Process for producing alkylene oxide adduct and alkylene oxide adduct

Abstract

A process for producing an alkylene oxide adduct can continuously produce the alkylene oxide adduct by using a microflow reactor having a tubular flow passage and a micromixer connected to a supply port of the microflow reactor. Liquid state alkylene oxide, alkylene catalyst and an organic compound having an active hydrogen atom(s) are reacted while passing therethrough under the conditions of a temperature of the flow passage of 70 to 200 C. and a pressure of the supply port of the flow passage of 1 to 10 MPa.

Claims

1. A process for producing an alkylene oxide adduct, comprising: using a microflow reactor having a tubular flow passage and a micromixer connected to a supply port of the microflow reactor, wherein an apparatus having a flow passage with an inner diameter of 0.15 to 2.5 mm and a length of at least 10 m is used as the microflow reactor, and an apparatus having two or more independent supply routes and a discharge route connected to a confluence part of the supply routes and having inner diameters of the supply routes and the discharge route of 0.07 to 0.2 mm is used as the micromixer, supplying a liquid alkylene oxide reactant to a first supply route of the micromixer, supplying an organic compound reactant having an active hydrogen atom(s) and an alkaline catalyst reactant in a liquid state to a second supply route into the micromixer, and discharging a mixed material mixed in the micromixer from the discharge route of the micromixer into the flow passage of the microflow reactor via the supply port of the microflow reactor, wherein the reactants are reacted while passing through the microflow reactor under conditions of a temperature of the flow passage of the microflow reactor of 70 to 200 C., a pressure at a supply port of the flow passage of 1 to 10 MPa, and with a retention time in the flow passage of at least 20 minutes, to produce an alkylene oxide adduct having a platinum-cobalt scale number of between 0 and 20 and a Mw/Mn ratio of no more than 1.1.

2. The production process of the alkylene oxide adduct according to claim 1, wherein the alkylene oxide is ethylene oxide and/or propylene oxide.

3. The production process of the alkylene oxide adduct according to claim 2, wherein the organic compound having an active hydrogen atom(s) is one or two or more selected from a monovalent aliphatic alcohol having 1 to 6 carbon atoms and a monoalkylamine having 1 to 6 carbon atoms.

4. The production process of the alkylene oxide adduct according to claim 1, wherein the alkylene oxide reactant is ethylene oxide, the organic compound having an active hydrogen atom(s) reactant is methyl alcohol, and the alkaline catalyst reactant is sodium methoxide.

5. The production process of the alkylene oxide adduct according to claim 1, wherein the conditions of the tubular flow passage of the microflow reactor are a temperature of 90 to 160 C. and a pressure at the supply port of 2 to 5 MPa, while passing through the flow passage for 20 to 60 minutes to obtain an alkylene oxide adduct.

Description

EXAMPLES

(1) Test Division 1 (Production of Alkylene Oxide Adduct)

Example 1

(2) As a supply port of a microflow reactor, an apparatus in which a T-shaped micro mixer to which a discharge port (liquid feeding port) had been connected was used. Ethylene oxide was continuously supplied with a fixed quantity to the first supply route (an inner diameter: 0.2 mm) of the T-shaped micro mixer and a mixed solution of methyl alcohol and sodium methoxide was continuously supplied with a fixed quantity to the second supply route (inner diameter: 0.2 mm) simultaneously, whereby ethylene oxide, methyl alcohol and sodium methoxide are joined at the discharge route (inner diameter: 0.2 mm) of the T-shaped micro mixer and mixed. Subsequently, the liquid state mixture was continuously supplied with a fixed quantity from the discharge port of the T-shaped micro mixer to the tubular flow passage (made of SUS316, inner diameter: 1 mm, length: 20 m) through the supply port of the microflow reactor, and reacted under the conditions of a temperature of the tubular flow passage of the microflow reactor of 90 C. and a pressure at the supply port of 2.6 MPa while passing through the flow passage for 20 minutes to obtain an alkylene oxide adduct.

Examples 2 to 12

(3) In the same manner as in Example 1, alkylene oxide adducts of the respective Examples were obtained using the specification of the apparatus and under the reaction conditions mentioned in Table 1.

Comparative Example 1

(4) In the same manner as in Example 1, an alkylene oxide adduct was obtained. The specification of the apparatus and the reaction conditions are as shown in Table 1, and a flow reactor having a flow passage with an inner diameter of 81 mm was herein used and the reaction was carried out under the condition of a pressure of the supply port of 0.4 MPa.

Comparative Example 2

(5) Into an autoclave made of stainless having an inner volume of 2 L were charged 100 g of methyl alcohol and 4 g of sodium methoxide, and after replacing inside the autoclave with nitrogen three times, 1330 g of a mixture of ethylene oxide/propylene oxide=43/57 (mass ratio) was introduced therein over 2 hours under the condition of a temperature at 90 C., during which the temperature was raised to 140 C. Ripening was further carried out for one hour to complete the reaction. The reaction system was cooled to room temperature, the remaining minute amounts of the ethylene oxide and the propylene oxide were removed under reduced pressure to obtain an alkylene oxide adduct.

Comparative Example 3

(6) Into an autoclave made of stainless having an inner volume of 10 L were charged 600 g of methyl alcohol and 24.4 g of sodium methoxide, and after replacing inside the autoclave with nitrogen three times, when 7,425 g of ethylene oxide were introduced therein over 2 hours under the condition at a temperature of 90 C., then, an abnormal reaction occurred accompanied by abrupt temperature-raising and pressure-raising, so that the reaction was stopped and ripening was further carried out for one hour to obtain an alkylene oxide adduct.

(7) Specification of the apparatus used in the above-mentioned respective examples and reaction conditions, etc., were shown in Table 1 all together.

(8) TABLE-US-00001 TABLE 1 T-shaped micro mixer First supply route Second supply route Inner Supply Inner CA/M Supply diameter Kind of AO diameter Kind Kind (mass of CA + M Division (mm) of AO (g/min) (mm) of M of CA ratio) (g/min) Example 1 0.2 AO-1 0.65 0.2 M-1 CA-1 4.06 0.05 2 0.1 AO-2 0.27 0.1 M-2 CA-3 1.62 0.02 3 0.2 AO-1 0.22 0.2 M-3 CA-2 4.07 0.02 4 0.08 AO-2 0.64 0.08 M-4 CA-4 2.26 0.06 5 0.07 AO-1 0.61 0.07 M-5 CA-2 0.33 0.14 6 0.2 AO-1 0.09 0.2 M-1 CA-1 0.31 0.02 7 0.4 AO-2 0.03 0.6 M-5 CA-3 0.43 0.03 8 0.4 AO-1 0.66 0.03 M-1 CA-4 7.19 0.04 9 0.6 AO-1 1.03 0.6 M-2 CA-1 2.43 0.14 10 0.6 AO-2 0.10 0.6 M-2 CA-3 1.49 0.01 11 1 AO-1 0.35 1 M-1 CA-1 8.75 0.01 12 2 AO-1 0.75 2 M-5 CA-1 1.20 0.14 Comparative example 1 9 AO-1 11950 13 M-1 CA-1 4.06 900 2 *2 AO-2 *2 M-1 CA-1 4.06 3 *3 AO-1 *3 M-1 CA-1 4.06 T-shaped micro mixer Flow passage of Discharge microflow reactor route (liquid Pressure feeding route) at Inner Flow Inner Retention supply diameter amount diameter Length time Temperature port Division (mm) (g/min) (mm) (m) (min) ( C.) (MPa) Example 1 0.2 0.70 1 20 20 90 2 2 0.07 0.29 1 + 2 10 + 4 60 140 3 3 0.15 0.23 0.5 40 30 120 2.5 4 0.08 0.71 0.25 + 10 + 40 160 5 0.5 + 20 + 1 + 2 20 + 4 5 0.07 0.75 1 30 30 100 4 6 0.15 0.11 0.1 80 5 80 8 7 0.4 0.05 2 1 60 90 1.4 8 0.4 0.70 1 20 20 90 3.4 9 1 1.17 1 50 30 120 2.9 10 1 0.11 1 10 60 140 3.5 11 1 0.35 1 + 2 20 + 10 120 140 4 12 2 0.89 1 + 2 + 3 1 + 2 + 3 30 100 2 Comparative example 1 81 12850 81 67 24 120 0.4 2 *2 *2 *2 *2 90-140 0.5 3 *3 *3 *3 *3 90-140 0.9

(9) In Table 1, AO: Alkylene oxide AO-1: Ethylene oxide AO-2: Ethylene oxide/propylene oxide=43/57(mass ratio) M: Organic compound having active hydrogen atom(s) M-1: Methyl alcohol M-2: Normal butyl alcohol M-3: Propylamine M-4: Diethylene glycol M-5: Glycerin CA: Alkali catalyst CA-1: Sodium methoxide CA-2: Sodium hydroxide CA-3: Potassium hydroxide CA-4: Potassium tertiary butoxide

(10) Inner diameter and length of flow passage of microflow reactor: when a plural number of microflow reactors having different diameter of flow passage were connected, for example, from the micro mixer side, when a microflow reactor having a flow passage with an inner diameter of 0.5 mm and a length of 10 m and a microflow reactor having a flow passage with an inner diameter of 1 mm and a length of 20 m were connected, the inner diameter was shown by 0.5+1, and the length was shown by 10+20.

(11) *2: As mentioned above, the conditions where the reaction was carried out by using an autoclave made of stainless having an inner volume of 2 L (a supply port pressure is the maximum pressure in the autoclave).

(12) *3: As mentioned above, the conditions where the reaction was carried out by using an autoclave made of stainless having an inner volume of 10 L (a supply port pressure is the maximum reached pressure in the autoclave, actually the safety valve which acts with 0.9 MPa in the reaction opened 4 times).

(13) The above are the same as in Table 2.

(14) Test Division 2 (Physical Property of Produced Alkylene Oxide Adduct)

(15) With regard to the alkylene oxide adducts produced in the respective examples of Test division 1, AO/M (mass ratio), M/EO/PO (molar ratio and mass ratio, EO is ethylene oxide and PO is propylene oxide) were obtained. Also, color hue was evaluated by the following standard. Further, a ratio of Mw/Mn was obtained by the following mentioned method. The results were shown in Table 2 all together.

(16) Evaluation of Color Hue

(17) Color hue was evaluated based on JIS-K0071-1: 1998

(18) (Testing Method for Colour of Chemical Products-Part I: Hazen unit color number (platinum-cobalt scale)) according to the following standard.

(19) : It corresponds to 0 to 20 with a number of the standard matching solution : It corresponds to 30 to 50 with a number of the standard matching solution : It corresponds to 60 to 150 with a number of the standard matching solution : It corresponds to 200 or more with a number of the standard matching solution

(20) Mw: Weight average molecular weight in terms of polystyrene by GPC (gel permeation chromatography)

(21) Mn: Number average molecular weight in terms of polystyrene by GPC (gel permeation chromatography)

(22) TABLE-US-00002 TABLE 2 Alkylene oxide adduct M/EO/PO M/EO/PO AO/M (molar (mass Color Division (wt) ratio) ratio) hue Mw/Mn Example 1 13.3 1/9/0 7/93/0 1.1 2 13.3 1/11/11 7/41/52 1.1 3 13.3 1/17/0 7/93/0 1.1 4 10.1 1/11/11 9/40/51 1.1 5 4.3 1/10/0 17/83/0 1.1 6 4.0 1/3/0 20/80/0 1.1 7 1.1 1/1/1 48/23/29 1.2 8 15.7 1/12/0 6/94/0 1.2 9 7.3 1/12/0 12/88/0 1.2 10 13.3 1/10/10 7/41/52 1.2 11 49.0 1/32/0 2/98/0 1.3 12 5.3 1/5/5 16/37/47 1.3 Comparative 1 13.3 1/9/0 7/93/0 1.3 example 2 13.3 1/4/4 7/41/52 X 1.3 3 13.3 1/9/0 7/93/0 X 1.2

(23) As can be seen from the results shown in Table 2, according to the production process of the present invention, a high quality alkylene oxide adduct without coloring and narrow molecular weight distribution can be continuously produced.