JP4940598B2 - Method for producing organic peroxide - Google Patents
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- JP4940598B2 JP4940598B2 JP2005244334A JP2005244334A JP4940598B2 JP 4940598 B2 JP4940598 B2 JP 4940598B2 JP 2005244334 A JP2005244334 A JP 2005244334A JP 2005244334 A JP2005244334 A JP 2005244334A JP 4940598 B2 JP4940598 B2 JP 4940598B2
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- 150000001451 organic peroxides Chemical class 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 150000001875 compounds Chemical group 0.000 claims description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 150000002978 peroxides Chemical class 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 19
- 239000012074 organic phase Substances 0.000 claims description 18
- 239000008346 aqueous phase Substances 0.000 claims description 14
- 239000012933 diacyl peroxide Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 11
- -1 alkyl halogenated formate Chemical class 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims description 5
- 150000001266 acyl halides Chemical class 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012530 fluid Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 150000001265 acyl fluorides Chemical class 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000011027 product recovery Methods 0.000 description 5
- JVSFQJZRHXAUGT-UHFFFAOYSA-N 2,2-dimethylpropanoyl chloride Chemical compound CC(C)(C)C(Cl)=O JVSFQJZRHXAUGT-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- KEDSBJOHAWJRQU-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6-nonafluoro-6-(1,1,2,2,3,3,3-heptafluoropropyl)oxane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C1(F)OC(F)(F)C(F)(F)C(F)(F)C1(F)F KEDSBJOHAWJRQU-UHFFFAOYSA-N 0.000 description 2
- GBOMEIMCQWMHGB-UHFFFAOYSA-N 2-butyltetrahydrofuran Chemical compound CCCCC1CCCO1 GBOMEIMCQWMHGB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- LEQCMDRIOPTEDI-UHFFFAOYSA-N [2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]propanoyl] 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]propaneperoxoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC(F)(C(F)(F)F)C(F)(F)OC(F)(C(F)(F)F)C(=O)OOC(=O)C(F)(C(F)(F)F)OC(F)(F)C(F)(C(F)(F)F)OC(F)(F)C(F)(F)C(F)(F)F LEQCMDRIOPTEDI-UHFFFAOYSA-N 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- IVRIRQXJSNCSPQ-UHFFFAOYSA-N propan-2-yl carbonochloridate Chemical compound CC(C)OC(Cl)=O IVRIRQXJSNCSPQ-UHFFFAOYSA-N 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- BCLQALQSEBVVAD-UHFFFAOYSA-N 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propanoyl fluoride Chemical compound FC(=O)C(F)(C(F)(F)F)OC(F)(F)C(F)(F)C(F)(F)F BCLQALQSEBVVAD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical class [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Description
本発明は、管型反応器を用いた有機ペルオキシドの製造方法に関する。 The present invention relates to a method for producing an organic peroxide using a tubular reactor.
有機ペルオキシド、特にジアシルペルオキシドは、重合開始剤、架橋剤、プラスチックの表面処理剤等として有用な化合物である。 Organic peroxides, particularly diacyl peroxides, are useful compounds as polymerization initiators, crosslinking agents, plastic surface treatment agents, and the like.
従来、ジアシルペルオキシドは、槽型撹拌反応器を用いた回分操作により、アシルハライドおよび過酸化物を反応させて製造されている（例えば、特許文献１参照。）。 Conventionally, a diacyl peroxide is produced by reacting an acyl halide and a peroxide by a batch operation using a tank-type stirred reactor (see, for example, Patent Document 1).
ジアシルペルオキシドを製造する反応は大きな発熱を伴い、回分操作による製造方法では厳密な温度制御が困難であることから、生成したジアシルペルオキシドが熱分解し収率が低かった。また、ジアシルペルオキシドは自己分解性があり、ジアシルペルオキシドを運搬する際に振動や熱により爆発する恐れがある。 The reaction for producing diacyl peroxide has a large exotherm, and it is difficult to strictly control the temperature by the production method by batch operation. Therefore, the produced diacyl peroxide is thermally decomposed and the yield is low. In addition, diacyl peroxide is self-degradable and may explode due to vibration or heat when the diacyl peroxide is transported.
一方、種々の製品の大量生産には、生成物の品質が安定することから連続操作が採用されている。ジアシルペルオキシドの製造に連続操作を適用した例として、激しい撹拌を与える手段と組み合わせる方法が提案されている（例えば、特許文献２参照。）。しかし、この方法では激しく撹拌しながらジアシルペルオキシドを製造するため、副生するカルボン酸等が原因で反応液が泡立ち、反応後、有機相と水相との分離が困難である問題がある。 On the other hand, continuous operation is adopted for mass production of various products because the quality of the product is stable. As an example in which continuous operation is applied to the production of diacyl peroxide, a method combined with means for giving vigorous stirring has been proposed (see, for example, Patent Document 2). However, since this method produces diacyl peroxide with vigorous stirring, there is a problem that the reaction solution is foamed due to by-product carboxylic acid and the like, and it is difficult to separate the organic phase and the aqueous phase after the reaction.
本発明の目的は、上記のような問題点を解決し、除熱性に優れ、大量生産性に優れ、収率に優れ、安全性に優れた有機ペルオキシドの製造方法を提供することである。 The object of the present invention is to solve the above-mentioned problems and to provide a method for producing an organic peroxide that is excellent in heat removal, excellent in mass productivity, excellent in yield, and excellent in safety.
ＲＣ（＝Ｏ）Ｘ（ここで、ＲはＲ’またはＲ’Ｏを表し、Ｒ’はアルキル基（ただし、アルキル基Ｒ’にはフッ素原子が含まれていてもよく、エーテル性の酸素原子が含まれていてもよい。）であり、Ｘはハロゲン原子である。）で表される化合物と過酸化物とをアルカリ化合物の存在下に反応させてＲＣ（＝Ｏ）ＯＯＣ（＝Ｏ）Ｒで表される有機ペルオキシドを製造する方法であって、ＲＣ（＝Ｏ）Ｘを含む有機相と過酸化物およびアルカリ化合物を含む水相とを管型反応器内に導入し、管型反応器内での有機相および水相のレイノルズ数を１０００以下の層流状態に保持してＲＣ（＝Ｏ）Ｘと過酸化物との反応を行い、生成する有機ペルオキシドを含む反応混合物を管型反応器から連続的に取り出すことを特徴とする有機ペルオキシドの製造方法を提供する。 RC (═O) X (where R represents R ′ or R′O, R ′ represents an alkyl group (provided that the alkyl group R ′ may contain a fluorine atom, and an etheric oxygen atom) And X is a halogen atom, and a compound represented by (2) is reacted with a peroxide in the presence of an alkali compound to produce RC (= O) OOC (= O). A method for producing an organic peroxide represented by R, wherein an organic phase containing RC (= O) X and an aqueous phase containing a peroxide and an alkali compound are introduced into a tubular reactor, and a tubular reaction is conducted. The reaction mixture containing the organic peroxide produced by the reaction of RC (= O) X and peroxide is carried out while maintaining the Reynolds number of the organic phase and aqueous phase in the vessel in a laminar flow state of 1000 or less. Process for producing organic peroxides characterized by continuous removal from the reactor Provide law.
本発明の製造方法によれば、除熱性に優れ、大量生産性に優れ、生成物の収率に優れ、安全性に優れる方法でジアシルペルオキシドまたはジアルキルペルオキシジカーボネートが得られるので、工業的価値が極めて高い。 According to the production method of the present invention, diacyl peroxide or dialkyl peroxydicarbonate can be obtained by a method that is excellent in heat removal, excellent in mass productivity, excellent in product yield, and excellent in safety. Extremely expensive.
本発明における管型反応器は、以下マイクロリアクターともいう。本発明におけるマイクロリアクターとしては、基板の表面に、積層、貼付、エッチング、ＬＩＧＡプロセス、切削、鋳型成形などの方法により流路が形成されるか、または、細管を用いて流路が形成された３次元構造体等を用いることができる。 Hereinafter, the tubular reactor in the present invention is also referred to as a microreactor. As a microreactor in the present invention, a channel is formed on the surface of a substrate by a method such as lamination, sticking, etching, LIGA process, cutting, molding, or the like, or a channel is formed using a thin tube. A three-dimensional structure or the like can be used.
マイクロリアクターの形状としては、基板の表面に流路が形成されたチップ型マイクロリアクターが好ましい。流路の断面形状としては、三角形、四角形、円形、楕円形等が挙げられる。細管を用いて流路が形成されたマイクロリアクターの流路の形状としては、直管状、曲管状、円形コイル状、楕円形コイル状、正方形、長方形等の四角形コイル状等が挙げられる。マイクロリアクターの形状としては、流路の断面形状が四角形のチップ型マイクロリアクターがより好ましい。 As the shape of the microreactor, a chip type microreactor in which a channel is formed on the surface of the substrate is preferable. Examples of the cross-sectional shape of the channel include a triangle, a quadrangle, a circle, and an ellipse. Examples of the shape of the flow path of the microreactor in which the flow path is formed using a thin tube include a straight tubular shape, a curved tubular shape, a circular coil shape, an elliptical coil shape, and a square coil shape such as a square and a rectangle. As the shape of the microreactor, a chip type microreactor having a square cross-sectional shape of the flow path is more preferable.
マイクロリアクターには、流体の供給口、排出口につながる１つ以上の流路があり、複数の流体が接触する連続反応部を有する。連続反応部は、層流を維持しながら、複数の流体が接触または混合できる空間であれば特に限定されず、例えば、流路がＴ字またはＹ字に形成された構造、それらを多層に積み重ねた構造等が好ましい。 The microreactor has one or more flow paths connected to a fluid supply port and a fluid discharge port, and has a continuous reaction unit in contact with a plurality of fluids. The continuous reaction section is not particularly limited as long as it is a space where a plurality of fluids can contact or mix while maintaining a laminar flow. For example, a structure in which a flow path is formed in a T shape or a Y shape, and these layers are stacked in multiple layers. The structure etc. are preferable.
マイクロリアクターとしては、非混和性の水性流体および有機性流体が層流状態で交互に接する流れを構築できる構造がより好ましい。具体的な構造の例としては、図１に示す構造が挙げられる。 As the microreactor, a structure capable of constructing a flow in which an immiscible aqueous fluid and an organic fluid are alternately contacted in a laminar flow state is more preferable. An example of a specific structure is the structure shown in FIG.
ＲＣ（＝Ｏ）Ｘで表される化合物を含む有機相を供給口１より供給し、過酸化物およびアルカリ化合物を含む水相を供給口２より供給する。各相は連続流路３を通り、連続反応部４に供給される。連続反応部４で有機ペルオキシドが生成し、排出口５より連続的に取り出される。
An organic phase containing a compound represented by RC (═O) X is supplied from the
本発明におけるマイクロリアクターの流路の断面積は、１．０×１０−５〜０．８ｃｍ２であることが好ましい。断面積が該範囲であると、マイクロリアクターの製作が容易であり、単位体積当たりの壁面積が大きくなるため除熱効率に優れ、有機ペルオキシドの収率が高い。 The cross-sectional area of the flow path of the microreactor in the present invention is preferably 1.0 × 10 −5 to 0.8 cm 2 . When the cross-sectional area is within this range, the production of the microreactor is easy, the wall area per unit volume is large, and the heat removal efficiency is excellent, and the yield of organic peroxide is high.
本発明においては、マイクロリアクター内での有機相および水相のレイノルズ数（以下、Ｒｅと記す。）を１０００以下の層流状態に保持してアシルハライドまたはアシルハロゲン化ホルメートと、過酸化物との反応を行う。Ｒｅが該範囲であると、流体の流れは層流であり、反応の進行が安定し、有機ペルオキシドの収率が高い。 In the present invention, an acyl halide or acyl halide formate, a peroxide, and a Reynolds number (hereinafter referred to as Re) of the organic phase and aqueous phase in the microreactor are maintained in a laminar flow state of 1000 or less. Perform the reaction. When Re is within this range, the fluid flow is laminar, the progress of the reaction is stable, and the yield of organic peroxide is high.
Ｒｅとは、平均流体速度、流路の寸法および流体の動力学的速度から計算される、流体の状態を表す無次元数であり、例えば、Ｒｅ＝ｌρｕ／μ（ｌは流体を代表する長さ、ρは流体の密度、ｕは管内の流体の平均流速、μは粘度を示す。）の式を用いて計算できる。 Re is a dimensionless number representing the state of the fluid, calculated from the average fluid velocity, the dimensions of the flow path, and the dynamic velocity of the fluid. For example, Re = lρu / μ (l is a length representing a fluid) Ρ is the density of the fluid, u is the average flow velocity of the fluid in the tube, and μ is the viscosity.
本発明においては、マイクロリアクター内での有機相と水相の接触界面積が０．１ｍｍ２／ｍｍ３以上であることが好ましく、０．５ｍｍ２／ｍｍ３以上がより好ましく、０．８ｍｍ２／ｍｍ３以上が最も好ましい。接触界面積が該範囲であると、有機相と水相との接触面積が充分となり、有機ペルオキシドの収率が高い。 In the present invention, the contact interface area between the organic phase and the aqueous phase in the microreactor is preferably 0.1 mm 2 / mm 3 or more, more preferably 0.5 mm 2 / mm 3 or more, and 0.8 mm 2. / Mm 3 or more is most preferable. When the contact interface area is within this range, the contact area between the organic phase and the aqueous phase is sufficient, and the yield of organic peroxide is high.
ＲＣ（＝Ｏ）Ｘで表される化合物と過酸化物との連続反応部としては、有機相、水相、反応混合物等が連続的に供給および排出ができる構造であれば特に限定されない。連続反応部は、昇温・冷却ができる構造を有することが好ましい。連続反応部の設置方向としては、特に限定されず、垂直方向、水平方向、斜め方向等が採用される。 The continuous reaction portion between the compound represented by RC (═O) X and the peroxide is not particularly limited as long as the organic phase, the aqueous phase, the reaction mixture, and the like can be continuously supplied and discharged. The continuous reaction part preferably has a structure capable of heating and cooling. The installation direction of the continuous reaction unit is not particularly limited, and a vertical direction, a horizontal direction, an oblique direction, and the like are employed.
連続反応部の長さは０．００５〜１０００ｍが好ましく、０．０１〜１０ｍがより好ましい。連続反応部の長さが該範囲であると、原料の滞留時間が充分となり、有機ペルオキシドの収率が高く、原料の供給口と反応混合物の排出口の間の圧力損失を小さくでき、連続反応器内の流体の流れが安定し、層流状態が保持できる。滞留時間は０．１秒〜５時間が好ましく、０．２秒〜２時間がより好ましく、０．５秒〜１時間が最も好ましい。 The length of the continuous reaction part is preferably 0.005 to 1000 m, and more preferably 0.01 to 10 m. When the length of the continuous reaction part is within this range, the residence time of the raw material becomes sufficient, the yield of organic peroxide is high, the pressure loss between the raw material supply port and the reaction mixture discharge port can be reduced, and the continuous reaction The flow of fluid in the vessel is stabilized and a laminar flow state can be maintained. The residence time is preferably 0.1 seconds to 5 hours, more preferably 0.2 seconds to 2 hours, and most preferably 0.5 seconds to 1 hour.
本発明において、連続反応部は単独で用いてもよく、複数個並列して用いてもよい。複数個並列して用いる場合には、１〜１０００個が好ましく、１〜１００個がより好ましい。複数個用いることにより、有機ペルオキシドの生産量を制御できる。 In this invention, a continuous reaction part may be used independently and may be used in parallel. When using in parallel, 1 to 1000 is preferable, and 1 to 100 is more preferable. By using a plurality, the production amount of organic peroxide can be controlled.
本発明におけるＲＣ（＝Ｏ）Ｘで表される化合物としては、アシルハライド（Ｒがアルキル基Ｒ’である場合）およびアルキルハロゲン化ホルメート（Ｒがアルコキシ基Ｒ’Ｏである場合）が好ましい。ただし、アルキル基Ｒ’にはフッ素原子が含まれていてもよく、エーテル性の酸素原子が含まれていてもよい。ＸはＣｌ、Ｆ、ＢｒまたはＩを示す。Ｘとしては、ＦまたはＣｌが好ましい。 As the compound represented by RC (═O) X in the present invention, acyl halide (when R is an alkyl group R ′) and alkyl halide formate (when R is an alkoxy group R′O) are preferable. However, the alkyl group R ′ may contain a fluorine atom or an etheric oxygen atom. X represents Cl, F, Br or I. X is preferably F or Cl.
Ｒ’としては、（１）炭素数２〜２０の炭化水素基、（２）炭素数２〜２０の含フッ素炭化水素基、（３）エーテル性の酸素原子を含む炭素数２〜２０の炭化水素基、（４）エーテル性の酸素原子を含む炭素数２〜２０の含フッ素炭化水素基が好ましい。なお、（１）〜（４）の炭化水素基または含フッ素炭化水素基は、直鎖状でも分岐状でも環状でもよい。 R ′ includes (1) a hydrocarbon group having 2 to 20 carbon atoms, (2) a fluorine-containing hydrocarbon group having 2 to 20 carbon atoms, and (3) a carbon atom having 2 to 20 carbon atoms containing an etheric oxygen atom. A hydrogen group and (4) a fluorine-containing hydrocarbon group having 2 to 20 carbon atoms containing an etheric oxygen atom are preferred. In addition, the hydrocarbon group or fluorine-containing hydrocarbon group of (1) to (4) may be linear, branched or cyclic.
該（１）〜（４）としては、それぞれ以下の基が好ましい。
（１）ＣｍＨ２ｍ＋１−（ｍは２〜２０の整数。）、Ｃ６Ｈ５−、Ｃ６Ｈ１１−、
（２）ＣｎＦ２ｎ＋１−（ｎは２〜２０の整数。）、Ｃ６Ｆ５−、Ｃ６Ｆ１１−、
（３）ＣｐＨ２ｐ＋１−ｄ（ＯＣｇＨ２ｇ＋１）ｄＯＣｑＨ２ｑ−（ｐ、ｇ、ｑはそれぞれ独立に１〜７の整数、ｄは０または１〜５の整数、ｐ＋ｇ×ｄ＋ｑ≦２０。）、ＣｕＨ２ｕ＋１Ｏ（ＣｖＨ２ｖＯ）ｅＣｗＨ２ｗ−（ｕ、ｖ、ｗはそれぞれ独立に１〜７の整数、ｅは１〜５の整数、ｕ＋ｖ×ｅ＋ｗ≦２０。）、
（４）ＣｈＦ２ｈ＋１−ａ（ＯＣｉＦ２ｉ＋１）ａＯＣｊＦ２ｊ−（ｈ、ｉ、ｊはそれぞれ独立に１〜７の整数、ａは０または１〜５の整数、ｈ＋ｉ×ａ＋ｊ≦２０。）、ＣｋＦ２ｋ＋１Ｏ（ＣｓＦ２ｓＯ）ｂＣｔＦ２ｔ−（ｋ、ｓ、ｔはそれぞれ独立に１〜７の整数、ｂは１〜５の整数、ｋ＋ｓ×ｂ＋ｔ≦２０。）、下式で表される基（ただし、Ｒｆは炭素数１〜３のポリフルオロアルキル基を示す。）。
As said (1)-(4), the following groups are respectively preferable.
(1) C m H 2m + 1 - (m is 2-20 of integral.), C 6 H 5 - , C 6 H 11 -,
(2) C n F 2n + 1 - (n is 2-20 integer.), C 6 F 5 - , C 6 F 11 -,
(3) C p H 2p + 1-d (OC g H 2g + 1) d OC q H 2q - (p, g, q are each independently 1-7 integer, d is 0 or an integer of 1 to 5, p + g × d + q ≦ 20.), C u H 2u + 1 O (C v H 2v O) e C w H 2w − (u, v, w are each independently an integer of 1-7, e is an integer of 1-5, u + v × e + w ≦ 20.),
(4) Ch F 2h + 1-a (OC i F 2i + 1 ) a OC j F 2j − (h, i, j are each independently an integer of 1-7, a is an integer of 0 or 1-5, h + i × a + j ≦ 20.), C k F 2k + 1 O (C s F 2s O) b C t F 2t − (k, s, t are each independently an integer of 1-7, b is an integer of 1-5, k + s × b + t ≦ 20.), A group represented by the following formula (where R f represents a polyfluoroalkyl group having 1 to 3 carbon atoms).
ＲＣ（＝Ｏ）Ｘで表される化合物であるアシルハライド、アルキルハロゲン化ホルメートとしては、以下の化合物が好ましく挙げられる。
（１）ＣＨ３ＣＨ（ＣＨ３）ＣＯＦ、ＣＨ３Ｃ（ＣＨ３）２ＣＨ２ＣＨ（ＣＨ３）ＣＨ２ＣＯＦ、ＣＨ３（ＣＨ２）６ＣＯＦ、ＣＨ３ＣＨ２ＣＨ２ＯＣＯＦ、ＣＨ３ＣＨ２ＣＨ（ＣＨ３）ＯＣＯＦ、ＣＨ３（ＣＨ２）３ＣＨ（Ｃ２Ｈ５）ＣＨ２ＯＣＯＦ、ＣＨ３ＣＨ（ＣＨ３）ＣＯＣｌ、ＣＨ３Ｃ（ＣＨ３）２ＣＨ２ＣＨ（ＣＨ３）ＣＨ２ＣＯＣｌ、ＣＨ３（ＣＨ２）６ＣＯＦ、ＣＨ３ＣＨ２ＣＨ２ＯＣＯＣｌ、ＣＨ３ＣＨ２ＣＨ（ＣＨ３）ＯＣＯＣｌ、ＣＨ３（ＣＨ２）３ＣＨ（Ｃ２Ｈ５）ＣＨ２ＯＣＯＣｌ、
（２）ＣＦ３ＣＦ２ＣＦ２ＣＯＦ、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＯＦ、Ｃ６Ｆ５ＣＯＦ、Ｃ６Ｆ１１ＣＯＦ、ＣＦ３ＣＦ２ＣＦ２ＣＯＣｌ、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＯＣｌ、Ｃ６Ｆ５ＣＯＣｌ、Ｃ６Ｆ１１ＣＯＣｌ、
（３）ＣＨ３ＣＨ２ＯＣＨ２ＣＨ２ＯＣＯＦ、ＣＨ３ＣＨ（ＯＣＨ３）ＣＨ２ＣＨ２ＯＣＯＦ、ＣＨ３ＣＨ２ＯＣＨ２ＣＨ２ＯＣＯＣｌ、ＣＨ３ＣＨ（ＯＣＨ３）ＣＨ２ＣＨ２ＯＣＯＣｌ、
（４）Ｃ３Ｆ７ＯＣＦ（ＣＦ３）ＣＯＦ、Ｃ３Ｆ７ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＯＦ、Ｃ３Ｆ７ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＯＦ、ＣＦ３ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ４）ＣＯＦ、ＣＦ３ＣＦ２ＣＦ２ＣＯＦ、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＯＦ、ＣＦ３ＯＣＦ２ＣＦ２ＯＣＦ２ＣＯＦ、ＣＦ３Ｏ（ＣＦ２ＣＦ２Ｏ）２ＣＦ２ＣＯＦ、ＣＦ３Ｏ（ＣＦ２ＣＦ２Ｏ）３ＣＦ２ＣＯＦ、ＣＦ３ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＯＦ、ＣＦ３Ｏ［ＣＦ（ＣＦ３）ＣＦ２］２ＯＣＦ２ＣＯＦ、ＣＦ３ＯＣＦ（ＣＦ３）ＣＦ２（ＯＣＦ２）２ＣＯＦ、ＣＦ３Ｏ［ＣＦ（ＣＦ３）ＣＦ２］２（ＯＣＦ２）２ＣＯＦ、Ｃ３Ｆ７ＯＣＦ（ＣＦ３）ＣＯＣｌ、Ｃ３Ｆ７ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＯＣｌ、Ｃ３Ｆ７ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＯＣｌ、ＣＦ３ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ４）ＣＯＣｌ、ＣＦ３ＣＦ２ＣＦ２ＣＯＣｌ、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＯＣｌ、ＣＦ３ＯＣＦ２ＣＦ２ＯＣＦ２ＣＯＣｌ、ＣＦ３Ｏ（ＣＦ２ＣＦ２Ｏ）２ＣＦ２ＣＯＣｌ、ＣＦ３Ｏ（ＣＦ２ＣＦ２Ｏ）３ＣＦ２ＣＯＣｌ、ＣＦ３ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＯＣｌ、ＣＦ３Ｏ［ＣＦ（ＣＦ３）ＣＦ２］２ＯＣＦ２ＣＯＣｌ、ＣＦ３ＯＣＦ（ＣＦ３）ＣＦ２（ＯＣＦ２）２ＣＯＣｌ、ＣＦ３Ｏ［ＣＦ（ＣＦ３）ＣＦ２］２（ＯＣＦ２）２ＣＯＣｌ、下記化合物。
Preferred examples of the acyl halide and alkyl halide formate that are compounds represented by RC (═O) X include the following compounds.
(1) CH 3 CH (CH 3) COF, CH 3 C (CH 3) 2 CH 2 CH (CH 3) CH 2 COF, CH 3 (CH 2) 6 COF, CH 3 CH 2 CH 2 OCOF, CH 3 CH 2 CH (CH 3) OCOF , CH 3 (CH 2) 3 CH (C 2 H 5) CH 2 OCOF, CH 3 CH (CH 3) COCl, CH 3 C (CH 3) 2 CH 2 CH (CH 3 ) CH 2 COCl, CH 3 (CH 2 ) 6 COF, CH 3 CH 2 CH 2 OCOCl, CH 3 CH 2 CH (CH 3 ) OCOCl, CH 3 (CH 2 ) 3 CH (C 2 H 5 ) CH 2 OCOCl ,
(2) CF 3 CF 2 CF 2 COF, CF 3 CF 2 CF 2 CF 2 COF, C 6 F 5 COF, C 6 F 11 COF, CF 3 CF 2 CF 2 COCl, CF 3 CF 2 CF 2 CF 2 COCl , C 6 F 5 COCl, C 6 F 11 COCl,
(3) CH 3 CH 2 OCH 2
(4) C 3 F 7 OCF (CF 3) COF, C 3 F 7 OCF (CF 3) CF 2 OCF (CF 3) COF, C 3 F 7 OCF (CF 3) CF 2 OCF (CF 3) CF 2 OCF (CF 3 ) COF, CF 3 OCF (CF 3 ) CF 2 OCF (CF 4 ) COF, CF 3 CF 2 CF 2 COF, CF 3 CF 2 CF 2 CF 2 COF, CF 3 OCF 2 CF 2 OCF 2 COF , CF 3 O (CF 2 CF 2 O) 2 CF 2 COF, CF 3 O (CF 2 CF 2 O) 3 CF 2 COF, CF 3 OCF (CF 3 ) CF 2 OCF 2 COF, CF 3 O [CF ( CF 3 ) CF 2 ] 2 OCF 2 COF, CF 3 OCF (CF 3 ) CF 2 (OCF 2 ) 2 COF, CF 3 O [CF (CF 3 ) CF 2 ] 2 (OCF 2 ) 2 COF, C 3 F 7 OCF (CF 3 ) COCl, C 3 F 7 OCF (CF 3 ) CF 2 OCF (CF 3 ) COCl, C 3 F 7 OCF (CF 3 ) CF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) COCl, CF 3 OCF (CF 3 ) CF 2 OCF (CF 4 ) COCl, CF 3 CF 2 CF 2 COCl, CF 3 CF 2 CF 2 CF 2 COCl, CF 3 OCF 2 CF 2 OCF 2 COCl , CF 3 O (CF 2 CF 2 O) 2 CF 2 COCl, CF 3 O (CF 2 CF 2 O) 3 CF 2 COCl, CF 3 OCF (CF 3) CF 2 OCF 2 COCl, CF 3 O [CF ( CF 3) CF 2] 2 OCF 2 COCl, CF 3 OCF (CF 3) CF 2 (OCF 2) 2 COCl, CF 3 O [CF (CF ) CF 2] 2 (OCF 2 ) 2 COCl, the following compound.
本発明におけるジアシルペルオキシドとしては［Ｒ’（Ｃ＝Ｏ）Ｏ］２が好ましく、ジアルキルペルオキシジカーボネートとしては［Ｒ’Ｏ（Ｃ＝Ｏ）Ｏ］２が好ましい。ただし、式中のＲ’は前記と同じ意味を示す。ジアシルペルオキシド、ジアルキルペルオキシジカーボネートとしては、以下の化合物が好ましく挙げられる。 In the present invention, the diacyl peroxide is preferably [R ′ (C═O) O] 2 , and the dialkyl peroxydicarbonate is preferably [R′O (C═O) O] 2 . However, R ′ in the formula has the same meaning as described above. Preferred examples of diacyl peroxide and dialkyl peroxydicarbonate include the following compounds.
（１）［ＣＨ３ＣＨ（ＣＨ３）ＣＯＯ］２、［ＣＨ３Ｃ（ＣＨ３）２ＣＨ２ＣＨ（ＣＨ３）ＣＨ２ＣＯＯ］２、［ＣＨ３（ＣＨ２）６ＣＯＯ］２、［ＣＨ３ＣＨ２ＣＨ２ＯＣＯＯ］２、［ＣＨ３ＣＨ（ＣＨ３）ＯＣＯＯ］２、［ＣＨ３ＣＨ２ＣＨ（ＣＨ３）ＯＣＯＯ］２、［ＣＨ３（ＣＨ２）３ＣＨ（Ｃ２Ｈ５）ＣＨ２ＯＣＯＯ］２、
（２）［ＣＦ３ＣＦ２ＣＦ２ＣＯＯ］２、［ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＯＯ］２、［Ｃ６Ｆ５ＣＯＯ］２、［Ｃ６Ｆ１１ＣＯＯ］２、
（３）［ＣＨ３ＣＨ２ＯＣＨ２ＣＨ２ＯＣＯＯ］２、［ＣＨ３ＣＨ（ＯＣＨ３）ＣＨ２ＣＨ２ＯＣＯＯ］２、
（４）［Ｃ３Ｆ７ＯＣＦ（ＣＦ３）ＣＯＯ］２、［Ｃ３Ｆ７ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＯＯ］２、［Ｃ３Ｆ７ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＯＯ］２、［ＣＦ３ＯＣＦ（ＣＦ３）ＣＯＯ］２、［ＣＦ３ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＯＯ］２、［ＣＦ３ＯＣＦ２ＣＦ２ＯＣＦ２ＣＯＯ］２、［ＣＦ３Ｏ（ＣＦ２ＣＦ２Ｏ）２ＣＦ２ＣＯＯ］２、［ＣＦ３Ｏ（ＣＦ２ＣＦ２Ｏ）３ＣＦ２ＣＯＯ］２、［ＣＦ３ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＯＯ］２、［ＣＦ３Ｏ［ＣＦ（ＣＦ３）ＣＦ２］２ＯＣＦ２ＣＯＯ］２、［ＣＦ３ＯＣＦ（ＣＦ３）ＣＦ２（ＯＣＦ２）２ＣＯＯ］２、［ＣＦ３Ｏ［ＣＦ（ＣＦ３）ＣＦ２］２（ＯＣＦ２）２ＣＯＯ］２、下記有機ペルオキシド。
(1) [CH 3 CH (CH 3 ) COO] 2 , [CH 3 C (CH 3 ) 2 CH 2 CH (CH 3 ) CH 2 COO] 2 , [CH 3 (CH 2 ) 6 COO] 2 , [ CH 3 CH 2 CH 2 OCOO] 2, [
(2) [CF 3 CF 2 CF 2 COO] 2 , [CF 3 CF 2 CF 2 CF 2 COO] 2 , [C 6 F 5 COO] 2 , [C 6 F 11 COO] 2 ,
(3) [CH 3 CH 2 OCH 2 CH 2 OCOO] 2 , [CH 3 CH (OCH 3 ) CH 2 CH 2 OCOO] 2 ,
(4) [C 3 F 7 OCF (CF 3) COO] 2, [C 3
本発明の製造方法と同様の方法を用いて、以下の有機化合物を製造することができる。 The following organic compounds can be produced using a method similar to the production method of the present invention.
ＣＨ３ＣＨ（ＣＨ３）ＯＯＨ、ＣＨ３ＣＨ（ＣＨ３）ＣＯＯＣＨ（ＣＨ３）ＣＨ３、ＣＨ３ＣＨ（ＣＨ３）Ｃ（Ｏ）ＯＯＨ、ＣＨ３ＣＨ（ＣＨ３）Ｃ（Ｏ）ＯＯＣＨ（ＣＨ３）ＣＨ３、ＣＨ３ＣＨ（ＣＨ３）Ｃ（Ｏ）ＯＯＣ（Ｏ）ＣＨ（ＣＨ３）ＣＨ３。
CH 3 CH (CH 3 ) OOH, CH 3 CH (CH 3 ) COOCH (CH 3 ) CH 3 , CH 3 CH (CH 3 ) C (O) OOH, CH 3 CH (CH 3 ) C (O) OOCH ( CH 3) CH 3, CH 3 CH (CH 3) C (O) OOC (O) CH (CH 3)
本発明においては、有機ペルオキシドを製造する際に溶媒を用いることが好ましい。該溶媒としては、ＲＣ（＝Ｏ）Ｘで表される化合物および有機ペルオキシドの溶解性に優れ、過酸化物との反応性がない溶媒が好ましい。溶媒は１種を用いてもよく、２種以上を用いてもよい。 In the present invention, it is preferable to use a solvent when producing the organic peroxide. As the solvent, a solvent excellent in solubility of the compound represented by RC (═O) X and the organic peroxide and having no reactivity with the peroxide is preferable. 1 type may be used for a solvent and 2 or more types may be used for it.
有機ペルオキシドが含フッ素化合物の場合の溶媒としては、フルオロカーボンが好ましく、ＣＦ３ＣＨ２ＣＦ２Ｈ、ＣＦ３ＣＦ２ＣＨ２ＣＦ２Ｈ、ＣＨＣｌＦＣＦ２ＣＦ２Ｃｌ、Ｆ（ＣＦ２）４ＯＣＨ３、Ｆ（ＣＦ２）４ＯＣ２Ｈ５、Ｈ（ＣＦ２）４ＯＣＨ３、Ｈ（ＣＦ２）４ＯＣ２Ｈ５、ペルフルオロ（ブチルテトラヒドロフラン）、ペルフルオロ（プロピルテトラヒドロピラン）等がより好ましい。 As the solvent in the case where the organic peroxide is a fluorine-containing compound, fluorocarbon is preferable, and CF 3 CH 2 CF 2 H, CF 3 CF 2 CH 2 CF 2 H, CHClFCF 2 CF 2 Cl, F (CF 2 ) 4 OCH 3 , More preferred are F (CF 2 ) 4 OC 2 H 5 , H (CF 2 ) 4 OCH 3 , H (CF 2 ) 4 OC 2 H 5 , perfluoro (butyltetrahydrofuran), perfluoro (propyltetrahydropyran) and the like.
また、有機ペルオキシドが含フッ素化合物以外の化合物の場合の溶媒としては、ハイドロカーボンまたはフルオロカーボンが好ましく、ヘキサン、シクロヘキサン、トルエン、ミネラルスピリッツ、ＣＦ３ＣＨ２ＣＦ２Ｈ、ＣＦ３ＣＦ２ＣＨ２ＣＦ２Ｈ、ＣＨＣｌＦＣＦ２ＣＦ２Ｃｌ、Ｆ（ＣＦ２）４ＯＣＨ３、Ｆ（ＣＦ２）４ＯＣ２Ｈ５、Ｈ（ＣＦ２）４ＯＣＨ３、Ｈ（ＣＦ２）４ＯＣ２Ｈ５、ペルフルオロ（ブチルテトラヒドロフラン）、ペルフルオロ（プロピルテトラヒドロピラン）等がより好ましい。 Further, as the solvent when the organic peroxide is a compound other than the fluorine-containing compound, hydrocarbon or fluorocarbon is preferable, and hexane, cyclohexane, toluene, mineral spirits, CF 3 CH 2 CF 2 H, CF 3 CF 2 CH 2 CF 2. H, CHClFCF 2 CF 2 Cl, F (CF 2 ) 4 OCH 3 , F (CF 2 ) 4 OC 2 H 5 , H (CF 2 ) 4 OCH 3 , H (CF 2 ) 4 OC 2 H 5 , perfluoro ( Butyltetrahydrofuran), perfluoro (propyltetrahydropyran) and the like are more preferable.
本発明における過酸化物としては、過酸化水素、過酸化ナトリウム、過酸化バリウムまたは過酸化カリウムが好ましく、過酸化水素がより好ましい。過酸化物は、１種を用いるのが好ましい。該過酸化物は、水溶液として用いることが好ましい。 As the peroxide in the present invention, hydrogen peroxide, sodium peroxide, barium peroxide or potassium peroxide is preferable, and hydrogen peroxide is more preferable. One peroxide is preferably used. The peroxide is preferably used as an aqueous solution.
本発明におけるアルカリ化合物としては、アルカリ金属水酸化物が好ましく、水酸化ナトリウム、水酸化カリウム、水酸化リチウムまたは水酸化セシウムがより好ましく、水酸化ナトリウム、水酸化カリウムが最も好ましい。該アルカリ化合物は、水溶液として用いるのが好ましい。 The alkali compound in the present invention is preferably an alkali metal hydroxide, more preferably sodium hydroxide, potassium hydroxide, lithium hydroxide or cesium hydroxide, and most preferably sodium hydroxide or potassium hydroxide. The alkali compound is preferably used as an aqueous solution.
過酸化物として過酸化水素を用いる場合の原料の供給量はモル比で、ＲＣ（＝Ｏ）Ｘで表される化合物／過酸化水素／アルカリ化合物＝１／０．３〜２０／０．３〜１０が好ましく、１／０．５〜１０／０．５〜７がより好ましい。また過酸化水素以外の過酸化物を用いる場合の原料の供給量はモル比で、ＲＣ（＝Ｏ）Ｘで表される化合物／過酸化物／アルカリ化合物＝１／０．３〜２０／０．３〜１０が好ましく、１／０．５〜１５／０．５〜７がより好ましい。該範囲であると、有機ペルオキシドの収率が高く、反応に要する時間が短い。 When hydrogen peroxide is used as the peroxide, the feed amount of the raw material is a molar ratio of a compound represented by RC (= O) X / hydrogen peroxide / alkali compound = 1 / 0.3 to 20 / 0.3. To 10 is preferable, and 1 / 0.5 to 10 / 0.5 to 7 is more preferable. In addition, when a peroxide other than hydrogen peroxide is used, the supply amount of the raw material is a molar ratio of a compound represented by RC (= O) X / peroxide / alkali compound = 1 / 0.3 to 20/0. 3 to 10 is preferable, and 1 / 0.5 to 15 / 0.5 to 7 is more preferable. Within this range, the yield of organic peroxide is high and the time required for the reaction is short.
過酸化物およびアルカリ化合物を水溶液として用いる場合の水溶液の濃度は、合計で１〜６０質量％が好ましく、５〜３０質量％がより好ましい。該範囲であると、有機ペルオキシドの収率が高い。本発明の製造方法における反応の温度は、−３０〜５０℃が好ましい。該温度であると、反応時間が短く、生成した有機ペルオキシドが分解しにくく、有機ペルオキシドの収率が高い。 When the peroxide and the alkali compound are used as the aqueous solution, the concentration of the aqueous solution is preferably 1 to 60% by mass in total, and more preferably 5 to 30% by mass. Within this range, the yield of organic peroxide is high. The reaction temperature in the production method of the present invention is preferably -30 to 50 ° C. If it is this temperature, reaction time is short, the produced | generated organic peroxide is hard to decompose | disassemble, and the yield of an organic peroxide is high.
本発明において、連続反応部内を流れる有機相、水相および反応混合物の流速は０．００１〜１００ｍＬ／秒が好ましく、０．０１〜５０ｍＬ／秒がより好ましい。該範囲であると、単位時間当たりの有機ペルオキシドの生成量が多く、原料および反応混合物の流れが安定であり、有機ペルオキシドの収率が高い。 In the present invention, the flow rate of the organic phase, the aqueous phase and the reaction mixture flowing in the continuous reaction part is preferably 0.001 to 100 mL / second, more preferably 0.01 to 50 mL / second. Within this range, the amount of organic peroxide produced per unit time is large, the flow of raw materials and reaction mixture is stable, and the yield of organic peroxide is high.
以下に、実施例（例１、２）、比較例（例３）、参考例（例４）を用いて本発明を詳細に説明するが、本発明はこれらに限定されない。 Hereinafter, the present invention will be described in detail using Examples (Examples 1 and 2), Comparative Examples (Example 3), and Reference Examples (Example 4), but the present invention is not limited thereto.
なお、有機ペルオキシドの分析方法は以下に示すヨードメトリー法を用いた。
内容積２００ｍＬの共栓付き三角フラスコに、イソプロピルアルコールの３０ｍＬ、氷酢酸の２ｍＬ、飽和ヨウ化カリウム水溶液の２ｍＬをこの順序で入れ、ついで有機ペルオキシドを含む試料の５ｇを秤量型ピペットを用いて正しくはかり入れる。密栓してフラスコを軽くゆり動かして内容物を混合し、暗所で１０分間反応させた後、チオ硫酸ナトリウム（０．１モル／Ｌ）溶液を用いてヨウ素の色が消えるまで滴定する。滴定に要したチオ硫酸ナトリウムの体積（単位：ｍＬ）を用いて、質量百分率＝（ｎ×Ｆ×１００×Ｍｗ）／（２００００×Ｓａ）の式により、試料に含まれる有機ペルオキシドの質量百分率（単位：質量％）を算出する。ただし、前記式における記号は以下の意味を示す。
ｎ：滴定に要したチオ硫酸ナトリウム溶液（０．１モル／Ｌ）の体積［ｍＬ］
Ｆ：チオ硫酸ナトリウム溶液（０．１モル／Ｌ）のファクター
Ｍｗ：有機ペルオキシドの分子量
Ｓａ：試料の質量［ｇ］。
In addition, the iodometry method shown below was used for the analysis method of organic peroxide.
Into a 200 mL stoppered Erlenmeyer flask, add 30 mL of isopropyl alcohol, 2 mL of glacial acetic acid, and 2 mL of saturated potassium iodide aqueous solution in this order, and then correctly transfer 5 g of the sample containing organic peroxide using a weighing pipette. Scale in. Seal the flask and gently shake the flask to mix the contents, react for 10 minutes in the dark, and then titrate with the sodium thiosulfate (0.1 mol / L) solution until the iodine color disappears. Using the volume of sodium thiosulfate required for titration (unit: mL), the mass of organic peroxide contained in the sample by the formula: mass percentage = (n × F × 100 × M w ) / (20000 × S a ) The percentage (unit: mass%) is calculated. However, the symbols in the above formulas have the following meanings.
n: Volume of sodium thiosulfate solution (0.1 mol / L) required for titration [mL]
F: Factor of sodium thiosulfate solution (0.1 mol / L) M w : Molecular weight of organic peroxide S a : Mass of sample [g].
［例１］
図２に示す装置（反応器の連続反応部１２の断面積は７．５ｍｍ２、長さは２ｃｍ。）を使用した。
原料として、シリンジ６に水酸化カリウムの水溶液（２．５モル／Ｌ）の２５ｇ、シリンジ７に過酸化水素の水溶液（１３．６質量％）の２２．０ｇ、シリンジ８にペルフルオロ（２，５−ジメチル−３，６−ジオキサノナノイルフルオリド）（以下、アシルフルオリドＡと記す。）の３．３ｇおよびＣＨＣｌＦＣＦ２ＣＦ２Ｃｌの２３．３ｇ（以下、合わせてアシルフルオリド溶液Ａと記す。）を充填した。
[Example 1]
The apparatus shown in FIG. 2 (the cross-sectional area of the continuous reaction part 12 of the reactor is 7.5 mm 2 and the length is 2 cm) is used.
As raw materials, 25 g of an aqueous potassium hydroxide solution (2.5 mol / L) was added to the syringe 6, 22.0 g of an aqueous hydrogen peroxide solution (13.6% by mass) to the
シリンジ６、７、８から製品回収タンク１３までの装置全体を、ジャケット方式の冷媒を用いて５℃に冷却し、５℃に保持しながら、各原料を送液プランジャー９、１０、１１を用いて、水酸化カリウムの水溶液を０．７８ｍＬ／分、過酸化水素の水溶液を０．２０ｍＬ／分、アシルフルオリド溶液Ａを１．０ｍＬ／分の流速で、連続反応部でのＲｅが９１．５となるように２０分間かけて送液し、反応を行って反応混合物を得た。
The entire apparatus from the
２相分離用装置１３に回収されたジアシルペルオキシドを含む反応混合物は２相分離しており、上相が水層、下相がジアシルペルオキシドを含む有機相であった。下相を製品回収タンク１４に回収後、回収液と同量の冷水を用いて洗浄を２回行った。さらに硫酸マグネシウムを用いて脱水を行い、有機ペルオキシドを含む溶液の２５．１ｇを得た。１９Ｆ−ＮＭＲを用いて有機ペルオキシドのすべてがジ（ペルフルオロ−２，５−ジメチル−３，６−ジオキサノナノイル）ペルオキシドであることを確認した。ヨードメトリー法による分析結果の収量は２．９７ｇであり、アシルフルオリド溶液Ａを基準とした収率は９０モル％であった。 The reaction mixture containing diacyl peroxide recovered in the two-phase separation apparatus 13 was separated into two phases, the upper phase being an aqueous layer and the lower phase being an organic phase containing diacyl peroxide. After the lower phase was recovered in the product recovery tank 14, washing was performed twice using the same amount of cold water as the recovered liquid. Furthermore, dehydration was performed using magnesium sulfate to obtain 25.1 g of a solution containing an organic peroxide. 19 F-NMR was used to confirm that all of the organic peroxide was di (perfluoro-2,5-dimethyl-3,6-dioxanonanoyl) peroxide. The yield of the analysis result by the iodometry method was 2.97 g, and the yield based on the acyl fluoride solution A was 90 mol%.
［例２］
例１と同じ装置を使用し、シリンジ６に水酸化カリウムの水溶液（５．５モル／Ｌ）の２５ｇ、シリンジ７に過酸化水素の水溶液（３０質量％）の２２．０ｇ、シリンジ８にイソプロピルクロロホルメートの１．７６ｇおよびＣＨＣｌＦＣＦ２ＣＦ２Ｃｌの２３．３ｇを充填し、水酸化カリウムの水溶液を０．７８ｍＬ／分、過酸化水素の水溶液を０．２０ｍＬ／分、イソプロピルクロロホルメートを０．１２ｍＬ／分の流速、Ｒｅを４１．９とした以外は例１と同様にして反応混合物を得た。
[Example 2]
Using the same apparatus as in Example 1, 25 g of an aqueous potassium hydroxide solution (5.5 mol / L) was added to the syringe 6, 22.0 g of an aqueous hydrogen peroxide solution (30% by mass) was added to the
２相分離用装置１３に回収されたペルオキシジカーボネートを含む反応混合物は２相分離しており、上相が水相、下相がジアルキルペルオキシジカーボネートを含む有機相であった。下相を製品回収タンク１４に回収後、例１と同様にして洗浄、脱水を行った。１Ｈ−ＮＭＲを用いて有機ペルオキシドのすべてがジイソプロピルペルオキシジカーボネートであることを確認した。ヨードメトリー法による分析結果の収量は１．４８ｇであり、イソプロピルクロロホルメートを基準とした収率は８４モル％であった。 The reaction mixture containing peroxydicarbonate recovered in the two-phase separation apparatus 13 was separated into two phases, the upper phase being an aqueous phase and the lower phase being an organic phase containing dialkylperoxydicarbonate. The lower phase was recovered in the product recovery tank 14, and then washed and dehydrated in the same manner as in Example 1. 1 H-NMR was used to confirm that all of the organic peroxide was diisopropyl peroxydicarbonate. The yield of the analysis result by the iodometry method was 1.48 g, and the yield based on isopropyl chloroformate was 84 mol%.
［例３］
撹拌装置、温度計および滴下漏斗を備えた３００ｍＬの四つ口フラスコに、水酸化ナトリウムの２．４ｇ（０．０６モル）および水の１１７．６ｇを入れて溶解させた。次に、撹拌下にて、溶媒のＣＨＣｌＦＣＦ２ＣＦ２Ｃｌの１２０ｇを添加し、約−５℃に冷却した後、過酸化水素水の水溶液（３０質量％）の６．６ｇ（０．０６モル）を添加した。
[Example 3]
In a 300 mL four-necked flask equipped with a stirrer, a thermometer, and a dropping funnel, 2.4 g (0.06 mol) of sodium hydroxide and 117.6 g of water were dissolved. Next, 120 g of the solvent CHClFCF 2 CF 2 Cl was added under stirring and cooled to about −5 ° C., and then 6.6 g (0.06 mol) of an aqueous solution of hydrogen peroxide (30% by mass). ) Was added.
次いでアシルフルオリド溶液Ａの２０ｇ（０．０４モル）とＣＨＣｌＦＣＦ２ＣＦ２Ｃｌのｌ２０ｇとを、−５℃〜５℃の範囲に保ちながら２０分間かけて滴下し、撹拌下にて３０分間反応を行い反応液を得た。反応終了後、かなりの泡立ちが観察され、水相と有機相にきれいに２相分離しなかった。 Next, 20 g (0.04 mol) of acyl fluoride solution A and 120 g of CHClFCF 2 CF 2 Cl were added dropwise over 20 minutes while maintaining the temperature in the range of −5 ° C. to 5 ° C., and the reaction was performed for 30 minutes with stirring. To obtain a reaction solution. After completion of the reaction, considerable foaming was observed, and the two phases were not separated cleanly into the aqueous phase and the organic phase.
アシルペルオキシドを含む有機相を分離した後、２００ｍＬの水を用いて該有機相を２回洗浄し、有機ペルオキシドを含む溶液の１１５．４ｇを得た。１９Ｆ−ＮＭＲを用いて有機ペルオキシドのすべてがジ（ペルフルオロ−２，５−ジメチル−３，６−ジオキサノナノイル）ペルオキシドであることを確認した。ヨードメトリー法による分析結果の収量は１０．０ｇであり、アシルフルオリドＡを基準とした収率は５０モル％であった。 After separating the organic phase containing the acyl peroxide, the organic phase was washed twice with 200 mL of water to obtain 115.4 g of a solution containing the organic peroxide. 19 F-NMR was used to confirm that all of the organic peroxide was di (perfluoro-2,5-dimethyl-3,6-dioxanonanoyl) peroxide. The yield of the analysis result by the iodometry method was 10.0 g, and the yield based on acyl fluoride A was 50 mol%.
［例４］ｔＢｕＣ（Ｏ）ＯＯｔＢｕ（ＴＢＰＰ）合成
＜反応式＞ｔＢｕＣ（Ｏ）Ｃｌ（化合物名：ピバロイルクロリド）＋ｔＢｕＯＯＨ（略称：ＴＢＨＰ）＋ＫＯＨ→ｔＢｕＣ（Ｏ）ＯＯｔＢｕ（略称：ＴＢＰＰ）
装置は、流路幅５００μｍ、反応流路長４５０ｍｍのマイクロリアクターを使用した。シリンジ６に蒸留水の４ｍＬに水酸化カリウムの２４ｍｍｏｌ（１．８８ｇ）を溶解したもの、シリンジ７にＣ６Ｆ１３Ｈの２．６ｍＬにピバロイルクロリドの２０ｍｍｏｌ（２．４２ｇ）を溶解したもの、シリンジ８に７０％のＴＢＨＰ水溶液の６．１８ｇ（ＴＢＨＰの４８ｍｍｏｌに相当）を充填した。シリンジポンプから製品回収タンクまでは例１の装置と同様にしてジャケット方式の冷媒を用いて０℃に冷却し、０℃に保持しながら、各原料を送液プランジャーを用いて、水酸化カリウムの水溶液を１ｍＬ／分、ピバロイルクロリド溶液を１ｍＬ／分、ＴＢＨＰ水溶液を１．３３ｍＬ／分の流速で、連続反応部でのＲｅが１２５となるように５分間かけて送液し、反応を行って粗反応混合物を得た。
[Example 4] t BuC (O) OO t Bu (TBPP) Synthesis <Reaction formula> t BuC (O) Cl (Compound name: pivaloyl chloride) + t BuOOH (abbreviated: TBHP) + KOH → t BuC (O) OO t Bu (abbreviation: TBPP)
The apparatus used was a microreactor having a channel width of 500 μm and a reaction channel length of 450 mm. In syringe 6, 24 mmol (1.88 g) of potassium hydroxide was dissolved in 4 mL of distilled water, and in
得られた粗反応生成物を、分液ロートを用いて分離し、有機相を炭酸水素ナトリウム水溶液および食塩水を用いて洗浄し、ついで硫酸マグネシウムを用いて脱水し、ＴＢＰＰを含む生成物の１０．９ｇを得た。１Ｈ−ＮＭＲ、ＩＲを用いて生成物のすべてがＴＢＰＰであることを確認した。ヨードメトリー法による分析結果の収量は２．９９ｇであり、ピバロイルクロリドを基準とした収率は８６モル％であった。 The resulting crude reaction product is separated using a separatory funnel, and the organic phase is washed with aqueous sodium bicarbonate and brine, then dehydrated with magnesium sulfate, and 10% of the product containing TBPP. .9 g was obtained. All of the products were confirmed to be TBPP using 1 H-NMR and IR. The yield of the analysis result by the iodometry method was 2.99 g, and the yield based on pivaloyl chloride was 86 mol%.
本発明の製造方法によれば、有機ペルオキシドを収率よく、安全に、大量生産できる。 According to the production method of the present invention, an organic peroxide can be mass-produced with good yield and safely.
１：供給口（１）
２：供給口（２）
３：連続流路
４：連続反応部
５：排出口
６：アルカリ化合物供給用シリンジ
７：過酸化物供給用シリンジ
８：ＲＣ（＝Ｏ）Ｘ供給用シリンジ
９：送液プランジャー
１０：送液プランジャー
１１：送液プランジャー
１２：連続反応部
１３：２相分離用装置
１４：製品回収タンク
1: Supply port (1)
2: Supply port (2)
3: Continuous flow path 4: Continuous reaction part 5: Discharge port 6: Syringe for supplying alkali compound 7: Syringe for supplying peroxide 8: Syringe for supplying RC (= O) X 9: Liquid feeding plunger 10: Liquid feeding Plunger 11: Liquid feeding plunger 12: Continuous reaction unit 13: Two-phase separation device 14: Product recovery tank
Claims (6)
The method according to claim 1, 2, 3, 4 or 5, wherein the alkali compound is sodium hydroxide, potassium hydroxide, lithium hydroxide or cesium hydroxide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9550731B2 (en) | 2014-05-22 | 2017-01-24 | Honeywell Federal Manufacturing & Technologies, Llc | Method for phase transfer synthesis of organic peroxides |
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| JP4835050B2 (en) * | 2005-06-29 | 2011-12-14 | 旭硝子株式会社 | Method for producing fluorinated solvent solution of organic peroxide |
| EP2418199B1 (en) * | 2009-04-08 | 2018-06-06 | Asahi Glass Company, Limited | Method of manufacturing a perfluoro organic peroxide |
| JP2011178678A (en) * | 2010-02-26 | 2011-09-15 | Dic Corp | Method for producing alkyl-substituted benzenediol |
| CN104496874A (en) * | 2014-11-26 | 2015-04-08 | 淄博正华助剂股份有限公司 | Method for continuous flow preparation of cumyl peroxyneodecanoate (CNP) |
| JP2017105944A (en) * | 2015-12-10 | 2017-06-15 | ダイキン工業株式会社 | Manufacturing method of peroxidized perfluoropolyoxyalkylene compound |
| CN109553560A (en) * | 2017-08-12 | 2019-04-02 | 上海惠和化德生物科技有限公司 | A kind of online Total continuity stream production technology directly preparing organic peroxide by alcohol or alkane |
| CN109535054A (en) * | 2018-12-04 | 2019-03-29 | 浙江巨圣氟化学有限公司 | A kind of continuous preparation method of perfluoroacyl peroxides |
| CN113260639A (en) * | 2018-12-20 | 2021-08-13 | 索尔维特殊聚合物意大利有限公司 | Process for preparing perhaloacyl peroxides |
| CN111333559A (en) * | 2020-03-18 | 2020-06-26 | 中国天辰工程有限公司 | Method for rapidly preparing peroxyacetic acid by continuous flow |
| CN111233728A (en) * | 2020-03-18 | 2020-06-05 | 中国天辰工程有限公司 | Method for rapidly preparing high-concentration peroxyacetic acid |
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| JPS559067A (en) * | 1978-06-30 | 1980-01-22 | Ppg Industries Inc | Manufacture of peroxydicarbonates |
| JPH0597797A (en) * | 1991-10-14 | 1993-04-20 | Nippon Oil & Fats Co Ltd | Method for producing difluoroalkanoyl peroxide |
| JPH06172303A (en) * | 1992-12-09 | 1994-06-21 | Nippon Oil & Fats Co Ltd | Production of fluoroalkanoyl peroxide |
| JPH10175950A (en) * | 1996-12-19 | 1998-06-30 | Asahi Glass Co Ltd | Production of functional group-containing and fluorine-containing peroxide |
| JP2004099491A (en) * | 2002-09-06 | 2004-04-02 | Nof Corp | Method for producing dialkyl peroxide |
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| US9550731B2 (en) | 2014-05-22 | 2017-01-24 | Honeywell Federal Manufacturing & Technologies, Llc | Method for phase transfer synthesis of organic peroxides |
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