JP5610646B2 - Method for producing alkylene oxide adduct - Google Patents

Description

  The present invention relates to a method for producing an alkylene oxide adduct, and more particularly to a method for producing an alkylene oxide adduct using a microflow reactor having a tube-shaped flow path and a micromixer connected thereto.

  Conventionally, alkylene oxide adducts are generally produced by a batch reaction method. The batch-type reaction method is a method in which an organic compound having active hydrogen atoms as a raw material and a catalyst are charged into an autoclave and injected with alkylene oxide, and then reacted at a predetermined temperature under pressure to produce an alkylene oxide adduct. (For example, see Patent Documents 1 to 3). However, the production method of an alkylene oxide adduct by such a batch type reaction method is 1) the alkylene oxide adduct cannot be continuously produced, and 2) there is a risk of explosion because the addition reaction under a high pressure is performed in a large apparatus. 3) Since it is carried out by gas-liquid reaction, it is difficult to control the temperature and pressure at the time of the addition reaction, coloration is caused, and the molecular weight distribution is widened. 4) The production apparatus is expensive. There are problems such as. As an improvement of such a batch reaction method, a continuous reaction method using a tubular reactor (for example, see Patent Documents 4 and 5) has been proposed. The production method has the following problems: 1) the temperature and pressure during the addition reaction are still difficult to control, coloring occurs, the molecular weight distribution is widened, the quality is lowered, and 2) mass production is difficult.

JP-A-7-48305 JP 2008-50293 A JP 2008-120737 A JP 52-151108 A JP-A-53-90208

  The problem to be solved by the present invention is that an alkylene oxide adduct can be continuously produced at an arbitrary scale from a small scale to a large scale, and the temperature and pressure during the addition reaction can be controlled with high accuracy, resulting in no coloration. The present invention provides a process for producing an alkylene oxide adduct capable of continuously producing a high-quality alkylene oxide adduct having a narrow molecular weight distribution and simultaneously achieving the above.

  As a result of researches to solve the above-mentioned problems, the present inventors have, as a method for producing an alkylene oxide adduct, a microflow reactor having a tube-like channel having a specific inner diameter and a micromixer connected thereto. A predetermined amount of alkylene oxide, an organic compound having a predetermined amount of active hydrogen atoms and an alkali catalyst are continuously supplied from the micromixer to the flow path of the microflow reactor, It has been found that the method of reacting under conditions is correct and suitable.

  That is, the present invention relates to a method for producing an alkylene oxide adduct using a microflow reactor having a tube-shaped flow path and a micromixer connected to a supply port of the microflow reactor. The one having a flow path of ˜2.5 mm, and having two or more independent supply paths as a micromixer and one discharge path connected to the junction of these supply paths, and these supply paths And a discharge passage having an inner diameter of 0.04 to 0.8 mm, a predetermined amount of liquid alkylene oxide from one supply passage of the micromixer, and a predetermined amount of active hydrogen atoms from another supply passage. The organic compound and the alkali catalyst are continuously fed into the micromixer in a liquid state and mixed in the micromixer. The product is continuously discharged from the discharge path and continuously supplied to the microflow reactor, and the reaction is performed while passing under the conditions of the temperature of the flow path of the microflow reactor of 70 to 200 ° C. and the pressure of the supply port of the flow path of 1 to 10 MPa. The present invention relates to a method for producing an alkylene oxide adduct.

  The method for producing an alkylene oxide adduct according to the present invention (hereinafter, simply referred to as the production method of the present invention) uses a specific microflow reactor and a micromixer connected thereto, from the micromixer to the microflow reactor. A method in which an alkylene oxide adduct is obtained by reacting in a flow channel while continuously supplying a predetermined amount of alkylene oxide to the flow channel, and an organic compound having a predetermined amount of active hydrogen atoms and an alkali catalyst in a liquid state. is there.

  The microflow reactor used in the production method of the present invention has a tubular flow path, and the flow path has an inner diameter of 0.15 to 2.5 mm. In the production method of the present invention, a plurality of such microflow reactors can be connected in series and / or in parallel. The plurality of microflow reactors do not necessarily have to have channels having the same inner diameter, and those having channels having different inner diameters can be connected within the above-described range of the inner diameter as necessary. The length of the channel of each microflow reactor, the material of the constituent material, and the like can be appropriately selected depending on the type of the alkylene oxide adduct to be produced.

  Examples of the alkylene oxide to be used in the production method of the present invention include ethylene oxide, propylene oxide, 1,2-butylene oxide, tetrahydrofuran and the like, and among these, ethylene oxide and / or propylene oxide are preferable.

  Examples of the organic compound having an active hydrogen atom used in the production method of the present invention are 1) methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, decyl alcohol, dodecyl alcohol, ethylene 1 to 6 carbon aliphatic alcohols having 1 to 22 carbon atoms such as glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, sorbitol and pentaerythritol, 2) diethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether , Diglycerol, tetraethylene glycol, propylene glycol 1-monomethyl ether and tetrahydrofurf 1 to 6-valent aliphatic alcohols having an ether group such as alcohol, 3) 1 carbon number such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine and dodecylamine ~ 22 monoalkylamines, 4) dimethylamine, diethylamine, propylmethylamine, dibutylamine, pentylmethylamine, hexylmethylamine, octylmethylamine, dinonylamine, dilaurylamine, myristylmethylamine, dicetylamine, stearylmethylamine, arachi Nylmethylamine, 2-tetradecenylmethylamine, 2-pentadecenylmethylamine, 2-octadecenylmethylamine, 15-hexadecenylmethylamine, oleylmethyl C1-22 dialkylamines such as min, linoleylmethylamine and eleostearylmethylamine, 5) in molecules such as monoethanolamine, monoisopropanolamine, diethanolamine, dipropanolamine, triethanolamine and triisopropanolamine 6) Alkyl dialkanol amines and dialkyls having an alkyl group of 1 to 18 carbon atoms such as diethylethanolamine, dibutylethanolamine, ethyldiethanolamine, butyldiethanolamine, stearyldiisopropanolamine, etc. Alkanolamine, 7) N-2-hydroxyethylaminoethylamine, N, N-di (2-hydroxyethyl) aminopropylamine, N, N, N ′, N′- Molecules such as tetra (2-hydroxypropyl) -ethylenediamine and N, N-di (2-hydroxypropyl) -N′-2-hydroxypropyl-N ″, N ″ -di (2-hydroxypropyl) -diethylenetriamine Alkoxylated polyamines having 1 to 5 hydroxyl groups, 8) 1 to 5 hydroxyl groups in molecules such as glycolic acid, lactic acid, malic acid, hydroxybutyric acid, hydroxystearic acid, tartaric acid, tetrahydroxysuccinic acid and gluconic acid 9) Hydroxycarboxylic acid having 9 units, 1 mol of saturated or unsaturated aliphatic monocarboxylic acid having 6 to 18 carbon atoms such as hexanoic acid, octanoic acid, lauric acid, stearic acid, palmitooleic acid, oleic acid, etc. and ethylene glycol Fatty acid monoester of a divalent aliphatic alcohol obtained from 1 mol of butanediol Fatty acid mono- or diester of a trivalent aliphatic alcohol obtained from 1 to 2 mol of the aliphatic monocarboxylic acid and 1 mol of glycerin or trimethylolpropane, 1 to 3 mol of the aliphatic monocarboxylic acid and pentaerythritol 1 A fatty acid mono-triester of a tetravalent aliphatic alcohol obtained from 1 mol of a fatty acid mono-pentaester of a hexavalent aliphatic alcohol obtained from 1-5 mol of the aliphatic monocarboxylic acid and 1 mol of sorbitol, and Examples thereof include partial esters obtained from the above aliphatic monocarboxylic acids and sorbitan or sorbite. Especially, as an organic compound which has an active hydrogen atom, C1-C6 monohydric aliphatic alcohol, C1-C4 bivalent aliphatic alcohol, glycerol, diglycerol, pentaerythritol, carbon number 1 1-6 monoalkylamines and 1-6 carbon dialkylamines are preferred, and monovalent aliphatic alcohols having 1-6 carbon atoms and monoalkylamines having 1-6 carbon atoms are more preferred.

  In the production method of the present invention, an alkali catalyst is used. Examples of such an alkali catalyst include sodium hydroxide, potassium hydroxide, sodium alkoxide, potassium alkoxide and the like. Of these, sodium hydroxide, potassium hydroxide, sodium methoxide and potassium tertiarybutoxide are preferable. Such an alkali catalyst is mixed with an organic compound having an active hydrogen atom and then supplied to the flow path of the microflow reactor.

  In the production method of the present invention, a predetermined amount of alkylene oxide, an organic compound having a predetermined amount of active hydrogen atoms and an alkali catalyst are continuously supplied in a liquid state to the flow path of the microflow reactor, and these are supplied to the microflow reactor. The temperature of the flow path is 70 to 200 ° C., preferably 80 to 180 ° C., and the pressure of the supply port of the flow path is 1 to 10 MPa, preferably 1.5 to 5 MPa, usually 0.5 to 600 minutes, preferably Is reacted for 1 to 200 minutes while passing through the flow path.

  In the production method of the present invention, an alkylene oxide, an organic compound having an active hydrogen atom, and an alkali catalyst are mixed using a micromixer, and the mixture is supplied to a microflow reactor. Such a micromixer has two or more independent supply passages and one discharge passage (liquid feed passage) connected to the junction of these supply passages, and a liquid alkylene oxide from one supply passage. In addition, an organic compound having an active hydrogen atom and an alkali catalyst are continuously supplied to the micromixer in a liquid state from another supply path, and the mixture in the micromixer is continuously discharged from the discharge path to obtain a microflow reactor. Use what you supply to.

  As the micromixer, a micro mixer having an inner diameter of 0.04 to 0.8 mm is used. The cross-sectional shapes of the supply path and the discharge path are not particularly limited, and can be appropriately selected according to the purpose.

  Examples of the micromixer having two supply paths include a T-shaped micromixer and a Y-shaped micromixer. Moreover, a cross-shaped micromixer etc. are mentioned as what has three supply paths.

  Commercially available products can be used as the micromixer described above. For example, a single-mixer and a caterpillar mixer manufactured by Institute Hugh Microtechnique Mainz (IMM), and a trade name Micro manufactured by Microglass. Glass Reactor, CPC Systems' product name Cytos, Yamatake's product name YM-1 type mixer and YM-2 type mixer, Shimadzu GLC's product name mixing tea, Micro Chemical Co., Ltd. product name IMT Examples include chip reactors, trade name Micro High Mixer manufactured by Toray Engineering, and trade name Union Tea manufactured by Swagelok.

  There is no particular limitation on the method of supplying the alkylene oxide, the organic compound having an active hydrogen atom, and the alkali catalyst in the liquid state to the supply path of the micromixer. For example, an organic compound having an active hydrogen atom and an alkali catalyst can be mixed in advance and the mixed solution can be supplied to the supply path of the micromixer.

  In the production method of the present invention, devices such as a flow feeding device, a liquid amount controller, a storage container, a liquid reservoir device, a temperature adjusting device, and a sensor device can be appropriately installed and used according to the purpose.

  According to the present invention, an alkylene oxide adduct can be continuously produced at an arbitrary scale from a small scale to a large scale, and the temperature and pressure during the addition reaction can be controlled with high accuracy, resulting in no coloration and a narrow molecular weight distribution. There is an effect that a high-quality alkylene oxide adduct can be continuously produced and the above can be achieved simultaneously.

  Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.

Test Category 1 (Production of alkylene oxide adduct)
Example 1
A device in which the discharge port (liquid feeding port) of the T-shaped micromixer was connected to the supply port of the microflow reactor was used. A constant amount of ethylene oxide is continuously supplied to the first supply path (inner diameter 0.2 mm) of the T-shaped micromixer, and a mixed solution of methyl alcohol and sodium methoxide is simultaneously determined into the second supply path (inner diameter 0.2 mm). Continuously supplied, ethylene oxide, methyl alcohol, and sodium methoxide were combined and mixed in the discharge path (inner diameter 0.2 mm) of the T-shaped micromixer. Subsequently, the liquid mixture is continuously supplied in a fixed amount from the discharge port of the T-shaped micromixer through the supply port of the microflow reactor to the tube-like channel (made of SUS316, inner diameter 1 mm, length 20 m). An alkylene oxide adduct was obtained by allowing the flow channel to react for 20 minutes under conditions of a tube-shaped flow path temperature of 90 ° C. and a supply port pressure of 2.6 MPa.

-Examples or Reference Examples 2 to 8 and 10
In the same manner as in Example 1, the alkylene oxide adduct of each Example was obtained under the apparatus specifications and reaction conditions described in Table 1.

Comparative Example 1
In the same manner as in Example 1, an alkylene oxide adduct was obtained. The apparatus specifications and reaction conditions are as shown in Table 1. Here, a flow reactor having a flow path with an inner diameter of 81 mm was used, and the reaction was carried out under the condition of a pressure at its supply port of 0.4 MPa.

Comparative Example 2
Contents 2 L of stainless steel autoclave was charged with 100 g of methyl alcohol and 4 g of sodium methoxide, and the inside of the autoclave was replaced with nitrogen three times. Then, ethylene oxide / propylene oxide = 43/57 (mass ratio) at a temperature of 90 ° C. ) Was introduced over 2 hours, during which time the temperature was raised to 140 ° C. Further, aging was performed for 1 hour to complete the reaction. After cooling the reaction system to room temperature, residual traces of ethylene oxide and propylene oxide were removed under reduced pressure to obtain an alkylene oxide adduct.

Comparative Example 3
Contents A 10-liter stainless steel autoclave was charged with 600 g of methyl alcohol and 24.4 g of sodium methoxide, and the interior of the autoclave was replaced with nitrogen three times. Then, 7425 g of ethylene oxide was introduced over 2 hours at a temperature of 90 ° C. As a result, an abnormal reaction accompanied with a rapid temperature rise and pressure rise occurred, so the reaction was stopped, and the mixture was further aged for 1 hour to obtain an alkylene oxide adduct.

Table 1 summarizes the specifications and reaction conditions of the devices used in the above examples.

In Table 1,
AO: alkylene oxide AO-1: ethylene oxide AO-2: ethylene oxide / propylene oxide = 43/57 (mass ratio)
M: Organic compound having an active hydrogen atom M-1: Methyl alcohol M-2: Normal butyl alcohol M-3: Propylamine M-4: Diethylene glycol M-5: Glycerin CA: Alkaline catalyst CA-1: Sodium methoxide CA -2: Sodium hydroxide CA-3: Potassium hydroxide CA-4: Potassium tertiary carboxide Internal diameter and length of microflow reactor: When multiple microflow reactors with different diameters are connected For example, when a microflow reactor having an internal diameter of 0.5 mm and a flow path of 10 m from the micromixer side and a microflow reactor having an internal diameter of 1 mm and a flow path of 20 m are connected, the internal diameter is indicated by 0.5 + 1, The length is indicated by 10 + 20.
Comparative Example 2: As described above, conditions when reaction was performed using a stainless steel autoclave having a content of 2 L (supply port pressure is the maximum pressure in the autoclave).
Comparative Example 3: As described above, the conditions when the reaction was carried out using a 10 L stainless steel autoclave (the supply port pressure was the maximum ultimate pressure in the autoclave, and actually a safety valve operated at 0.9 MPa during the reaction) Opened 4 times).
The same applies to Table 2.

Test Category 2 (Physical properties of produced alkylene oxide adduct)
AO / M (mass ratio), M / EO / PO (molar ratio and mass ratio, EO is ethylene oxide, PO is propylene oxide) were determined for the alkylene oxide adducts produced in each example of test category 1. The hue was evaluated according to the following criteria. Further, the Mw / Mn ratio was determined by the following method. The results are summarized in Table 2.

Evaluation of hue The hue was visually evaluated according to the following criteria.
◎: Colorless ○: Very light color △: Light color ×: Clearly yellow or more Mw: Weight average molecular weight in terms of polystyrene by GPC (gel permeation chromatography) Mn: In terms of polystyrene by GPC (gel permeation chromatography) Number average molecular weight

  As is clear from the results in Table 2, according to the production method of the present invention, a high-quality alkylene oxide adduct having no coloration and a narrow molecular weight distribution can be continuously produced.

Claims (4)

A method of using a micro-mixer connected to the microflow reactor over a supply port of the micro-flow reactor having a tubular flow channel for producing an alkylene oxide adduct, an inner diameter of a micro-flow reactor 0.15 to 2. with 5 having a mm of the channel, also two or more independent supply channel and connected and having a single discharge path of the supply passage and discharge the confluent portion of the supply passage as the micromixer An organic compound having an inner diameter of 0.04 to 0.8 mm and having a predetermined amount of liquid alkylene oxide from one supply path of such a micromixer and a predetermined amount of active hydrogen atoms from the other supply path A compound and an alkali catalyst are continuously supplied into a micromixer in a liquid state, and mixed in the micromixer from a discharge passage. It is characterized by being continuously discharged and continuously supplied to a microflow reactor and reacting while passing under conditions of a temperature of a flow path of the microflow reactor of 70 to 200 ° C. and a pressure of a supply port of the flow path of 1 to 10 MPa. A process for producing an alkylene oxide adduct. The method for producing an alkylene oxide adduct according to claim 1 , wherein the micromixer is a T-shaped micromixer, a Y-shaped micromixer, or a cross-shaped micromixer . Alkylene oxide, method for producing ethylene oxide and / or propylene oxide in a claim 1 Symbol placement of alkylene oxide adducts.   The organic compound having an active hydrogen atom is one or two or more selected from monovalent aliphatic alcohols having 1 to 6 carbon atoms and monoalkylamines having 1 to 6 carbon atoms. A method for producing an alkylene oxide adduct according to one item.