JP2003004544A - Method of measuring solution temperature, reaction apparatus using microwave, and method of manufacturing copper phthalocyanine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of measuring a solution temperature heated by microwaves, a method of measuring/controlling the temperature of a reaction liquid in a reaction apparatus using microwave, a reaction apparatus using microwaves having the method of measuring/controlling, and a method of manufacturing copper phthalocyanine using the method of measuring/controlling and the reaction apparatus, without using expensive temperature measuring devices, at a low price, and with substantially necessary and sufficient precision. SOLUTION: The method of measuring/controlling a solution temperature heated by microwaves is characterized in that it uses a liquid expansion type thermometer enclosing a liquid having a loss coefficient (ε×tanδ), which is the product of the dielectric constant (ε) and the dielectric loss angle (tanδ), of not larger than 3. The reaction apparatus using microwaves has, within the apparatus provided with a heating device by microwaves, a vessel containing a chemical reaction liquid and the liquid expansion type thermometer enclosing a liquid having a loss coefficient (ε×tanδ), which is the product of the dielectric constant (ε) and the dielectric loss angle (tanδ), of not larger than 3. The method of manufacturing copper phthalocyanine uses the reaction apparatus.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid phase chemical reaction using microwave heating, which is expected to be capable of high-speed reaction as compared with a conventional chemical reaction apparatus. A method for measuring the temperature of a reaction solution which is extremely inexpensive and which has substantially necessary and sufficient accuracy without using a measuring instrument, a reactor equipped with the temperature measuring method, and a method for producing copper phthalocyanine using microwave heating I will provide a.

[0002]

2. Description of the Related Art Heating of a material by microwaves is performed in proportion to a loss coefficient (ε × tanδ) obtained by multiplying a dielectric constant (ε) peculiar to the material to be heated and a dielectric loss angle (tanδ). Since it generates heat by itself, compared to the conventional heat conduction method, it has the feature that it can uniformly heat the substance to be heated in a short time, and as a practical application, household microwave ovens are widely used.

If chemical synthesis is carried out by utilizing this characteristic, it is expected that the reaction time will be shortened, the selective reaction will proceed and the by-products will be suppressed. Therefore, many studies have been conducted in recent years.
On the other hand, it is needless to say that the monitoring and control of the reaction temperature are important matters in chemical reactions. However, since temperature measurement in microwaves is temperature measurement in a strong electromagnetic field, it is necessary to use a measurement method that is not affected by microwaves.

In a conventional microwave heating chemical reaction device, a chemical reaction liquid contained in a quartz glass or plastic container in which heating by microwaves can be substantially ignored has a structure for heating a chemical reaction liquid which is a substance to be heated. It has been done by installing it in a microwave irradiation enclosure. As the microwave irradiation housing, a microwave oven type housing whose dimensions can be freely designed is often used, and FOS (fiber optic sensor) and infrared thermometer are often used for temperature measurement and control. There is.

The FOS is a device for directly measuring a reaction solution placed in a microwave by bringing a sensor into contact therewith, and a temperature sensor such as a fine fluorescent screen is attached to the tip of an optical fiber to detect a change in fluorescence or the like depending on temperature. It is a method of measuring outside the microwave irradiation housing through an optical fiber. However, FOS has the disadvantage of being expensive.

The infrared thermometer measures the temperature from outside the microwave irradiation housing without contact, and the measurable temperature is only the surface of the container or the chemical reaction liquid, and the internal temperature cannot be directly measured. There are drawbacks. Other than this, a method of extracting a part of the chemical reaction liquid to the outside of the microwave irradiation case for quick measurement, or a temperature-pressure relationship inside the sealed container in advance, and measuring the pressure A method of estimating the temperature from the value is known.

On the other hand, in liquid expansion thermometers such as mercury thermometers and alcohol thermometers, which are frequently used on a daily basis, it is presumed that mercury and alcohol themselves are heated by microwaves and cannot be used as a measuring method. Its use was never considered.

If the temperature of the reaction solution can be easily measured, the chemical reaction utilizing microwave heating can dramatically expand the range of use. For example, as an industrial synthesis method of copper phthalocyanine, which is widely used as a coloring agent for printing inks and paints, a production method using phthalodinitrile and copper sulfate in a solvent such as ethylene glycol is known. However, there are problems such that it takes time to raise the temperature of the reaction solution and it is difficult to control the temperature. Therefore, an apparatus capable of heating in a short time and controlling the reaction temperature is desired.

[0009]

The problem to be solved by the present invention is to provide a solution which is heated by microwaves without using an expensive temperature measuring device, at an extremely low cost and with substantially necessary and sufficient accuracy. For measuring the temperature of a liquid, a method for measuring / controlling the temperature of a reaction solution in a reaction device using microwaves, a reaction device using microwaves having the measurement / control method, and a measurement / control method, and a reaction device Using
A method for producing copper phthalocyanine is provided.

[0010]

As a result of intensive studies to solve the above problems, the present inventors have found that these problems can be solved by the methods described below, and have completed the present invention. .

That is, in the present invention, the loss coefficient (ε × tanδ) obtained by the product of the dielectric constant (ε) and the dielectric loss angle (tanδ) is 3
A method for measuring the temperature of a solution heated by microwaves, characterized in that a liquid expansion thermometer enclosing a liquid is used, and heating by microwaves using the temperature measured by the measurement method A method for controlling the temperature of a reaction liquid in a reactor is provided.

Further, according to the present invention, a container containing a chemical reaction solution inside a device equipped with a microwave heating device and a loss coefficient (product of the dielectric constant (ε) and the dielectric loss angle (tan δ) ( Provided is a reactor using a microwave, which is provided with a liquid expansion thermometer enclosing a liquid having ε × tan δ) of 3 or less. The present invention also provides a method for producing copper phthalocyanine using the measurement / control method and the reaction device.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION An inexpensive and sufficiently accurate method for measuring the temperature of a solution which is substantially unaffected by microwaves is obtained by multiplying the dielectric constant (ε) by the dielectric loss angle (tan δ). This can be achieved by a method for measuring the temperature of a solution heated by microwaves using a liquid expansion thermometer in which a liquid having a loss coefficient (ε × tan δ) of 3 or less is enclosed. Further, the method of controlling the temperature of the reaction solution in the reaction apparatus heated by the microwave can be solved by the same means.

The liquid expansion thermometer referred to here may be a commercially available one usually called "alcohol thermometer". Also, as the liquid used for the liquid expansion thermometer,
The loss coefficient obtained by the product of the dielectric constant (ε) and the dielectric loss angle (tanδ) can be used as long as it is a liquid that is smaller than the loss coefficient of the solution heated by the microwave. A liquid having a loss coefficient of 3 or less is suitable, and a liquid having a loss coefficient of 0.1 or less is suitable for more accurate temperature measurement.

The loss factor of glass containers and ceramics used in household microwave ovens is usually about 0.1, and it is easy to understand that these containers do not show a large temperature rise in household microwave ovens. Examples of such liquids having a loss factor of 3 or less include ethanol and butanol.
Further, examples of the liquid having a loss coefficient of 0.1 or less include kerosene, light oil, silicone oil and the like.

Further, it is also within the scope of the measuring method of the present invention to enclose these liquids in a closed container and detect the volume expansion due to temperature change with a pressure sensor. A mercury thermometer, which is one of the liquid expansion thermometers, is used to measure the temperature of a solution heated by microwaves because the mercury or mercury amalgam enclosed in the thermometer is rapidly heated by microwaves. Cannot be used.

In the case of a commercially available “alcohol thermometer”, the upper limit of the measurable temperature range is around 200 ° C., but many chemical reactions are carried out at temperatures below this temperature, so it is practically sufficient. It is a wide measurement range.

Another property required for liquids used in liquid expansion thermometers is to have a favorable coefficient of expansion (volume expansion coefficient). For example, the expansion coefficient of ethanol is 0.0011 deg ⁻¹ and the expansion coefficient of methanol is 0.
001 19 deg ^-1 , isopropyl alcohol 0.00
106deg ^-1 , n-butanol 0.00093de
g ⁻¹ and cresol 0.00076 deg ⁻¹ .

On the other hand, kerosene and light oil are the components contained in them.
Although the numerical value varies depending on the composition, it is generally 0.001 to 0.
0015deg^-1It is in the range of
The value varies slightly depending on the component composition of
0096-0.0013deg ^-1Is in the range. these
Depending on the temperature range used and the size of the display,
In consideration of the expansion coefficient of
You can use it. Also, if necessary, use these together.
However, they may be mixed and used.

The reaction apparatus using the microwave of the present invention is
Inside the device equipped with a microwave heating device, the container containing the chemical reaction liquid, the dielectric constant (ε) and the dielectric loss angle (tan
A liquid expansion thermometer in which a liquid having a loss coefficient (ε × tan δ) obtained by the product of δ) is 3 or less is installed,
It is a reaction device using microwaves.

As a method of attaching the thermometer to the reaction apparatus heated by microwaves, a part of the reaction vessel is penetrated to the outside of the microwave irradiation housing as shown in FIG. It is preferable to insert an "alcohol thermometer", but it is not defined in the same manner. The material of the reaction vessel is preferably a material that is not substantially heated by microwaves, such as glass, quartz, quartz glass, and Teflon (registered trademark), but its shape is generally used for chemical reactions. It may be the same as the containers to be used.

The liquid expansion type thermometer inserted into the chemical reaction vessel for microwave heating preferably has a temperature measuring portion in contact with the reaction solution, so that the temperature of the reaction solution can be measured more accurately. As the microwave irradiation case, it is preferable to use a microwave oven-type case whose size can be designed according to the size of the reaction vessel.

In order to know the actual temperature of the reaction solution by measuring the temperature using a liquid expansion thermometer, it is necessary to correct the indicated temperature. As has been clarified by the present inventors, a constant temperature is maintained between the temperature indicated by the thermometer, which is measured by bringing the temperature-measuring part into contact with the solution in the reactor heated by microwaves, and the actual temperature of the solution. There is a relationship of, for example, ethylene glycol has the relationship shown in FIG. That is, the temperature was measured lower than the actual temperature.

A measuring device such as FOS may be used as a method for measuring the actual temperature, but the indicated temperature at the time of microwave irradiation and the actual temperature at the time of interruption of microwave irradiation are measured at several temperature points and measured. It is practically sufficient to create a temperature-actual temperature graph. As a correction method, a device that automatically detects a change in the liquid column of a liquid expansion thermometer, for example, solid-state imaging (C
The fluctuation of the liquid column may be detected by using a CD) element, a level sensor, etc., and automatically corrected by using a correction formula stored in a computer.

As the objects to be measured, those mainly containing water or an organic solvent can be considered. As the organic solvent, chloroform, ethyl acetate, acetone, ethanol, methanol,
Dimethyl sulfoxide, N.I. It has been confirmed that N-dimethylformamide and ethylene glycol can be measured, but the target organic solvent of the present invention is not limited thereto.

The shortening of the synthesis time of copper phthalocyanine, which is one of the objects of the present invention, can be achieved by heating the reaction solution by microwave. That is, when a reaction liquid obtained by adding phthalodinitrile and copper sulfate to ethylene glycol as a solvent is placed in a microwave oven-type casing and irradiated with a microwave of 500 W, the temperature of the reaction liquid reaches the reaction temperature in about 2 minutes. It reaches around 190 ° C.

The temperature measurement can be performed with sufficient accuracy by the above-mentioned commercially available "alcohol thermometer". After the liquid temperature reaches about 190 ℃, adjust the microwave output,
The reaction is completed in an extremely short time of about 5 minutes at 190 ° C., and copper phthalocyanine can be obtained.

As described above, in the microwave-using reaction device using the liquid expansion thermometer as the temperature measuring device, the temperature of the reaction liquid can be measured substantially without being affected by the microwave. This can be said to provide a convenient and inexpensive way to apply microwave chemistry, which has been performed empirically, using expensive measuring instruments.
Furthermore, while controlling the temperature using this device, it was possible to synthesize copper phthalocyanine in an extremely short time,
It can be said that this is an industrially useful method.

[0029]

EXAMPLES The present invention will be described in more detail below with reference to examples.

[Example 1] The microwave type microwave chemical reaction apparatus used was constructed so that changes in the course of the reaction can be visually recognized as shown in FIG. FIG. 2 shows a cross section of FIG. 1, and two holes 3, 2, and 3 are opened in the upper ceiling 1 of the microwave oven type microwave housing to obtain 200 ml or 300 m.
The 1-necked three-necked flask 5 was inserted from the inside of the casing, and the three ports were taken out of the casing and fixed.

Next, an alcohol thermometer 6, a stirrer 8 having a stirring rod 7 made of all Teflon or glass, and a dropping funnel 9 with a cooler or a bypass were attached to the mouth of the three-necked flask. The cooler was connected to a nitrogen gas flow tube 10. Reference numeral 11 in the figure is a wall for preventing the outside air from flowing into the magnetron oscillator and the power supply unit, and the wire netting 12 is for blocking microwaves leaking slightly from the three holes in the upper ceiling. The microwave housing used was 2.45 GHz, 500
The microwave irradiation was controlled by using a commercially available microwave oven of W and using the irradiation time adjusting device as it was.

[Example 2] Since the mouth portion of a commercially available three-necked flask is almost the same in the case of 200 ml and 300 ml, a 200 ml three-necked flask was used here, and 100 ml of water was put therein, and microwave heating was performed. The temperature at that time was measured with an alcohol thermometer. The temperature rise of water due to microwave heating was visually observed with an alcohol thermometer, and no abnormality was found in the alcohol thermometer.

When the water boiled, the alcohol thermometer showed about 90 ° C., and it was found that the alcohol thermometer does not show an accurate temperature but needs to be used as a correction value. The correction was to heat ethylene glycol to about 190 ° C. with this microwave oven type microwave reactor, stop microwave irradiation after that, and compare the temperatures measured using a thermocouple and an alcohol thermometer at the same time during cooling. Then, the correction value of the alcohol thermometer was determined. As shown in FIG. 3, it can be seen that there is a good correlation between the actual temperature and the indicated value of the alcohol thermometer.

[Example 3] 100 ml of ethylene glycol
Was put in a 200 ml three-necked flask, the temperature measuring part of the alcohol thermometer was put in ethylene glycol, and microwave heating was carried out while visually observing the temperature.
When the temperature reached 55 ° C, microwave irradiation was stopped, and when measured with a thermocouple thermometer, it showed 190 ° C, which was almost the same as the correction value. It was confirmed that the temperature of the liquid was measured. No microwave leakage or abnormal events occurred during microwave irradiation.

Example 4 As in Example 3, 200 ml
Chloroform, ethyl acetate, acetone, ethanol, methanol, dimethyl sulfoxide, N, N-dimethylformamide, and other organic solvents were placed in the three-necked flask, and heated by microwave while observing the alcohol thermometer. All of these could be safely heated as in the case of ethylene glycol.

For example, 100 ml of methanol is used for 5 minutes in 1 minute.
After heating to 8 ° C., the microwave irradiation was stopped immediately after that, and the temperature was measured with a thermocouple to find that it was 62 ° C.
From these experiments, it was found that the correction of the alcohol thermometer performed in Example 2 was effective. In addition, no abnormal events such as ignition occurred during microwave irradiation.

Example 5 100 ml of ethylene glycol and 8 mm of phthalodinitrile in a 200 ml three-necked flask.
ol and 2 mmol of copper sulfate were added and heated by microwave. While observing the alcohol thermometer, irradiate microwaves (2 minutes) until the scale of the alcohol thermometer reaches 155 ° C, and then control the microwave irradiation using the irradiation time adjusting device to 155 ° C for 5 minutes. When kept, a blue liquid was obtained.

As a result of filtering the liquid and subjecting the obtained solid to X-ray analysis, it was confirmed that copper phthalocyanine was synthesized. The produced copper phthalocyanine was purified and the yield was measured to be 90%. Surprisingly,
Good quality copper phthalocyanine was synthesized in a very short time of only 5 minutes.

[Example 6] The same test as in Example 5 was repeated. As a result, a reaction system of 100 ml of ethylene glycol, 8 mmol of phthalodinitrile and 2 mmol of cuprous oxide was heated at 155 ° C for 5 minutes to give copper phthalocyanine. Was confirmed. (Yield 85%)

[0040]

INDUSTRIAL APPLICABILITY The present invention provides a method for measuring the temperature of a solution heated by microwaves at a very low cost and with substantially necessary and sufficient accuracy without using an expensive temperature measuring device. A method for measuring / controlling the temperature of a reaction solution in a reaction apparatus used, a reaction apparatus using a microwave having the measurement / control method, and a method for measuring / controlling the reaction apparatus, and a method for producing copper phthalocyanine are provided. Can be provided.

[0041]

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of a reaction apparatus using a microwave of the present invention.

FIG. 2 is a cross-sectional view of the reaction device using the microwave shown in FIG.

FIG. 3 is a diagram (correction diagram) showing a relationship between an actual temperature of ethylene glycol and an instruction temperature of an alcohol thermometer during microwave irradiation in Example 3.

[Explanation of symbols]

1: Ceiling above the cabinet 2, 3 and 4: three-necked flask mouth hole 5: Three neck flask 6: Alcohol thermometer 7: Glass stirring rod 8: Stirrer 9: Cooler or dropping funnel 10: Nitrogen gas flow tube 11: Outside air inflow prevention wall 12: Microwave blocking wire mesh

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09B 47/067 C09B 47/067 H05B 6/68 320 H05B 6/68 320M 6/80 6/80 Z (72 ) Inventor Katsuyuki Naito 32-3 Sumiyoshi, Ueda-shi (72) Inventor Hirotsugu Hattori 1125 Bessho Onsen, Ueda-shi (72) Inventor Takeshi Hibisawa 631 Sakado, Sakura-shi, Chiba (72) Inventor Motokazu Ishimori Higashi-Fuka, Kamisu-cho, Ibaraki Prefecture 18 F term (reference) 3K086 AA01 AA02 AA10 BA08 CA05 CA20 CB04 CC02 FA07 3K090 LA00 PA00 4C050 PA14 PA20 4G075 AA62 AA63 BA10 CA26 CA57 DA02 EB01 EC11 EC25 FB06 FB11 FB12 FC15

Claims (7)

[Claims] 1. A liquid expansion thermometer in which a liquid having a loss coefficient (ε × tan δ) obtained by multiplying a dielectric constant (ε) and a dielectric loss angle (tan δ) is 3 or less is used. A method for measuring the temperature of a solution heated by microwave. 2. The solution temperature measuring method according to claim 1, wherein the display temperature of the liquid expansion thermometer is corrected to an actual temperature by using a correction table, a correction diagram, or a correction formula created in advance. 3. A method for controlling the temperature of a reaction solution in a reaction apparatus heated by microwaves using the temperature measured by the method for measuring a solution temperature according to claim 1. 4. A container containing a chemical reaction liquid inside a device equipped with a heating device using microwaves, and a loss coefficient (ε × tan) obtained by the product of the dielectric constant (ε) and the dielectric loss angle (tan δ).
A reaction device using a microwave, in which a liquid expansion thermometer enclosing a liquid having δ of 3 or less is installed. 5. The reaction device according to claim 4, wherein the temperature measuring portion of the liquid expansion thermometer is in contact with the reaction liquid. 6. A method for producing copper phthalocyanine using the reactor according to claim 4 or 5. 7. Using the method according to claim 1 or 2,
A method for producing copper phthalocyanine, which controls the temperature of a reaction solution.