JP2008012452A - Agitator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an agitator which can generate a strong vertical circulation flow without stagnation of a solution in an agitation tank to enable the efficient vertical circulation mixture of the solution in a wide viscosity range. <P>SOLUTION: An agitation blade 12 attached to a rotary shaft 10 arranged in the center of the agitation tank 2 comprises: a plate blade member 13 attached to the lower part of the rotary shaft 10; a pair of ribbon blade members 14 installed along the inside wall surface of the agitation tank 2 from both ends of the plate blade member 13 in the direction opposite to the rotation direction R of the rotary shaft 10 and in the oblique upward direction; and a lattice blade member 15 attached to the rotary shaft 10 and connected to the respective ribbon blade members 14 through a pair of connection pieces 15C. In the case where a viscosity dispersion range of a solution fed into the agitation tank 2 is within 25 Pa s and the maximum viscosity is 45 Pa s or lower, at least 200 revolutions of the agitation blade 12 through the rotary shaft 10 decreases the viscosity dispersion range of the solution to 1 Pa s or lower. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a stirrer, and in particular, it is possible to generate a strong vertical circulation flow without causing the solution in the stirring tank to stay, so that it is possible to efficiently perform the vertical circulation mixing of the solution in a wide viscosity range. The present invention relates to a stirrer.

  Conventionally, various devices have been proposed for stirring devices that perform mixing, dispersion, and reaction operations of various solutions in a so-called vertical batch container that is long in the vertical direction. For example, a disk turbine used in a comparatively low viscosity region in the range of several mPa · s to several Pa · s, a propeller-shaped stirring blade, and further used in a high viscosity range of several Pa · s to several hundred Pa · s level. There are helical ribbon wings. In recent years, many wide blades such as Max blend blades and full zone blades that can be mixed from a low viscosity to a relatively high viscosity are commercially available.

  Here, when the solution reaction of the solution is performed in this type of vertical batch container, the stirring efficiency often greatly affects the characteristics and productivity of the reaction product. For example, in the emulsion polymerization of acrylic, the uniformity of heat transfer efficiency greatly affects the emulsion particle distribution, and the stirring operation needs to be performed at a shear rate that does not destroy the generated particles.

  Further, for example, in the polycondensation reaction of polyester, it is necessary to improve the reflux efficiency, and from this, it is necessary to perform interfacial mixing at the gas-liquid interface better. Furthermore, for example, in the bulk thermal polymerization of acrylic, if a staying part is generated in the reaction tank, the reaction may partially proceed rapidly. Therefore, it is necessary to mix without a staying part even at high viscosity.

In order to meet the above requirements, for example, as a stirrer having high mixing performance, Japanese Patent Application Laid-Open No. 2003-159523 discloses a lattice blade attached along a rotation axis and a length longer than the length of the lattice blade. A paddle blade with a blade length extending to the bottom of the plate is provided at the lower part of the rotating shaft, the gap between the lower end of this paddle blade and the bottom of the stirring tank is set narrow, and the paddle blade has a slanting inclination angle. In such a stirrer, when the grid blade and the paddle blade are rotated, the solution at the bottom of the stirring tank becomes a vigorous upward flow by the paddle blade, and the bottom of the stirrer is described. The solution from the top to the top is dispersed and subdivided by the lattice blades.
JP 2003-159523 A

  Here, even with the stirrer described in JP-A-2003-159523, among the above reaction examples, particularly in the polycondensation reaction of polyester, low viscosity (several mPa · s) to high viscosity (several tens Pa · s). Although it is possible to efficiently perform the liquid circulation stirring in the vertical direction in a wide range up to 2), the vertical circulation performance is often weakened rapidly in the high viscosity region. The problem of lowering remains. As a result, the polycondensation time becomes longer, which is a cause of lowering productivity.

  The present invention has been made to solve the above-described problems in the prior art, and can generate a strong vertical circulation flow without causing the solution in the stirring tank to stay, so that it is efficient in a wide viscosity range. It is an object of the present invention to provide an agitator capable of well circulating the solution up and down.

  In order to achieve the above object, a stirrer according to claim 1 includes a stirring tank into which a solution is charged, a rotating shaft disposed in a central portion of the stirring tank, and a stirring blade attached to the rotating shaft. In the stirring device provided, the stirring blade includes a flat blade member attached to a lower portion of the rotary shaft, and a direction opposite to the rotation direction of the rotary shaft from both ends of the flat blade member and in an obliquely upward direction. A pair of ribbon-like wing members provided along the inner wall surface of the stirring tank, and a lattice-like wing attached to the rotary shaft and connected to the ribbon-like wing members via a pair of connecting pieces And the stirring blade is rotated at least 200 times through the rotating shaft when the viscosity variation range of the solution charged in the stirring vessel is within 25 Pa · s and the maximum viscosity is 45 Pa · s or less. Of the solution Degree variation range is characterized by comprising the following 1 Pa · s.

  Further, the stirring method according to claim 2 includes: a flat wing member attached to a lower portion of the rotating shaft disposed in the central portion of the stirring tank; and a rotation direction of the rotating shaft from both ends of the flat wing member. A pair of ribbon-like wing members provided along the inner wall surface of the stirring tank in the reverse direction and obliquely upward, and attached to the rotary shaft and connected to each ribbon-like wing member via a pair of connecting pieces A solution having a viscosity variation range of 25 Pa · s or less and a maximum viscosity of 45 Pa · s or less is stirred through the stirring blade provided with the lattice-shaped blade member formed, and the rotating shaft Thus, when the stirring blade is rotated at least 200 times, the viscosity variation range of the solution becomes 1 Pa · s or less.

  A product according to claim 3 is obtained by the stirring device according to claim 1 or the stirring method according to claim 2.

In the stirring device according to claim 1, the stirring blade attached to the rotating shaft disposed in the central portion of the stirring tank includes the flat blade member attached to the lower portion of the rotating shaft, and the flat blade member. A pair of ribbon-like wing members provided along the inner wall surface of the agitation tank from both ends in a direction opposite to the rotation direction of the rotating shaft and obliquely upward, and attached to the rotating shaft and a pair of couplings Since the grid-like wing member is connected to each ribbon-like wing member via a piece, the solution can be efficiently circulated and mixed in a wide range of viscosity. In particular, it can reliably and efficiently eliminate the phenomenon that causes reaction and phase change at the gas-liquid interface of the solution, and is therefore very useful for the phenomenon that causes reaction and phase change at the gas-liquid interface of the solution. A simple stirring device can be provided.
In particular, when the viscosity variation range of the solution charged in the stirring tank is within 25 Pa · s and the maximum viscosity is 45 Pa · s or less, the solution is obtained when the stirring blade is rotated at least 200 times through the rotating shaft. Therefore, the viscosity of the solution can be made uniform over the entire stirring tank in a short time with a small number of rotations that rotate the stirring blade 200 times.

Further, in the agitation method according to claim 2, the solution charged into the agitation tank is divided into a flat wing member attached to the lower part of the rotating shaft disposed at the center of the agitation tank, and both ends of the flat wing member. A pair of ribbon-like wing members provided along the inner wall surface of the agitation tank in a direction opposite to the rotation direction of the rotary shaft from the portion and obliquely upward, and attached to the rotary shaft and via a pair of connecting pieces Thus, stirring is performed via a stirring blade provided with a lattice-like wing member connected to each ribbon-like wing member, so that it is possible to efficiently perform up-down circulation mixing in a wide viscosity range of the solution. In particular, it can reliably and efficiently eliminate the phenomenon that causes reaction and phase change at the gas-liquid interface of the solution, and is therefore very useful for the phenomenon that causes reaction and phase change at the gas-liquid interface of the solution. A simple stirring method can be provided.
In particular, when the viscosity variation range of the solution charged in the stirring tank is within 25 Pa · s and the maximum viscosity is 45 Pa · s or less, the solution is obtained when the stirring blade is rotated at least 200 times through the rotating shaft. Therefore, the viscosity of the solution can be made uniform over the entire stirring tank in a short time with a small number of rotations that rotate the stirring blade 200 times.

  Further, the product according to claim 3 is obtained by the stirring device according to claim 1 or the stirring method according to claim 2. In addition, there exists an adhesive used for an adhesive sheet etc. as this product, for example.

DESCRIPTION OF EMBODIMENTS Hereinafter, a stirrer according to the present invention will be described in detail with reference to the drawings based on this embodiment that embodies the present invention.
First, based on FIG. 1, the structure of the stirring apparatus which concerns on this embodiment is demonstrated. FIG. 1 is an explanatory view schematically showing a stirring device.
In FIG. 1, the stirring device 1 basically includes a stirring tank 2 into which various solutions are charged and a lid 3 that seals the upper part of the stirring tank 2. A motor 4 is attached to the top of the lid 3, and a motor shaft 5 of the motor 4 is inserted into the lid 3. A flange 6 is provided at the lower end of the motor shaft 5.

Further, an exhaust pipe 7 is communicated with the lid 3, and the exhaust rod 7 is bifurcated in an upward direction and a downward direction. A condenser 8 is attached to the exhaust pipe 7 branched upward, and a pot 9 is connected to the exhaust pipe 7 branched downward.
Here, for example, when the solution put into the stirring tank 2 is a polymer polymerization solution that generates a polymer by performing a polycondensation reaction, the exhaust tank 7 has an action of discharging water vapor that is generated along with the polycondensation reaction. I do. Further, the water vapor guided to the exhaust pipe 7 is cooled and liquefied by the condenser 8, and the liquefied water is stored in the lower pot 9.

  The flange 6 provided at the lower end of the motor shaft 5 is connected to a flange 11 formed at the upper end of the rotating shaft 10 via a bolt or the like, whereby the rotating shaft 10 is, as shown in FIG. Arranged in the center of the stirring tank 2.

  A stirring blade 12 is attached to the lower portion of the rotating shaft 10, and the stirring blade 12 is rotated based on the rotation of the rotating shaft 10 according to the rotation of the rotating shaft 5 of the motor 4, and the solution in the stirring tank 2 is rotated. Is stirred.

Here, the structure of the stirring blade 12 is demonstrated based on FIG.2 and FIG.3. FIG. 2 is an explanatory diagram illustrating the agitating blade in a multifaceted manner. FIG. 2A is a plan view showing the agitating blade as viewed from above, FIG. 2B is a front view of the agitating blade, and FIG. Is a side view of the stirring blade, and FIG. 2 (D) is an explanatory view showing the tip of the ribbon-like blade member in the stirring blade. FIG. 3 is a perspective view schematically showing a stirring blade.
2 and 3, the stirring blade 12 is attached to the lower portion of the rotating shaft 10, and the stirring blade 12 includes a flat blade member 13, a pair of ribbon blade members 14, and a lattice blade member 15. ing.

The flat blade member 13 includes a semi-elliptical portion 13A having a lower end portion along the inner wall surface of the bottom of the stirring tank 2, and a rectangular portion 13B integrally formed above the semi-elliptical portion 13A. It is configured. The flat blade member 13 stirs the solution present at the bottom of the stirring tank 2.
When the diameter of the stirring tank 2 is D (see FIG. 2A), the thickness t1 (see FIG. 2C) of the flat blade member 13 is set to 0.007D to 0.02D. In addition, the height h1 of the rectangular portion 13B is set to 0.1D to 0.25D.

As shown in FIG. 3, the pair of ribbon-like wing members 14 are integrally formed at both ends of the rectangular portion 13 </ b> B of the flat plate-like wing member 13. The ribbon-shaped wing member 14 has an inner wall surface of the stirring tank 2 from both ends of the rectangular portion 13B in the direction opposite to the rotation direction R of the rotary shaft 10 (see FIG. 2A) and obliquely upward. It is provided along.
Here, similarly to the above, when the diameter of the stirring tank 2 is D (see FIG. 2A), the width W1 (see FIG. 2D) of each ribbon-shaped wing member 14 is 0.05D to 0. And d1: d2 at the outer ellipse diameter of each ribbon-like wing member 14 is set to 0.85D to 0.99D: 1.1D to 5.8D. The thickness t2 (see FIG. 2C) of the wing member 14 is set to 0.007D to 0.02D.
Further, as shown in FIG. 2C, each ribbon-shaped wing member 14 formed as described above is inclined from the rectangular portion 13B so that the angle θ1 formed with the horizontal direction is 30 ° to 80 °. It is extended upward.

The lattice-like wing member 15 is a pair of rod-like portions 15A erected from a substantially central position between the end portion and the rotary shaft 10 in the rectangular portion 13B of the flat plate-like wing member 13, and in the vertical direction of each rod-like portion 15A. A pair of fixing portions 15B that extend horizontally from a substantially central position and fix each rod-like portion 15A and the rotary shaft 10, and each rod-like shape that extends horizontally from the position where each fixing portion 15B is formed. It is comprised from a pair of connection piece 15C which connects 15A and each ribbon-like wing | blade member 14. FIG.
Here, similarly to the above, when the diameter of the stirring tank 2 is D (see FIG. 2A), the width b1 (see FIG. 2B) of each rod-shaped portion 15A is 0.02D to 0.08D. The thickness t3 (see FIG. 2C) of the rod-like portion 15A is set to 0.007D to 0.02D.

Then, when stirring the solution thrown in the stirring tank 2 using the stirring blade 12 provided in the stirring apparatus 1 comprised as mentioned above, in order to verify the stirring performance by the stirring blade 12 Based on an analysis model having the same configuration as that of the stirring apparatus 1 of the present embodiment shown in FIG. 4, a numerical flow simulation analysis of the solution in the stirring tank 2 was performed.
At this time, the numerical flow simulation was performed under the following conditions.
Analysis software program: FLUENT 6.2
Number of rotations of rotating shaft: 60rpm
Solution viscosity: 20 Pa · s
Solution density: 1 g / cm3

  FIG. 4 is an explanatory diagram schematically showing an analysis model used in the numerical flow simulation. The analysis model shown in FIG. 4 has the same configuration as the stirring device 1 of the present embodiment shown in FIG.

When the numerical flow simulation was performed under the above-described conditions, the simulation results shown in FIGS. 5 and 6 were obtained.
FIG. 5 is an explanatory diagram showing a velocity vector in a section parallel to the rotational axis direction and including the rotational axis. FIG. 6 is an explanatory diagram showing a trajectory in which particles arranged on the liquid surface of the solution move within a predetermined time. It is.

  As is clear from FIG. 5, it can be seen that the solution flows uniformly over the entire stirring tank without being localized in the upper and lower parts in the stirring tank. Similarly, as is apparent from FIG. 6, it can be seen that the particles on the liquid surface flow throughout the stirring tank. From this, it can be seen that in the stirring device based on the analysis model, the vertical circulation flow of the solution can be generated strongly in the stirring tank.

Here, in order to make a comparison with the numerical flow simulation based on the analysis model shown in FIG. 4, the numerical flow simulation was performed under the same conditions as described above using the comparative analysis model shown in FIG.
FIG. 7 is an explanatory diagram schematically showing a comparative analysis model. In the comparative analysis model shown in FIG. 7, the stirring blade 12 attached to the rotary shaft 10 includes a flat blade member 13 and a lattice blade member formed separately from the flat blade member 13. 15 and the ribbon-like blade member 14 as in the stirring blade 12 of the present embodiment is not provided.
Note that the lattice-shaped wing member 15 has a larger number of lattices than the lattice-shaped wing member 15 in the present embodiment, and the flat plate-shaped wing member 13 is disposed in an intersecting state with the lattice-shaped member 15.

When the numerical flow simulation was performed based on the above comparative analysis model, the simulation results shown in FIGS. 8 and 9 were obtained.
FIG. 8 is an explanatory diagram showing velocity vectors in a cross section including the rotation axis parallel to the rotation axis direction in the comparative analysis model, and FIG. 9 shows the particles arranged on the liquid surface of the solution in the comparative analysis model within a certain time. It is explanatory drawing which shows the locus | trajectory which moves to.

  Compared to the velocity vector diagram shown in FIG. 5, in the velocity vector diagram shown in FIG. 8, the solution has a poorer fluidity in the upper part than the lower part in the stirring tank, and the fluidity is slightly uneven. I understand. Further, compared with the locus shown in FIG. 6, it can be seen from the locus shown in FIG. 9 that the fluidity of the particles on the liquid surface in the stirring tank is slightly inferior.

  As described above, in the stirring device 1 according to the present embodiment, the stirring blade 12 attached to the rotating shaft 10 disposed in the central portion of the stirring tank 2 is a flat blade attached to the lower portion of the rotating shaft 10. A pair of ribbon-shaped blades provided along the inner wall surface of the stirring tank 2 from the both ends of the member 13 and the plate-shaped blade portion 13 in the direction opposite to the rotation direction R of the rotary shaft 10 and obliquely upward. Based on the fact that the member 14 and the lattice-like wing member 15 attached to the ribbon-like wing member 14 through the pair of connecting sides 15C are attached to the rotary shaft 10, the solution is efficiently circulated in the vertical direction. Mixing can be performed. In particular, it can reliably and efficiently eliminate the phenomenon that causes reaction and phase change at the gas-liquid interface of the solution, and is therefore very useful for the phenomenon that causes reaction and phase change at the gas-liquid interface A simple stirring device can be provided.

  Next, Example 1 applied to the polyester polycondensation reaction using the stirring device 1 configured as described above will be described. In the following, the amount of each component is expressed in parts by weight.

First, in a stirrer 1 shown in FIG. 1, polycarbonate diol ["PLACCEL CD220PL" manufactured by Daicel Chemical Industries, Ltd., hydroxyl value: 56.1 KOHmg / g] 50 kg, sebacic acid 5.05 kg, tetra-n as a catalyst -0.0175 kg of butyl titanate was charged, and the temperature was raised to 180 degrees at a stirring rotational speed of 60 rpm in the presence of 10 kg of xylene as a reaction water drainage solvent, and this temperature was maintained.
After a while, outflow separation of water was recognized by the dehydration reaction accompanying the polycondensation reaction, and the polycondensation reaction started to proceed. Thereafter, the reaction was completed in about 15 hours, and polyester was produced.

(Comparative Example 1)
On the basis of the comparative analysis model shown in FIG. 7, the stirring blade 12 is composed of a flat blade member 13 and a stirring blade member 15 configured separately from the flat blade member 13 and separately. Except for the change to the blade 12, the polycondensation reaction was carried out under the same composition and the same conditions as in the case of Example 1. As in the case of Example 1, water outflow separation was observed, and the reaction proceeded. The reaction was completed in about 22 hours from the beginning, and a polyester having substantially the same physical properties as the polyester obtained in Example 1 was produced.

  As is clear from comparison between Example 1 and Comparative Example 1, the surface of the gas-liquid interface is efficiently stirred by using the stirring blade 12 according to this embodiment, and as a result, in a short time. The reaction could be completed.

In Example 2, the stirring apparatus shown in FIG. 10 was used.
Here, the stirring apparatus shown in FIG. 10 will be described. FIG. 10 is an explanatory view schematically showing the stirring device used in Example 2. The stirring device shown in FIG. 10 basically has the same configuration as that of the stirring device 1 shown in FIG. 1, and therefore only the configuration different from that of the stirring device 1 shown in FIG. 1 will be described below.

In FIG. 10, an ultraviolet irradiation device 20 is disposed on the lid 3 that seals the upper part of the stirring tank 2. One end of an optical fiber 21 is connected to the ultraviolet irradiation device 20, and the other end of the optical fiber 21 is connected to an ultraviolet light source 22.
Here, the stirrer 1 is a stirrer used when photopolymerization with ultraviolet rays (UV) is performed, and the ultraviolet rays emitted from the ultraviolet light source 22 are transmitted through the optical fiber 21 and are transmitted from the ultraviolet irradiation device 20. The photopolymerization solution put in the stirring tank 2 is irradiated.

In Example 2, the stirring device 2 shown in FIG. 10 is applied to the UV prepolymerization reaction.
First, 45 kg of 2-ethylhexyl acrylate, 5 kg of acrylic acid, and 0.05 kg of Irgacure 651 [Nippon Ciba-Geigy] are charged in the stirring apparatus 1 shown in FIG. 10, the stirring rotational speed is 60 rpm, the outer bath is 20 ° C., and the bottom of the stirring tank 2 Further, nitrogen substitution was performed at 20 L / min for 1 hour.

Subsequently, UV irradiation was performed through the ultraviolet irradiation device 20 at a liquid surface illuminance of about 5 mW / cm 2, and UV polymerization was performed until the liquid viscosity reached 20 Pa · s. After completion of the polymerization, the mixture was stirred for about 1 hour in an open atmosphere.
While stirring as described above, the solution was sampled from the upper surface and the lower surface in the stirring tank 2, and the viscosity was measured with a BH viscometer. The result is shown in FIG.

  As shown in FIG. 11, in Example 2, the viscosity of the solution sampled from the upper surface of the stirring vessel 2 and the viscosity of the solution sampled from the lower surface of the stirring vessel 2 are both when stirring for about 5 minutes from the start of stirring. It is a stable value of about 28 Pa · s. From this, in Example 2, it turns out that the viscosity of the solution in the stirring tank 2 becomes substantially uniform in a short time throughout the stirring tank 2.

(Comparative Example 2)
Subsequently, as in the case of Comparative Example 1, based on the comparative analysis model shown in FIG. 7, the stirring blade 12 was configured separately from the flat blade member 13 and the flat blade member 13. The photopolymerization reaction was carried out under the same formulation and the same conditions as in Example 2 except that the stirring blade 12 was changed to the lattice blade member 15.
That is, as in the case of Example 2, UV polymerization is performed until the liquid viscosity reaches 20 Pa · s, and after completion of the polymerization, the mixture is stirred for about 1 hour in an open air state. Were sampled and the viscosity was measured with a BH viscometer. The result is shown in FIG.

  As shown in FIG. 11, in Comparative Example 2, the viscosity of the solution sampled from the upper surface of the stirring tank 2 has a difference in the upper and lower viscosity of 10 Pa · s or more even after about 5 minutes from the start of stirring. Even after a lapse of more than minutes, a uniform viscosity was not reached.

As is clear from the comparison between Example 2 and Comparative Example 2, in Example 2, by using the stirring blade of FIG. 4 according to this embodiment, a substantially uniform reaction product is obtained in a short time. On the other hand, in Comparative Example 2 using the stirring blade of FIG. 7 based on the comparative analysis model, it can be seen that the viscosity of the reactant remains non-uniform even after a considerable time has elapsed.
As described above, according to the stirring blade of FIG. 4 according to the present embodiment, the viscosity of the solution can be made uniform by stirring for a short time.

Next, the outline of the experiment performed in Example 3 will be described with reference to FIG. FIG. 12 is an explanatory view schematically showing the outline of the experiment conducted in Example 3.
As shown in FIG. 12, first, a high-viscosity solution is charged at the bottom of the stirring tank, and a low-viscosity solution is charged above the high-viscosity solution. Thereafter, the stirring blade 12 is rotated at a predetermined rotational speed for a predetermined time via the rotating shaft 10 to stir the solution in the stirring tank 2. After stirring in this way, the solution is sampled from the upper part and the lower part of the stirring tank 2, and the viscosity of each sampled solution is measured with a BH viscometer. Then, the relationship between the viscosity difference obtained by subtracting the viscosity of the solution in the upper part from the viscosity of the solution in the lower part of the stirring tank 1 and the rotation speed of the stirring blade is examined.

  In Example 3, a stirrer 1 having a 100 L (liter) scale stirring tank 2 is used, and a prepolymer produced in Example 2 and having a viscosity of 45 Pa · s is provided at the bottom of the stirring tank 2. While charging 33.3 L, 66.7 L of the prepolymer produced in Example 2 and having a viscosity of 20 Pa · s was charged in the upper part of the stirring tank 2.

  Thereafter, the prepolymer is stirred with the stirring blade 12 at a rotation speed of 43 rpm, the prepolymer is sampled from the upper part and the lower part of the stirring tank 2 every predetermined time, and the viscosity of each sampled prepolymer is set to the BH type viscosity. It was measured by a meter. And the viscosity difference which deducted the viscosity value measured from the prepolymer in the upper part of the stirring tank 2 from the viscosity value measured from the prepolymer in the lower part of the stirring tank 2 thus measured, and the rotational speed of the stirring blade 12 ( The relationship between the rotational speed and the numerical value obtained by multiplying the stirring time was investigated. The result is shown in a graph G1 (indicated by ●) in FIG.

(Comparative Example 3)
In Comparative Example 3, as in Comparative Examples 1 and 2, based on the comparative analysis model shown in FIG. 7, the stirring blade 12 is made independent of the flat blade member 13 and the flat blade member 13. According to the same conditions as in the case of Example 3 except that the stirring blade 12 is composed of the lattice-shaped blade member 15 configured separately and the rotation speed of the stirring blade 12 is changed to 50 rpm. The prepolymer was stirred.
The rotational speed of the stirring blade 12 in Comparative Example 3 is based on the condition that the power for stirring the prepolymer in the stirring tank 2 through the stirring blade 12 in Comparative Example 3 is the same as in Example 3. Set.

  In the comparative example 3, the viscosity difference obtained by subtracting the viscosity value measured from the prepolymer in the upper part of the stirring tank 2 from the viscosity value measured from the prepolymer in the lower part of the stirring tank 2 and the rotation speed (rotation) of the stirring blade 12 The measurement result showing the relationship between the speed and a numerical value obtained by multiplying the stirring time by a speed is shown in a graph G2 (indicated by a triangle) in FIG.

(Comparative Example 4)
In Comparative Example 4, the prepolymer in the stirring tank was stirred using the stirring device shown in FIG.
Here, based on FIG. 13, it demonstrates per schematic structure of the stirring apparatus used in the comparative example 4. FIG. FIG. 13 is an explanatory view schematically showing a stirring device used in Comparative Example 4. FIG. 13 (A) is a plan view showing a planar state of the stirring blade, and FIG. 13 (B) is a schematic view of the stirring device. It is explanatory drawing shown. The stirrer shown in FIG. 13 is a Bicester stirrer manufactured by Nissen Co., Ltd., and is generally commercially available. Therefore, the detailed description is omitted and only the schematic configuration is described. Moreover, the same code | symbol is attached | subjected and demonstrated about the same element and member as in the stirring apparatus used in above-mentioned Example 1 and Example 2. FIG.

  In the stirring apparatus 1 shown in FIG. 13, a motor 4 is installed on the base 30, and a speed reduction mechanism 31 is attached to the motor 4. The speed reduction mechanism 31 is provided with a drive shaft 32, and a crank gear 33 is fixed to the end of the drive shaft 32. Further, the rotating shaft 10 is rotatably supported on the base 30, and a bevel gear 34 that transmits the rotation of the crank 33 in a right angle direction is fixed to the upper end portion of the rotating shaft 10. The rotating shaft 10 is moved up and down in the agitation tank 2 through a vertical movement mechanism (not shown) during rotation.

A first stirring blade 35 is fixed to the lower end portion of the rotating shaft 10, and a second stirring blade 36 is fixed at an upper position than the first stirring blade 35. The first stirring blade 35 mainly performs an action of stirring the solution existing in the lower portion of the stirring tank 2.
Further, each of the first stirring blade 35 and the second stirring blade 36 includes two support members 37 fixed to the rotating shaft 10, and the support member 37 of the second stirring blade 36 (FIG. 13A). ) An inner blade 38 and an outer blade 39 are provided on the support member 37 extending in the middle horizontal direction and the support member 37 in FIG. 13B from the rotating shaft side, respectively, and the first stirring blade 35 is provided. These two support members 37 (supports 37 extending in the vertical direction in FIG. 13A) are provided with only the inner wings 38. As shown in FIG. 13B, the first stirring blade 35 and the second stirring blade 36 configured as described above are provided at the lower end position and the center position in the vertical direction of the rotary shaft 10 in the stirring tank 2, respectively. The solution in the agitation tank 2 is agitated and circulated in the upward and downward directions to promote the vertical circulation convection.

In Comparative Example 4, the stirring device 1 configured as described above was used. At this time, the rotational speed of the first and second stirring blades 35 and 36 was set to 56 rpm, and the vertical movement of the rotary shaft 10 by the vertical movement mechanism was set to 50 strokes / min. Except for these conditions, the prepolymer was stirred according to the same conditions as in Example 3.
The rotation speed of the first and second stirring blades 35 and 36 in Comparative Example 4 is such that the power for stirring the prepolymer in the stirring tank 2 via the first and second stirring blades 35 and 36 in Comparative Example 4 is as follows. The conditions were set based on the same conditions as in Example 3.

  In the comparative example 4, the viscosity difference obtained by subtracting the viscosity value measured from the prepolymer in the upper part of the stirring tank 2 from the viscosity value measured from the prepolymer in the lower part of the stirring tank 2, and the first and second stirring blades 35 The measurement results showing the relationship with the number of rotations of 36 (a value obtained by multiplying the rotation speed by the stirring time) are shown in a graph G3 (indicated by ■) in FIG.

  Next, measurement results obtained in Example 3, Comparative Example 3, and Comparative Example 4 will be described with reference to FIG. FIG. 14 shows the difference in viscosity obtained by subtracting the viscosity value measured from the prepolymer in the upper part of the stirring tank from the viscosity value measured from the prepolymer in the lower part of the stirring tank in Example 3, Comparative Example 3 and Comparative Example 4. It is a graph which shows the relationship with the rotation speed (The numerical value which multiplied the stirring time to the rotational speed) of a stirring blade.

  The measurement result obtained in Example 3 is shown by a graph G1, and the viscosity difference is 25 Pa · s when the rotation speed of the stirring blade is 0, but the rotation speed of the stirring blade is about 10 times. At that time, the viscosity difference is about -8. This is because the prepolymer viscosity in the lower part of the stirring tank suddenly decreased, while the prepolymer viscosity in the upper part of the stirring tank suddenly increased based on the high stirring efficiency of the prepolymer by the stirring blade. It is a phenomenon caused by

And when the rotation speed of the stirring blade is about 30 times, the viscosity of the prepolymer at the lower part of the stirring tank becomes high, and the viscosity of the prepolymer at the upper part of the stirring tank becomes low, and the viscosity difference is about 3 Pa · s. become. Thereafter, when the rotation speed of the stirring blade becomes about 70 times, the viscosity difference gradually starts to settle, and when the rotation speed of the stirring blade becomes about 160 times, the viscosity difference becomes about 1 Pa · s. Furthermore, as the rotation speed of the stirring blade increases, the viscosity difference gradually decreases, and the viscosity difference becomes 1 Pa · s or less before the rotation speed reaches 200 times. Thereafter, even if the number of revolutions of the stirring blade is further increased, the viscosity difference hardly changes and the value of 1 Pa · s or less is maintained.
Thus, in the stirring apparatus used in Example 3, when the viscosity variation range of the prepolymer charged into the stirring tank is within 25 Pa · s and the maximum viscosity is 45 Pa · s or less, the rotating shaft is When the stirring blade is rotated at least 200 times, the viscosity variation range of the prepolymer becomes 1 Pa · s or less, so that the viscosity of the prepolymer is stirred in a short time with a small number of rotations that rotate the stirring blade 200 times. It can be made uniform throughout the bath.

  Further, the measurement result obtained in Comparative Example 3 is shown by a graph G2, and when the rotation speed of the stirring blade is 0, the viscosity difference is 25 Pa · s as in the case of Example 3. When the blade speed reaches about 10 times, the viscosity difference is about 10 Pa · s. This is because the stirring efficiency of the prepolymer by the stirring blade is not so high, and therefore the viscosity of the prepolymer in the lower part of the stirring tank is low, while the viscosity of the prepolymer in the upper part of the stirring tank is high, The fluidity is a phenomenon caused by the fact that it is not so remarkable.

And when the rotation speed of the stirring blade is about 30 times, the viscosity of the prepolymer in the lower part of the stirring tank becomes high, and the viscosity of the prepolymer in the upper part of the stirring tank becomes low, but the viscosity difference is about 13 Pa · s. Has increased. From this, the stirring of the prepolymer in the stirring tank is still in a state of little progress. Thereafter, when the rotation speed of the stirring blade becomes about 80 times, the viscosity difference gradually starts to settle, and when the rotation speed of the stirring blade becomes about 190 times, the viscosity difference becomes about 8 Pa · s. Furthermore, as the rotation speed of the stirring blade increases, the viscosity difference gradually decreases, but even when the rotation speed reaches 380 times, the viscosity difference is still about 7 Pa · s. Even if the number of rotations is further increased, the viscosity difference hardly changes, and the value of about 7 Pa · s is maintained.
As described above, in the case of Comparative Example 3, the viscosity difference that was 25 Pa · s at the start of the rotation of the stirring blade was about 7 Pa · s even when the number of rotations of the stirring blade was about 380 times. Agitation of the prepolymer has not been performed as efficiently.

  Further, the measurement result obtained in Comparative Example 4 is shown by a graph G3. When the rotation speed of the stirring blade is 0, the viscosity difference is 25 Pa · s as in Example 3 and Comparative Example 3. However, the viscosity difference is about 6 Pa · s when the rotational speed of the stirring blade reaches about 10 times. From this, the stirring efficiency of the prepolymer by the stirring blade is slightly higher than in the case of Comparative Example 3, but is significantly inferior to that in Example 3, and therefore the viscosity of the prepolymer in the lower part of the stirring tank is low, On the other hand, although the viscosity of the prepolymer in the upper part of a stirring tank becomes high, it turns out that the fluidity | liquidity of a prepolymer is still inadequate.

  When the number of revolutions of the stirring blade is about 40 times, the viscosity of the prepolymer at the lower part of the stirring tank increases and the viscosity of the prepolymer at the upper part of the stirring tank decreases, but the viscosity difference is about 10 Pa · s. Has increased. From this, the stirring of the prepolymer in the stirring tank is still in a state of little progress. Thereafter, when the rotation speed of the stirring blade becomes about 90 times, the viscosity difference gradually begins to settle, and when the rotation speed of the stirring blade becomes about 210 times, the viscosity difference becomes about 3 Pa · s. Furthermore, as the rotational speed of the stirring blade increases, the viscosity difference gradually decreases. However, the viscosity difference becomes about 1 Pa · s only after the rotational speed reaches about 430 times. Thereafter, even if the number of revolutions of the stirring blade is further increased, the viscosity difference hardly changes and the value of about 1 Pa · s is maintained.

  As described above, in the case of Comparative Example 4, the viscosity difference that was 25 Pa · s at the start of the rotation of the stirring blade is still about 7 Pa · s when the rotation speed of the stirring blade is about 200 times. The viscosity difference finally becomes about 1 Pa · s when the rotation speed of the stirring blade is about 430 times. Therefore, the stirring blade used in Comparative Example 4 has a higher prepolymer stirring efficiency than the stirring blade used in Comparative Example 3, but the viscosity variation range of the prepolymer is about 1 Pa · s. Therefore, it is necessary to rotate the stirring blade 400 times or more, and compared with the stirring device of Example 3, the stirring efficiency of the prepolymer is still insufficient.

It is explanatory drawing which shows a stirring apparatus typically. FIG. 2A is a plan view showing the stirring blade as viewed from above, FIG. 2B is a front view of the stirring blade, and FIG. 2C is a stirring blade. FIG. 2D is an explanatory view showing the tip of the ribbon-like blade member in the stirring blade. It is a perspective view which shows a stirring blade typically. It is explanatory drawing which shows typically the analysis model used for the numerical flow simulation. It is explanatory drawing which shows the velocity vector in the cross section which is parallel to a rotating shaft direction and contains a rotating shaft. It is explanatory drawing which shows the locus | trajectory which the particle | grains arrange | positioned on the liquid level of a solution move within fixed time. It is explanatory drawing which shows a comparative analysis model typically. It is explanatory drawing which shows the velocity vector in the cross section which is parallel to the rotating shaft direction in a comparative analysis model, and contains a rotating shaft. It is explanatory drawing which shows the locus | trajectory which the particle | grains arrange | positioned on the liquid level of a solution move within a fixed time in a comparative analysis model. It is explanatory drawing which shows typically the stirring apparatus used in Example 2. FIG. It is a graph which shows the measurement result of the viscosity change in the polymerization solution of Example 2 and Comparative Example 2. It is explanatory drawing which shows typically the outline | summary of the experiment conducted in Example 3. FIG. It is explanatory drawing which shows typically the stirring apparatus used in the comparative example 4, FIG. 13 (A) is a top view which shows the planar state of a stirring blade, FIG.13 (B) is explanatory drawing which shows a stirring apparatus typically It is. In Example 3, Comparative Example 3 and Comparative Example 4, the viscosity difference obtained by subtracting the viscosity value measured from the prepolymer in the upper part of the stirring tank from the viscosity value measured from the prepolymer in the lower part of the stirring tank, and the stirring blade It is a graph which shows the relationship with the rotation speed (the numerical value which multiplied the stirring time to the rotation speed).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Stirring apparatus 2 Stirrer tank 4 Motor 10 Rotating shaft 12 Stirring blade 13 Flat blade member 13A Semi-elliptical portion 13B Rectangular portion 14 Ribbon blade member 15 Grid blade member 15A Rod portion 15B Fixed portion 15C Connecting piece 20 UV irradiation Device 21 Optical fiber 22 Ultraviolet light source

Claims (3)

A stirred tank into which the solution is charged;
A rotating shaft disposed in a central portion of the stirring tank;
In a stirring device comprising a stirring blade attached to the rotating shaft,
The stirring blade is
A flat wing member attached to the lower portion of the rotating shaft;
A pair of ribbon-like wing members provided along the inner wall surface of the stirring tank in the opposite direction to the rotation direction of the rotation shaft from both ends of the flat plate-like wing member and obliquely upward,
A lattice-like wing member attached to the rotating shaft and connected to each ribbon-like wing member via a pair of connecting pieces;
When the viscosity variation range of the solution charged in the stirring vessel is within 25 Pa · s and the maximum viscosity is 45 Pa · s or less, when the stirring blade is rotated at least 200 times through the rotating shaft, A stirrer characterized in that the viscosity variation range of the solution is 1 Pa · s or less.   A flat blade member attached to the lower part of the rotating shaft disposed in the center of the stirring tank, and stirring from both ends of the flat blade member in a direction opposite to the rotation direction of the rotating shaft and obliquely upward Stirring provided with a pair of ribbon-like wing members provided along the inner wall surface of the tank, and a lattice-like wing member attached to the rotary shaft and connected to each ribbon-like wing member via a pair of connecting pieces When a solution having a viscosity variation range within 25 Pa · s and a maximum viscosity of 45 Pa · s or less is stirred through a blade and the stirring blade is rotated at least 200 times by the rotating shaft, The stirring method is characterized in that the viscosity variation range of the solution is 1 Pa · s or less.   The product obtained by the stirring apparatus of Claim 1, or the stirring method of Claim 2.