chloride, sodium acetate, tartaric acid Organic acid salts such as sodium and organic amine salts such as dimethylamine sulfate are effective, but sodium sulfate is particularly preferable.
【0016】また、これらの酸成分、塩基成分を、アル
カリ体やフリーの酸の形で反応直前に加え、反応系の中
で、塩形成させ使用する事も可能である。It is also possible to add these acid components and base components in the form of an alkali or a free acid immediately before the reaction, to form a salt in the reaction system before use.
【0017】塩類の使用量は、広範囲で効果的である
が、特には、0.5〜4.5更には、1.8〜2.2当量
(対 触媒酸)が良い。The amount of salts used is effective over a wide range, but is particularly preferably 0.5 to 4.5, and more preferably 1.8 to 2.2 equivalents (to the catalytic acid).
【0018】反応温度は、一般in-situ法と同様である
が、50〜90℃が良く、特には、60〜80℃の範囲
が良い。The reaction temperature is the same as that of the general in-situ method, but is preferably from 50 to 90 ° C., and particularly preferably from 60 to 80 ° C.
【0019】[0019]
【作用】in-situ法において、鉱酸等の強酸の役目は、
過酸化水素とカルボン酸とによる過酸の生成の促進にあ
る。従って、単に反応を促進するという立場からのみ考
えた場合には、強酸の酸性度が強いほど有利であるとい
うことになる。しかしながら、この強酸触媒は、同時に
エポキシ環の開裂反応や重合反応の触媒としても働く。
故に、この相反する要求をいかに満足していくかに、反
応の選択性が掛かってくるわけである。[Action] In the in-situ method, the role of a strong acid such as a mineral acid is
The purpose is to promote the production of peracid by hydrogen peroxide and carboxylic acid. Therefore, from the standpoint of merely accelerating the reaction, the stronger the acidity of the strong acid, the more advantageous. However, this strong acid catalyst also functions as a catalyst for the epoxy ring cleavage reaction and the polymerization reaction.
Therefore, how to satisfy these conflicting requirements depends on the selectivity of the reaction.
【0020】本発明における塩類の添加は、過酸形成の
触媒性能の低下をあまり起こさせないで、かつ、副反応
を抑制する様な酸性度を与える働きを持つものと推定さ
れる。以下に、本発明の実施例を示す。It is presumed that the addition of salts in the present invention does not cause a significant decrease in the catalytic performance of peracid formation and also has a function of giving an acidity so as to suppress a side reaction. Hereinafter, examples of the present invention will be described.
【0021】[0021]
【実施例】実施例1〜19及び比較例1〜6 撹拌装置、温度計、コンデンサーを備えた500ml容の
反応フラスコ中に、1.0モルのα−オレフィン、酢酸
30.g(0.5モル)、25%硫酸7.84g(正味1.
96g)、及び60%過酸化水素68.03g(1.2モ
ル)、塩類を仕込み、70℃、300rpmの条件下で
反応させた。 尚、オレフィン類のエポキシ化反応開始
時のpHは、0以下〜0.5の範囲であり、反応終了時
のpHは、0〜1.0の範囲であった。12hr後、反
応混合物を油相と水相に分離し、油相の一部を取り、ガ
スクロマトグラフィーで分析し、生成物の濃度を調べ、
残存率、収率等を計算した。得られたExamples 1 to 19 and Comparative Examples 1 to 6 In a 500 ml reaction flask equipped with a stirrer, a thermometer and a condenser, 1.0 mol of α-olefin and 30.g of acetic acid (0.5 g) were added. Mol), 7.84 g of 25% sulfuric acid (net 1.
96 g), 68.03 g (1.2 mol) of 60% hydrogen peroxide, and salts were charged and reacted at 70 ° C. and 300 rpm. In addition, epoxidation reaction of olefins started
PH at the end of the reaction is in the range of 0 to 0.5.
PH ranged from 0 to 1.0. After 12 hours, the reaction mixture was separated into an oil phase and an aqueous phase, a portion of the oil phase was taken and analyzed by gas chromatography to determine the concentration of the product,
The residual ratio, yield and the like were calculated. Got
【0022】なお表中のジオールとは、エポキシドに水
が付加して生成するアルカン−1,2−ジオールであ
り、その他の副生物の生成率は、100−(オレフィン
残存率+エポキシド収率+ジオール生成率)で計算して
いる。また、エポキシ化選択率は、エポキシド収率/
(100−オレフィン残存率)×100で計算した。The diol in the table is an alkane-1,2-diol formed by adding water to an epoxide, and the rate of formation of other by-products is 100- (olefin residual rate + epoxide yield + Diol formation rate). In addition, the epoxidation selectivity is determined by the epoxide yield /
It was calculated by (100-olefin residual ratio) × 100.
【0023】[0023]
【表1】 [Table 1]
【0024】[0024]
【発明の効果】本発明の方法に従えば、無溶媒条件下
で、選択率良くエポキシ化反応を進めることが出来る。
これによって、製造工程における、有機溶剤に起因する
火災危険性及び人体への有害性は、本質的に解決される
ことになる。また、製品中の、有機溶剤からもたらされ
るコンタミネーションは、皆無であり、品質面でも優れ
た製品を生産することが可能となる。このように、本発
明の持つ工業的意義は大きい。日本パーオキサイド株式
会社According to the method of the present invention, the epoxidation reaction can proceed with high selectivity under the condition of no solvent.
This essentially eliminates fire hazards and harm to the human body due to organic solvents in the manufacturing process. Further, there is no contamination caused by the organic solvent in the product, and a product excellent in quality can be produced. Thus, the present invention has great industrial significance. Nippon Peroxide Co., Ltd.
フロントページの続き (58)調査した分野(Int.Cl.6,DB名) C07D 301/00 - 301/16 Continuation of front page (58) Field surveyed (Int.Cl. 6 , DB name) C07D 301/00-301/16
Claims (2)
レフィン類を、酸性触媒存在下、カルボン酸及び過酸化
水素とから、反応系内において過酸を生成させながらエ
ポキシ化する方法において、前記酸性触媒に対して、
0.5〜4.5当量の塩類を添加して反応させることを
特徴とするオレフィンオキサイドの製造方法。1. An olefin having from 6 to 30 carbon atoms in a molecule is reacted with a carboxylic acid and a peroxide in the presence of an acidic catalyst.
While generating peracid in the reaction system from hydrogen,
In the method of poxifying, the acid catalyst is
A method for producing an olefin oxide, which comprises adding 0.5 to 4.5 equivalents of a salt to cause a reaction.
および酢酸塩からなる群から選ばれた少なくとも1種の
化合物である請求項1記載の方法。2. The salt comprises a sulfate, a nitrate, a perchlorate,
The method according to claim 1, which is at least one compound selected from the group consisting of acetic acid and acetate.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3266898A JP2968625B2 (en) | 1990-11-13 | 1991-09-19 | Method for producing olefin oxide |
US07/985,573 US5268493A (en) | 1990-11-13 | 1992-12-03 | Method of producing olefin oxide |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30406390 | 1990-11-13 | ||
JP2-304063 | 1990-11-13 | ||
JP3266898A JP2968625B2 (en) | 1990-11-13 | 1991-09-19 | Method for producing olefin oxide |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05320150A JPH05320150A (en) | 1993-12-03 |
JP2968625B2 true JP2968625B2 (en) | 1999-10-25 |
Family
ID=17928589
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3266898A Expired - Fee Related JP2968625B2 (en) | 1990-11-13 | 1991-09-19 | Method for producing olefin oxide |
Country Status (1)
Country | Link |
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JP (1) | JP2968625B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4444642B2 (en) | 2003-12-15 | 2010-03-31 | 高砂香料工業株式会社 | Novel multi-component oxidation catalyst and method for producing epoxy compound using the same |
JP2010106039A (en) * | 2010-01-12 | 2010-05-13 | Idemitsu Kosan Co Ltd | Method for producing 2-alkylalkane-1, 2-diols |
-
1991
- 1991-09-19 JP JP3266898A patent/JP2968625B2/en not_active Expired - Fee Related
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