JP2003252908A - Manufacturing method of hydrophobic liquid drops, their manufacturing apparatus, manufacturing method of polymer beads and their manufacturing apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of highly safe hydrophobic liquid drops each having a uniform particle diameter, their manufacturing apparatus, a manufacturing method of polymer beads and their manufacturing method. <P>SOLUTION: The hydrophobic liquid drops 24 each having a uniform particle diameter are formed by use of the manufacturing apparatus 10 of hydrophobic drops having a manufacturing vessel 12 of hydrophobic liquid drops keeping an aqueous medium 11, a storage tank 14 of hydrophobic liquid keeping the hydrophobic liquid 13, a supply means 15 of hydrophobic liquid supplying the hydrophobic liquid 13 to the manufacturing vessel 12 of the hydrophobic drops, a nozzle member 16 equipped with a jetting hole 20 jetting the hydrophobic liquid 13 and a vibration means 17 giving vibration to the aqueous medium 11. The formed hydrophobic liquid drops 24 and the water medium 11 are transferred to a polymerization vessel 28 via a hydrophobic transferring means 29 and polymerization is conducted while preventing coagulation and breakage of the hydrophobic liquid drops whereby the polymer beads each having a uniform particle diameter are manufactured. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing polymer beads having a uniform particle diameter and an apparatus for producing the same, and more specifically, a method for producing hydrophobic droplets having a uniform particle diameter by using a vibration method and an apparatus for producing the same. The present invention relates to a manufacturing method and a manufacturing apparatus for forming polymer beads having a uniform particle size from the obtained hydrophobic droplets.

[0002]

2. Description of the Related Art Conventionally, in the case of producing a granular resin, for example, in the case of producing particles of a styrene-divinylbenzene copolymer which has been used as a base bead of an ion exchange resin for a long time, it is usually conducted in an aqueous medium. A suspension polymerization method in which a hydrophobic monomer-containing liquid is dispersed and polymerized is used. In this method, the particle size of the polymer particles to be obtained depends on the particle size of the hydrophobic droplets in the aqueous medium, but the particle diameters of the monomer-containing droplets dispersed in water by the usual method vary. Therefore, there is a problem in that the particle size of the polymer particles obtained by the polymerization also varies. Therefore, prior to the polymerization, a method has been proposed in which an oil-in-water type dispersion liquid in which monomer-containing droplets having a uniform particle size are dispersed is produced by another apparatus, and the dispersion liquid is charged into a polymerization container to perform polymerization. . As a method of producing an oil-in-water dispersion having a uniform particle size, a nozzle plate with upwardly formed ejection holes is provided at the bottom of a container filled with water, and the monomer-containing liquid is supplied into water through the ejection holes. By doing so, there is a method of dispersing the monomer-containing droplets in water (for example, refer to Patent Document 1). In order to generate uniform monomer-containing droplets using this method, the flow rate for supplying the monomer-containing liquid must be uniquely determined by the diameter of the ejection holes, the physical properties of the monomer, and the like. If the monomer-containing liquid is supplied at a flow rate other than the uniquely determined flow rate, the particle size distribution of the obtained monomer-containing droplets will be in a wide range. Therefore, in order to obtain a monomer-containing droplet having a uniform particle size using the same method, it is necessary to supply the monomer-containing liquid within a limited operation range, and mass production is performed industrially. There are limits to what can be done.

Therefore, as a method for producing uniform monomer-containing droplets or polymer beads having a narrow particle size distribution,
A method of forcibly ejecting the monomer-containing liquid from the ejection hole while applying mechanical vibration to the monomer-containing liquid has been put into practical use. As a typical method of this, there is a method disclosed in Patent Document 2. In this method, when a polymerizable monomer phase having a laminar flow characteristic is discharged through a nozzle plate into a continuous phase that is immiscible with the monomer phase, the jet flow of the generated monomer phase is crushed by mechanical vibration to obtain a uniform particle size. It forms a monomer phase droplet. This method mechanically vibrates the monomer phase side with an electromagnetic vibrator to form monomer phase droplets, and polymer beads obtained by vibrating at a vibration frequency of 100 to 1000 Hz which is preferable in the method. Has a particle size of 100 to 1000 μm.

As another method, ultrasonic vibration having a frequency of 15 kHz or more is applied to the monomer phase side to forcibly break the jet flow of the monomer phase into monomer phase droplets (for example,
Patent Document 3) has been proposed. With the same method, 20
It is characterized in that it enables formation of monomer phase droplets of 0 μm or less. In this method, cooling water is caused to flow to the vibration part to suppress the generation of frictional heat due to vibration and suppress the influence of temperature on the particle size uniformity of the monomer phase droplets. When the temperature of the monomer phase near the ejection hole rises to 70 ° C and the polymerizable monomer phase containing a polymerization initiator such as a radical initiator is ejected, depending on the kind of the monomer used, the polymerization may start at the time of ejection. There is a problem that the ejection holes are closed and the ejection pressure rises. Further, in the method of applying mechanical vibration to the monomer phase as described above, the apparatus structure is complicated, and in order to carry out these methods industrially and continuously for a long time, deterioration of the apparatus due to vibration is caused. There are problems such as easy progress and the possibility of ignition from the monomer phase due to frictional heat, and it is necessary to take sufficient safety measures.

The uniform monomer phase droplets obtained by these methods are then polymerized using suspension polymerization techniques. Various methods have been proposed for the suspension polymerization technique for producing polymer beads having a uniform particle size by polymerizing the monomer phase droplets while maintaining the particle size uniformity. For example, in Patent Document 4, a mixture of a polymerizable monomer and a polymerization initiator is ejected through an ejection hole into an aqueous medium containing a suspension stabilizer forming a continuous phase to form a monomer phase droplet. A method of making and partially polymerizing the monomer phase droplets and then completing the polymerization of the partially polymerized monomer phase droplets in a reaction vessel is disclosed. This reactor is specially designed and has a stirring function for the polymerization of the monomer phase droplets. Therefore, if monomer phase droplets having a uniform particle size can be formed, polymer beads having a uniform particle size can be produced by polymerizing the monomer phase droplets using the disclosed method.

As another method, for example, Patent Document 5
Then, a droplet having a uniform particle size obtained by the method disclosed in the above-mentioned Patent Document 2 is raised in a suspension medium (a temperature of about 40 to 50 ° C.) having a density smaller than that of the droplet to carry out a polymerization reaction. It has been proposed to transfer to a vessel and then polymerize using conventional techniques. As described above, this polymerization technique is a conventionally known batch-type polymerization technique, in which the suspension medium is stirred while serving as a polymerization medium, and the monomer is heated under free radical forming conditions. In the conventional suspension polymerization technique, in continuous suspension polymerization of a vinyl compound, by mixing a small amount of a polymer to be produced in advance with a monomer to be suspended in a polymerization medium, or by changing the type or addition amount of a suspending agent, It is possible to reduce coalescence of suspended monomer droplets. Therefore, if suspension monomer droplets having a uniform particle size can be formed, it is possible to produce polymer beads having a uniform particle diameter by polymerizing the suspension monomer droplets using the proposed method. Become.

[0007]

[Patent Document 1] JP-A-49-55782

[Patent Document 2] Japanese Patent Publication No. 1-28761 (Japanese Patent Application Laid-Open No. 57-
No. 102905)

[Patent Document 3] Japanese Patent Laid-Open No. 7-39743

[Patent Document 4] US Pat. No. 3,922,255

[Patent Document 5] JP-A-5-194611

[0008]

As described above, in the method for forcibly breaking up the jet flow of the hydrophobic liquid by applying mechanical vibration to the hydrophobic liquid (liquid monomer phase) side, and its apparatus,
Although it is possible to obtain hydrophobic droplets having a uniform particle diameter, in order to safely generate hydrophobic droplets (monomer droplets) having a uniform particle diameter with a simple manufacturing apparatus, the manufacturing method thereof is used. I had to look back. The size of the hydrophobic droplets produced is appropriately determined depending on the purpose, but usually the diameter is 5 to 10
It is possible to produce droplets of 00 μm. The initial turbulence generated in the jet flow at the exit of the jet hole grows over time, and when the jet flow exceeds the diameter of the jet flow, the jet flow splits into droplets, and the initial turbulence is the flow rate of the jet flow at the exit of the jet hole. It is believed to be due to change. That is, the size of the obtained hydrophobic droplet is determined by the correlation between the diameter of the ejection hole provided in the nozzle member used and the supply flow rate of the hydrophobic liquid. At this time, the flow rate of the hydrophobic liquid that forms the initial turbulence of the jet flow is uniquely determined according to the jet flow diameter, and only under this determined flow rate condition, the hydrophobic particle having a narrow particle size distribution, that is, a hydrophobic particle having a uniform particle size is used. A sexual droplet is obtained. Then, except for the flow rate that is uniquely determined with respect to the diameter of the ejection hole, the uniformity of the particle size of the hydrophobic droplets decreases, and the particle size distribution becomes very wide. For this reason, it is necessary to discard the particle size portion of unnecessary size from the polymer beads obtained by polymerization, and it takes a long time to manufacture the polymer beads and the cost is high.

In order to remedy the above drawbacks, a vibration method has been proposed in which a jet flow of a hydrophobic liquid is broken into hydrophobic droplets by applying mechanical vibration to the hydrophobic liquid. In the vibrating method, when a hydrophobic liquid having a laminar flow property and having a polymerizing property is jetted through a nozzle member into an aqueous medium forming a continuous phase that is immiscible with the hydrophobic liquid, a mechanical force is applied to the hydrophobic liquid side. The initial turbulence generated in the jet flow of the hydrophobic liquid is accurately and stably generated by periodically changing the liquid pressure by applying dynamic vibration, and the jet flow is forced to have a uniform particle size. It is a method of breaking into liquid droplets. By using this proposed method, it is possible to generate hydrophobic droplets with very high particle size uniformity.

However, in this method of applying mechanical vibration to the hydrophobic liquid, the structure of the device becomes complicated. Therefore, when the device is deteriorated due to continuous operation, a great amount of time is wasted in repairing the device, etc. In addition, a large amount of expense is required. Further, since the underwater acoustic device is arranged on the side of the hydrophobic liquid, there is a danger that the hydrophobic liquid is heated by the frictional heat generated by the vibration and a fire starts. Therefore, it is necessary to operate the device in consideration of safety, but there is a great risk in terms of safety. In view of the drawbacks of the conventional techniques for generating hydrophobic droplets having a uniform particle size, it is highly desirable to establish a technique that can easily and safely generate hydrophobic droplets having a uniform particle size. Is desired. The present invention has been made in view of the above circumstances, and when the hydrophobic liquid is ejected from the ejection holes by the vibration method to form the hydrophobic droplets having a uniform particle diameter, the mechanical liquid is applied to the aqueous medium side instead of the hydrophobic liquid side. Of the hydrophobic droplet by applying a dynamic vibration, the structure of the apparatus for producing the hydrophobic droplet is simplified, and the safety of the operation is high, and the method and apparatus for producing the hydrophobic droplet having a uniform particle size are provided. An object of the present invention is to provide a manufacturing method and a manufacturing apparatus for manufacturing polymer beads by polymerizing hydrophobic droplets while maintaining the uniformity of the particle size.

[0011]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to solve the above-mentioned problems, and by a method of vibrating an aqueous medium on the continuous phase side, under a wide operating range, simply. In addition, hydrophobic droplets with excellent particle size uniformity can be obtained safely, and by optimizing the dispersion and stirring state, the particle size uniformity of the hydrophobic droplets can be maintained and They have found that polymer beads can be obtained, and completed the present invention. That is, the gist of the present invention is that when a hydrophobic liquid is jetted into a continuous phase aqueous medium through a nozzle member having a plurality of jet holes, the aqueous medium is subjected to mechanical vibration to achieve high uniformity of particle size. A hydrophobic droplet forming method and a hydrophobic droplet manufacturing apparatus for forming hydrophobic droplets, wherein the obtained hydrophobic droplets have a high uniformity of particle diameters. A method and an apparatus for producing polymer beads, which are polymerized as they are to form polymer beads.

The method for producing hydrophobic droplets according to the first aspect of the present invention, which is directed to the above object, comprises:
In a method for producing hydrophobic droplets, wherein a hydrophobic liquid that is immiscible with the aqueous medium is ejected through a nozzle member having ejection holes to form droplets of the hydrophobic liquid in the aqueous medium, The hydrophobic liquid is ejected from the nozzle member while applying mechanical vibration.

Water is usually used as the aqueous medium, but if necessary, various additives composed of water-soluble compounds such as inorganic acid salts and water-soluble polymers may be contained. The hydrophobic liquid needs to be a liquid that is incompatible with the aqueous medium and can form droplets in the aqueous medium. The phenomenon that the jet flow splits into droplets is explained as "The initial turbulence generated in the liquid column (jet flow) at the outlet of the jet hole grows over time and splits when the diameter of the liquid column is exceeded." It is considered that the initial turbulence is due to the change in the flow rate of the jet flow at the outlet of the jet hole. At this time, when mechanical vibration is applied to the aqueous medium side and the pressure of the aqueous medium is periodically changed, the initial turbulence generated in the liquid column of the hydrophobic liquid is caused accurately and stably, and the liquid column is forced. It becomes possible to form uniform droplets.

In the method for producing hydrophobic droplets according to the first invention, the hydrophobic liquid may be an ethylenic monomer containing a polymerization initiator. Since the ethylenic monomer is a medium excellent in polymerizability and compatibility, it can be used in combination with various monomers, hydrophobic solvents and polymer compounds.

In the method for producing hydrophobic droplets according to the first invention, the mechanical vibration can be applied by using an underwater acoustic device. As a result, the mechanical vibration source can be brought into direct contact with the aqueous medium, and the aqueous medium can be efficiently vibrated.

In the method for producing hydrophobic droplets according to the first aspect of the invention, it is preferable that the mechanical vibration is applied in a hydrophobic droplet producing tank holding the aqueous medium. Further, it is preferable that the mechanical vibration is applied in an aqueous medium supply means for supplying the aqueous medium to a hydrophobic liquid droplet production tank holding the aqueous medium. By applying mechanical vibration in the hydrophobic liquid droplet production tank, absorption of mechanical vibration in the hydrophobic liquid droplet production tank can be prevented, and the aqueous medium can be efficiently vibrated. Further, by applying mechanical vibration in the aqueous medium supplying means, the vibrated aqueous medium can be directly supplied into the hydrophobic droplet manufacturing tank.

In the method for producing hydrophobic droplets according to the first invention, the frequency of the mechanical vibration exceeds 0 and exceeds 10,000.
It can be set to Hz or less. In order to generate hydrophobic droplets having a uniform particle size, a frequency of 10000 Hz or less may be applied, but preferably 100 to 8000H.
z. Below 100 Hz and above 8000 Hz, uniform droplets can be obtained by changing the conditions that affect the uniformity of the particle size such as the flow rate (ejection speed) of the hydrophobic liquid, the vibration intensity, and the physical properties of the hydrophobic liquid. It is possible to control the particle size of the drops, but it is difficult to obtain the desired particle size.

In the method for manufacturing hydrophobic droplets according to the first aspect of the invention, the specific gravity of the hydrophobic liquid can be 0.8 to 1.4. Further, the difference between the specific gravity of the aqueous medium and the specific gravity of the hydrophobic liquid (specific gravity of the aqueous medium-specific gravity of the hydrophobic liquid)
Can be greater than 0 and less than or equal to 0.5. As a result, the formed hydrophobic droplets can be floated in the aqueous medium or can be stably floated in the aqueous medium.

In the method for producing hydrophobic droplets according to the first invention, the viscosity of the hydrophobic liquid is 0.1 to 200 cps.
Is preferred. By adjusting the viscosity of the hydrophobic liquid within the above range, hydrophobic droplets having a more uniform particle size can be easily formed.

In the method for producing hydrophobic droplets according to the first invention, the hydrophobic liquid has a molecular weight of 1000 to 1000.
00 polymer compounds can be included. By polymerizing hydrophobic droplets formed from a hydrophobic liquid containing a polymer compound, it is possible to produce polymer beads having pores formed therein.

According to a second aspect of the present invention, there is provided an apparatus for producing hydrophobic droplets, comprising: (a) a hydrophobic droplet production tank for holding an aqueous medium forming a continuous phase; and (b) the aqueous medium. A hydrophobic liquid reservoir holding an immiscible hydrophobic liquid, (c)
A hydrophobic liquid supply means for supplying the hydrophobic liquid stored in the hydrophobic liquid storage tank to the hydrophobic liquid droplet production tank;
(D) A nozzle member having ejection holes that come into contact with the aqueous medium and eject the hydrophobic liquid supplied from the hydrophobic liquid supply means into the aqueous medium; and (e) eject the nozzle from the nozzle member. And a vibrating means for vibrating the existing hydrophobic liquid.

With such a structure, the hydrophobic liquid transferred from the hydrophobic liquid storage tank through the hydrophobic liquid supply means into the aqueous medium which is held in the hydrophobic liquid droplet production tank and forms the continuous phase. The ionic liquid can be ejected from the ejection holes provided in the nozzle member to form a jet flow of the hydrophobic liquid. At that time, by vibrating the aqueous medium side by vibrating means, the jet flow can be crushed to form hydrophobic droplets having a uniform particle size.

In the hydrophobic droplet manufacturing apparatus according to the second aspect of the present invention, (f) an aqueous medium storage tank for storing the aqueous medium separately from the hydrophobic droplet manufacturing tank, and (g) the aqueous medium. It is preferable to include an aqueous medium supply means for supplying the aqueous medium stored in the storage tank to the hydrophobic droplet manufacturing tank. By supplying the aqueous medium into the hydrophobic droplet production tank, a flow of the aqueous medium can be formed in the hydrophobic droplet production tank, and the hydrophobic droplets generated by this flow can be moved. .

In the hydrophobic droplet manufacturing apparatus according to the second aspect of the present invention, the vibrating means includes (h) the inside of the hydrophobic droplet manufacturing tank, and (i) the inside of the tank wall of the hydrophobic droplet manufacturing tank. , And (j) it can be provided at any one or two or more sites in the aqueous medium supply means. By immersing the vibrating means in the aqueous medium in the hydrophobic droplet manufacturing tank, the aqueous medium can be locally and efficiently vibrated. Further, by providing the vibrating portion of the vibrating means inside the tank wall of the hydrophobic liquid droplet production tank so that the vibrating portion contacts the aqueous medium, it is possible to vibrate the entire aqueous medium in the hydrophobic liquid droplet production tank. Further, the vibrating aqueous medium can be supplied to the hydrophobic droplet manufacturing tank by housing the vibrating means in the aqueous medium supplying means.

In the hydrophobic droplet manufacturing apparatus according to the second aspect of the present invention, the vibrating means includes (h) the inside of the hydrophobic droplet manufacturing tank, and (i) the inside of the tank wall of the hydrophobic droplet manufacturing tank. And (j) It is preferable to provide two or more (plural) at least one portion in the aqueous medium supply means. In order to increase the production amount of hydrophobic droplets, it is necessary to increase the volume of the hydrophobic droplet production tank and increase the number of ejection holes provided in the nozzle member to increase the supply amount of the hydrophobic liquid. There is. Therefore, the area of the nozzle member is increased, and the hydrophobic liquid is supplied from a wide area. As a result, the aqueous medium in contact with the hydrophobic liquid will also be distributed over a wide range, and by providing two or more vibrating means in the hydrophobic droplet manufacturing tank, the aqueous medium over a wide range can be effectively distributed. It is possible to vibrate more efficiently.

Further, by providing two or more vibrating means inside the tank wall of the hydrophobic liquid droplet production tank, even if the volume of the hydrophobic liquid droplet production tank is increased, The whole aqueous medium can be vibrated more uniformly. Further, when the volume of the hydrophobic droplet manufacturing tank increases, it is necessary to increase the amount of the aqueous medium supplied by the aqueous medium supply means. Therefore, in order to effectively and more efficiently vibrate the aqueous medium having an increased supply amount, it is preferable to provide a plurality of vibrating means. When using a plurality of vibrating means, it is preferable to synchronize the frequency and phase of each vibrating means. It is considered that the larger the number of vibrating means, the more effectively and more efficiently the aqueous medium can be vibrated.
When the number is increased, the structure becomes complicated, so that it is usually preferably 20 or less.

Here, when a plurality of vibrating means are used in the hydrophobic liquid drop production tank or in the tank wall of the hydrophobic liquid drop production tank, various hydrophobic liquids are supplied from the ejection holes of the nozzle member. In the case where there is a spatial allowance or when the structure is not complicated, it is preferable to arrange them uniformly so that vibration can be applied from any direction. Further, even when a plurality of vibrating means are used in the aqueous medium supplying means, it is preferable that they are uniformly arranged as a whole so that vibration can be applied to the aqueous medium to be supplied from various directions. As an arrangement example in the case where a plurality of vibrating means are provided in a hydrophobic liquid droplet production tank in which a nozzle member in which ejection holes are annularly arranged is provided around the periphery except for the central portion, (A) two The central axis of the vibrating surface of the vibrating means is 0 ° outside the outer circumference of the nozzle member.
And (3) are arranged so as to intersect at an angle of 180 ° or less, (B) the three vibrating means are outside the outer periphery of the nozzle member, and the central axis of the vibrating surface of the vibrating means exceeds 0 °, In addition, there is a case where they are arranged so as to intersect at an angle of 180 ° or less. In this case, the vibrating means may or may not be installed on the same plane. Thus, by vibrating the hydrophobic liquid supplied from the ejection holes from various directions, the hydrophobic liquid can be efficiently vibrated through the aqueous medium.

In the hydrophobic droplet manufacturing apparatus according to the second aspect of the present invention, the vibrating means can be an underwater acoustic device. By using an underwater acoustic device as the vibrating means, a mechanical vibration source can be directly applied to the aqueous medium. Here, for example, an underwater speaker can be used as the underwater acoustic device.

In the hydrophobic droplet manufacturing apparatus according to the second aspect of the invention, the diameter of the ejection hole provided in the nozzle member is 20.
It may be in the range of up to 500 μm. The nozzle member is provided with, for example, a hard plate that exhibits corrosion resistance to a hydrophobic liquid such as a steel plate, and a plurality of ejection holes having substantially the same diameter are provided in the hard plate at predetermined intervals (for example, 2 mm or more). It is provided. Here, if the ejection holes are too close to each other, the generated ejection flows attract each other and the shape of the ejection flow changes, which is not preferable. Also, when changing the diameter of the ejection hole,
This is done by replacing the hard plate of the nozzle member. By changing the diameter of the ejection holes, hydrophobic droplets having a desired particle size can be formed. In the production of ordinary polymer beads, the diameter of the ejection hole is 20 to 500 μm, preferably 40 to 250 μm.

In the hydrophobic droplet manufacturing apparatus according to the second aspect of the present invention, the frequency of the vibrating means exceeds 0 and 10,000H.
It is preferably variable within the range of z or less. Since the frequency of the vibrating means is variable, even if the physical properties of the hydrophobic liquid, the flow rate of the hydrophobic liquid, the state of the aqueous medium, and other factors that affect the particle size of the formed hydrophobic droplets, It is possible to stably form hydrophobic droplets having a uniform particle size.

According to a third aspect of the present invention, which is directed to a method for producing polymer beads, the hydrophobic droplets made of an ethylenic monomer obtained by the method for producing hydrophobic droplets according to the first invention are treated with the aqueous solution. The hydrophobic droplets are transferred to a polymerization reaction tank together with the medium, and the hydrophobic droplets are converted into polymer beads by advancing the polymerization reaction while preventing the hydrophobic droplets from substantially coalescing or crushing in the aqueous medium. Change.

Since the hydrophobic droplets are transferred to the polymerization reaction tank together with the aqueous medium, coalescence and destruction of the hydrophobic droplets are unlikely to occur.
Since the hydrophobic droplets are transferred to the polymerization reaction tank and then polymerized, the polymerization reaction can be reliably caused. At this time, since the hydrophobic droplets are polymerized in a state of being dispersed in the aqueous medium, the polymerization reaction can be progressed while preventing the hydrophobic droplets from substantially crushing and coalescing.

According to a fourth aspect of the present invention, there is provided an apparatus for producing polymer beads which comprises: (a) a hydrophobic droplet production tank for holding an aqueous medium forming a continuous phase; and (b) an immiscible aqueous medium. A hydrophobic liquid storage tank for holding a hydrophobic liquid,
(C) a hydrophobic liquid supply means for supplying the hydrophobic liquid stored in the hydrophobic liquid storage tank to the hydrophobic liquid droplet production tank, and (d) a hydrophobic liquid supply means in contact with the aqueous medium. A nozzle member having ejection holes for ejecting the supplied hydrophobic liquid into the aqueous medium; (e) vibrating means for vibrating the hydrophobic liquid ejected from the nozzle member; A polymerization reaction tank in which hydrophobic droplets in the hydrophobic droplet manufacturing tank are transported together with the aqueous medium to prevent coalescence or crushing of the hydrophobic droplets to proceed with the polymerization reaction; ) A hydrophobic droplet transfer means for transferring the hydrophobic droplets together with the aqueous medium from the hydrophobic droplet manufacturing tank to the polymerization reaction tank.

With such a structure, the hydrophobic liquid transferred from the hydrophobic liquid storage tank through the hydrophobic liquid supply means into the aqueous medium held in the hydrophobic droplet manufacturing tank to form the continuous phase. The jet of the hydrophobic liquid can be formed by jetting the volatile liquid from the jet holes provided in the nozzle member. At that time, by vibrating the aqueous medium side by vibrating means, the jet flow can be crushed to form hydrophobic droplets having a uniform particle size. Since the hydrophobic droplet production tank is provided with a hydrophobic droplet transfer means and is connected to the polymerization reaction tank, the hydrophobic droplets produced in the hydrophobic droplet production tank together with the aqueous medium are combined with the polymerization reaction tank. Can be transferred to.

In the polymer bead manufacturing apparatus according to the fourth aspect of the invention, further, (f) the aqueous medium storage tank for storing the aqueous medium, and (g) the aqueous medium stored in the aqueous medium storage tank, the hydrophobic medium is used as the hydrophobic medium. It is preferable to include an aqueous medium supply means for supplying the liquid to the droplet manufacturing tank. by this,
By supplying the aqueous medium into the hydrophobic droplet manufacturing tank,
A stream of an aqueous medium can be formed in the hydrophobic droplet manufacturing tank, and the hydrophobic droplets generated by this stream can be continuously transferred to the polymerization reaction tank.

In the polymer bead manufacturing apparatus according to the fourth aspect of the invention, the vibrating means includes: (h) the inside of the hydrophobic droplet manufacturing tank, (i) the inside of the tank wall of the hydrophobic droplet manufacturing tank, and (J) It is preferable that one or a plurality are provided at any one or two or more sites in the aqueous medium supply means. By immersing one or more vibrating means in the aqueous medium in the hydrophobic droplet manufacturing tank, the aqueous medium can be efficiently vibrated over a desired region. The number of vibrating means is appropriately adjusted according to the size of the region to be efficiently vibrated and the internal structure of the hydrophobic droplet manufacturing tank. Also,
By providing one or more vibrating means inside the tank wall of the hydrophobic liquid droplet production tank so that the vibrating part of the vibrating means comes into contact with the aqueous medium, the entire aqueous medium in the hydrophobic liquid droplet production tank is vibrated. Can be shaken. Here, the number of vibrating means is appropriately adjusted according to the size of the hydrophobic liquid droplet production tank and the internal structure of the hydrophobic liquid droplet production tank. Further, by accommodating one or more vibrating means in the aqueous medium supplying means, the vibrating aqueous medium can be supplied to the hydrophobic droplet manufacturing tank. The number of vibrating means is appropriately adjusted according to the supply amount of the aqueous medium and the internal structure of the aqueous medium supply means.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION Next, referring to the attached drawings, an embodiment in which the present invention is embodied will be described to provide an understanding of the present invention. FIG. 1 is a side sectional view showing an outline of a polymer bead manufacturing apparatus having a hydrophobic droplet manufacturing apparatus according to an embodiment of the present invention, and FIG. 2 is a modification of the polymer bead manufacturing apparatus. FIG. As shown in FIG. 1, a hydrophobic droplet manufacturing apparatus 10 according to an embodiment of the present invention includes a hydrophobic droplet manufacturing tank 12 that holds an aqueous medium 11 that forms a continuous phase, and an aqueous medium 11. Hydrophobic liquid storage tank 14 for holding the immiscible hydrophobic liquid 13
And the hydrophobic liquid 1 stored in the hydrophobic liquid storage tank 14.
And a hydrophobic liquid supply pipe 15 which is an example of a hydrophobic liquid supply means for supplying 3 to the hydrophobic droplet manufacturing tank 12.
Further, in the hydrophobic droplet manufacturing apparatus 10, the nozzle member 16 provided with the ejection hole 20 that comes into contact with the aqueous medium 11 and ejects the hydrophobic liquid 13 supplied from the hydrophobic liquid supply pipe 15.
And an underwater acoustic device 17 which is an example of a vibrating means for mechanically vibrating the aqueous medium 11 in the hydrophobic droplet manufacturing tank 12.
And an aqueous medium storage tank 18 that stores the aqueous medium 11, and an aqueous medium supply pipe 19 that is an example of an aqueous medium supply unit that supplies the aqueous medium 11 stored in the aqueous medium storage tank 18 to the hydrophobic droplet manufacturing tank 12. It has and. Here, reference numeral 21
Indicates a hydrophobic liquid jetting storage tank, and reference numerals 22 and 23 indicate pumps for supplying a hydrophobic liquid and an aqueous medium, respectively.

With such a structure, the hydrophobic liquid storage tank 14 and the hydrophobic liquid supply pipe 15 are provided in the aqueous medium 11 which is held in the hydrophobic droplet manufacturing tank 12 to form a continuous phase. The hydrophobic liquid 13 transferred by the supply pump 22 can be ejected from the ejection holes 20 provided in the nozzle member 16 to form a jet flow of the hydrophobic liquid 13. At this time, by vibrating the side of the aqueous medium 11 with an underwater acoustic device 17 such as an underwater speaker, the jet flow is crushed and the hydrophobic droplets 24 having a uniform particle size are obtained.
Can be Here, the underwater acoustic device 17 can be provided in the hydrophobic droplet manufacturing tank 12 in the vicinity of the nozzle member 16 or inside the tank wall of the hydrophobic droplet manufacturing tank 12. However, when the underwater acoustic device 17 is provided inside the tank wall of the hydrophobic liquid drop manufacturing tank 12, a part of the vibration is absorbed by the hydrophobic liquid drop manufacturing tank 12 and the vibration acting on the jet flow is attenuated. The hydrophobic droplets 24 having a uniform particle diameter can be formed under a wider range of conditions by providing the hydrophobic droplets in the vicinity of the nozzle member 16 in the hydrophobic droplet manufacturing tank 12.

Further, when a plurality of underwater acoustic devices 17 are installed in the hydrophobic liquid drop production tank 12, the supplied hydrophobic liquid 1
3 can be vibrated efficiently and effectively, and the hydrophobic droplet 24 having a more uniform particle size can be formed. When a plurality of underwater acoustic devices 17 are installed, the underwater acoustics can be applied to the jet flow of the hydrophobic liquid 13 formed by the jet holes 20 provided in the nozzle member 16 from various directions. The device 17 is preferably located. For example, it is preferable to arrange the underwater acoustic device 17 so as to surround the nozzle member 16 from the outer circumference. Further, in each hydroacoustic apparatus 17, it is preferable to synchronize the frequency and the phase. Further, the larger the number of the underwater acoustic devices 17, the more preferable, but when the number is increased, the hydrophobic liquid drop production tank 1
Since there is a problem that the structure of 2 becomes complicated, it is usually preferable to set it to 20 or less. Forming a flow of the aqueous medium 11 in the hydrophobic droplet production tank 12 by supplying the aqueous medium 11 stored in the aqueous medium storage tank 18 into the hydrophobic droplet production tank 12 by the supply pump 23. Can
By this flow, the generated hydrophobic droplet 24 can be moved.

A hydrophobic liquid jetting storage tank 21 exists in the inner lower portion of the hydrophobic liquid droplet producing tank 12, and an jetting hole 20 that opens toward the aqueous medium 11 and jets the hydrophobic liquid 13 in the upper portion thereof. Is attached to the nozzle member 16.
Therefore, from the hydrophobic liquid storage tank 14, the hydrophobic liquid supply pipe 1
The hydrophobic liquid 13 supplied by the supply pump 22 via 5 is stored in the hydrophobic liquid ejection storage tank 21 and ejected straight upward from the ejection holes 20 provided in the nozzle member 16. The nozzle member 16 has a hydrophobic liquid 1
1 to a plurality of ejection holes 20 at a predetermined interval, for example, 2
It is arranged with an interval of mm or more. Further, the diameter of the ejection hole 20 can be variously used depending on the desired droplet size, and the ejection hole diameter in the production of ordinary polymer beads is 20 to 500 μm, preferably 20 to 500 μm.
It is 250 μm.

When the hydrophobic liquid 13 is ejected from the ejection holes 20 formed in the nozzle member 16 toward the inside of the aqueous medium 11, vibration is applied to the side of the aqueous medium 11 by using an underwater acoustic device 17 to obtain uniform particles. Hydrophobic droplets 24 having a diameter can be generated. The generated hydrophobic droplet 24 is
Although there is a possibility of coalescence and destruction immediately after generation, coalescence and destruction of the hydrophobic droplets 24 can be minimized by selecting the optimal combination of the aqueous medium 11 for the hydrophobic liquid 13. Becomes As a result, regardless of the type of the hydrophobic liquid 13, about 90% by volume of the generated hydrophobic liquid droplets 24 is in the range of about 0.9 to 1.1 times the volume average diameter of the generated hydrophobic liquid droplets 24. It is possible to sufficiently ensure the uniformity of the particle size.

Next, a method of manufacturing hydrophobic droplets according to an embodiment of the present invention will be described in detail. In the aqueous medium 11 (for example, aqueous phase) forming the continuous phase, the hydrophobic liquid 13 (for example, oil phase) supplied through the ejection holes 20 forms a jet flow having a liquid column shape, and the hydrophobic liquid is hydrophobic at the tip end side of the jet flow. The phenomenon of breaking up into droplets 24 has been known for a long time. Utilizing this phenomenon, for example, a method of producing a granular material having a uniform particle size has been proposed. In this case, the aqueous medium 11 is usually
Although water is used, various additives composed of a water-soluble compound such as an inorganic acid salt or a water-soluble polymer may be added to the aqueous medium 11 if necessary. On the other hand, as the hydrophobic liquid 13,
It is necessary that the liquid be incompatible with the aqueous medium 11 and capable of forming droplets in the aqueous medium 11.
The components of the hydrophobic liquid 13 can be appropriately selected according to the purpose. For example, in the case of producing the hydrophobic droplets 24 used in the suspension polymerization for producing the granular resin, the monomer may be used as it is as the hydrophobic liquid 13 or, if necessary, a solvent immiscible with water. It can also be used in the form of a monomer solution dissolved in. Further, in the hydrophobic liquid 13, a polymerization initiator (in the case of vinyl monomer)
Must be included.

In the method of manufacturing hydrophobic droplets of this embodiment, instead of vibrating the hydrophobic liquid 13 side, the aqueous medium 1 is used.
The 1 side is vibrating. In the vibration on the side of the aqueous medium 11, since 90% or more of the aqueous medium 11 is water, the risk of ignition is much lower than that of the vibration on the side of the hydrophobic liquid 13, and the safety is improved. Further, as compared with the case where the hydrophobic liquid 13 side is vibrated, the effect of breaking the jet flow by vibrating to form the hydrophobic droplets 24 is significantly improved, and the hydrophobic droplets 24 having a uniform particle size are manufactured. The operating range is wide. Also,
At the time of scale-up, in the excitation of the hydrophobic liquid 13 side, there is a limit in improving the ability of the device and a limit in safety measures in enhancing the excitation strength, whereas in the excitation on the aqueous medium 11 side. It is possible to easily scale up in terms of safety and vibration strength.

When the aqueous medium 11 is vibrated, the hydrophobic liquid 1
The specific conditions for breaking the jet flow of No. 3 into the hydrophobic droplets 24 having a uniform particle size, that is, the frequency of vibration and the flow rate of the hydrophobic liquid 13 are the physical properties of the hydrophobic liquid 13 (viscosity, interfacial tension, specific gravity, Density), the diameter size of the ejection holes 20, and other factors. That is, the frequency and the hydrophobic liquid 13
By selecting the flow rate and the diameter of the ejection hole 20, the hydrophobic droplet 24 having a desired particle size can be obtained. Aqueous medium 1
In order to generate the hydrophobic droplets 24 having a uniform particle size by the vibration of 1, the vibration having a frequency of more than 0 and 10,000 Hz or less may be applied, but preferably 100 to 800.
It is 0 Hz. Below 100 Hz and above 8000 Hz, by changing the conditions that affect the homogenization of the particle size of the hydrophobic droplet 24, such as the jetting speed, the vibration intensity, and the physical properties of the hydrophobic liquid 13, the hydrophobic property of uniform particle size is obtained. Although the droplets 24 are obtained, it is difficult to control the particle size of forming the hydrophobic droplets 24 having a desired size.

The hydrophobic liquid 13 is not particularly limited as an ethylenic monomer (polymerizable monomer), and any one can be used as long as it can be used for suspension polymerization. For example, styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4. -Styrene such as dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene and the like. Derivatives, polyvinyl aromatic compounds such as divinylbenzene divinyltoluene, divinylxylene and trivinylbenzene, organic acid vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate, methacrylic acid, methyl methacrylate, ethyl methacrylate, methacryl Propyl acid, n-butyl methacrylate, Methacrylic acid and its derivatives such as n-octyl tacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminomethyl methacrylate, acrylic acid, methyl acrylate, Acrylic acid and its derivatives such as ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, stearyl acrylate, phenyl acrylate, vinyl methyl ketone, vinyl hexyl ketone Such as vinyl ketones, N-vinyl pyrrole, N-vinyl carbazole, N-vinyl compounds such as N-vinyl pyrrolidone, vinyl naphthalene,
Polymerizable monomers such as acrylonitrile, methacrylonitrile and acrylamide can be used. These monomers can be used alone or in combination of two or more kinds in various compositions, if necessary.

As the polymerization initiator, a radical polymerization initiator which has been conventionally used for producing a polymer from the above-mentioned monomers is used. For example, a monomer-soluble radical polymerization initiator such as peroxide, for example, benzoyl peroxide or azobisisobutyronitrile, or a water-soluble radical polymerization initiator, for example, persulfate, hydrogen peroxide,
Alternatively, hydroperoxide is used. The pore-forming agent, that is, the material that imparts a porous structure to the produced polymer may be, for example, a solvent (an aliphatic hydrocarbon such as hexane, toluene and isooctane) that forms a solution with a monomer and does not dissolve the produced polymer, 1000 to 100,000 polymer compounds (for example, polyvinyl alcohol, ethylene-
Examples thereof include vinyl alcohol copolymer, polyvinyl acetate, polystyrene, nylon), but are not limited thereto. The hydrophobic liquid 13 is composed of a combination of one or more kinds of monomers, a radical polymerization initiator, and a pore-forming agent. The physical properties of the hydrophobic liquid 13 (viscosity, specific gravity, interfacial tension) depend on its composition and composition. Is very different. Therefore, the specific gravity of the hydrophobic liquid 13 is preferably 0.8 or more, more preferably 0.85 or more, and preferably 1.4 or less, more preferably 1.3 or less, and the viscosity is preferably 0.1 cps (centipoise) or more, more preferably 0.2 cps or more, particularly preferably 0.4 cps or more, and preferably 20.
0 cps or less, more preferably 100 cps or less,
Particularly preferably, it is adjusted to 50 cps or less. When the hydrophobic droplets 24 are suspended in the aqueous medium 11, the difference between the specific gravity of the aqueous medium 11 and the specific gravity of the hydrophobic droplets 24 (hydrophobic liquid 13) (specific gravity of the aqueous medium 11-hydrophobic liquid). The specific gravity of the droplet 24 is preferably more than 0 and 0.5 or less. The specific gravity of the hydrophobic liquid 13 is often 1 or less, but the specific gravity may exceed 1 depending on the composition such as when a monomer having a halogen atom is used. On the other hand, when the water-based medium 11 is mainly composed of water, the specific gravity is around 1. Therefore, when the specific gravity of the hydrophobic droplet 24 exceeds 1, the substance that does not affect the hydrophobic droplet 24, such as sodium chloride or calcium chloride, is dissolved in the aqueous medium 11 to dissolve the aqueous medium 11 in water. The specific gravity of 11 is increased so that the difference between the specific gravity of the aqueous medium 11 and the specific gravity of the hydrophobic droplet 24 exceeds 0 and is in the range of 0.5 or less, preferably 0.05 to 0.4.
It is preferable to adjust to the range. In addition, hydrophobic liquid 1
When the specific gravity of 3 is larger than that of the aqueous medium 11, the hydrophobic droplet 24 can be settled by reversing the hydrophobic droplet manufacturing apparatus 10 and directing the ejection holes 20 downward.

The aqueous medium 11 used in the continuous phase is immiscible with the hydrophobic liquid 13 (eg polymerizable monomer),
And it must be a suitable inert liquid in which the hydrophobic liquid 13 can be dispersed as droplets therein. Usually, the aqueous medium 11 contains a suspending agent. The suspending agents which can be used in a conventional manner depend on the type, composition and amount of the hydrophobic liquid 13 used. The suspending agent used here is not particularly limited, and may be a suspending agent used in ordinary suspension polymerization. Typically gelatin, polyvinyl alcohol, starch, polyacrylamide, water-inert inorganic compounds such as magnesium silicate, and cellulose ethers,
For example, carboxymethyl-methyl cellulose. However, in order to maintain the uniformity of the particle size without coalescing and crushing the generated hydrophobic droplets 24, the type of the aqueous medium 11 and the suspending agent are determined by the correlation with the physical properties of the hydrophobic liquid 13. Determine the concentration. In maintaining the uniformity of the particle size of the hydrophobic droplets 24, the suspending agent is
0.01 to 5% by weight, preferably 0.05 to 1.5% by weight, and 25 ° C or more and less than 100 ° C, preferably 30 to 40 in order to maintain the uniformity of the particle size with respect to temperature.
℃.

FIG. 2 shows a hydrophobic droplet manufacturing apparatus 2 which is a modification of the hydrophobic droplet manufacturing apparatus 10 according to the present embodiment.
5 is shown. The hydrophobic droplet manufacturing apparatus 25 is characterized in that an underwater acoustic device storage tank 26 is provided in the aqueous medium supply pipe 19, and the underwater acoustic device 17 is mounted therein.
Other configurations are the same as those of the hydrophobic droplet manufacturing apparatus 10. Therefore, detailed description of the hydrophobic droplet manufacturing apparatus 25 is omitted. When a plurality of underwater acoustic devices 17 are installed in the underwater acoustic device storage tank 26, the aqueous medium 11 to be supplied is supplied.
Can be efficiently and effectively vibrated to efficiently and effectively break up the ejected particles of the hydrophobic liquid 13 formed in the ejection holes 20 of the nozzle member 16, resulting in a more uniform hydrophobic droplet. Two
4 can be formed. Multiple underwater acoustic devices 1
When 7 is installed, it is preferable to uniformly arrange it on the entire inner wall surface of the underwater acoustic device storage tank 26 so that vibration can be applied to the aqueous medium 11 from various directions. Then, it is preferable that each hydroacoustic apparatus 17 be used with its frequency and phase being synchronized. Further, the more the number of the underwater acoustic equipments 17 is, the more preferable, but when the number is increased, the structure of the underwater acoustic equipment storage tank 26 becomes complicated,
There is a problem that the size becomes large, so
Normally, it should be 20 or less.

Further, in the hydrophobic droplet manufacturing apparatus 25, the aqueous medium 11 vibrated by the underwater acoustic device 17 flows out to the vicinity of the nozzle member 16. Therefore, the effect of breaking the jet flow generated from the jet holes 20 into the hydrophobic droplets 24 having a uniform particle diameter is the same as that of the hydrophobic droplet manufacturing apparatus 10. Therefore, the description of the method of manufacturing the hydrophobic droplet 24 using the hydrophobic droplet manufacturing apparatus 25 is omitted. The hydrophobic droplet manufacturing apparatus 25 has an advantage that the structure of the place where the nozzle member 16 is installed is simplified, and replacement and maintenance of the nozzle member 16 are facilitated. However, since the vibration is attenuated when the aqueous medium 11 moves inside the aqueous medium supply pipe 19, the hydrophobic droplet manufacturing apparatus 10 shown in FIG. 1 has a uniform particle size under a wider range of conditions. Hydrophobic droplets 24 can be formed.

Next, the polymer bead manufacturing apparatus 27 according to one embodiment of the present invention will be described. As shown in FIG. 1, a polymer bead manufacturing apparatus 27 includes a hydrophobic droplet manufacturing apparatus 10 and a hydrophobic droplet 24 in a hydrophobic droplet manufacturing tank 12 transferred together with an aqueous medium 11. 24
Polymerization reaction tank 2 for performing polymerization reaction without coalescing and crushing
8, and the hydrophobic droplet transfer means, which is an example of the hydrophobic droplet transfer means for transferring the hydrophobic droplets 24 from the hydrophobic droplet manufacturing tank 12 to the polymerization reaction tank 28 without adhering and crushing them together with the aqueous medium 11. And a tube 29. With such a configuration, the hydrophobic liquid is transferred from the hydrophobic liquid storage tank 14 through the hydrophobic liquid supply pipe 15 into the aqueous medium 11 which is held in the hydrophobic droplet manufacturing tank 12 and forms a continuous phase. Hydrophobic liquid 13
Can be ejected from the ejection hole 20 provided in the nozzle member 16 to form an ejection flow. At that time, the aqueous medium 1
By vibrating the 1st side with the underwater acoustic device 17,
The jet stream can be broken into hydrophobic droplets 24 having a uniform particle size. Since the hydrophobic liquid droplet production tank 12 is provided with the hydrophobic liquid droplet transfer pipe 29 and is connected to the polymerization reaction tank 28, the aqueous medium 11 is supplied from the aqueous medium storage tank 18 into the hydrophobic liquid droplet production tank 12. By doing so, a flow of the aqueous medium 11 can be formed in the hydrophobic droplet production tank 12, and the hydrophobic droplets 24 produced in the hydrophobic droplet production tank 12 are generated by this flow together with the aqueous medium 11. It can be continuously transferred to the polymerization reaction tank 28.

Next, a method for producing polymer beads using the polymer bead producing apparatus 27 according to the present embodiment will be described. The hydrophobic droplets (including a polymerization initiator) 24 having a uniform particle size manufactured by the hydrophobic droplet manufacturing apparatus 10 transfer the hydrophobic droplets while maintaining the particle size uniformity together with the aqueous medium 11. Polymerization reaction tank 28 through pipe 29
Sent to. A heating means (not shown) (for example, steam heating) is provided on the outer peripheral side of the polymerization reaction tank 28, and the contents in the polymerization reaction tank 28 can be heated to, for example, 70 to 80 ° C. Therefore, the hydrophobic droplets 24 transferred to the polymerization reaction tank 28 start polymerization due to the action of the polymerization initiator. Normally, the hydrophobic droplets 24 are transferred to the polymerization reaction tank 28 together with the floating upstream of the aqueous medium 11, and the transfer temperature of the hydrophobic droplets 24 is the temperature at which the hydrophobic droplets 24 are formed ( That is, the temperature of the aqueous medium 11) is 30 ° C.
As described above, the temperature is lower than 100 ° C, preferably 30 to 50 ° C, which is lower than the radical formation condition temperature.

Usually, a radical polymerization initiator, which is an example of a polymerization initiator, is added to the hydrophobic liquid 13, so that the temperature in the polymerization reaction tank 28 is raised under radical generation conditions to allow the polymerization reaction to proceed. To do. Here, the conditions of the polymerization reaction and the time of the polymerization reaction differ depending on the composition of the monomers constituting the hydrophobic droplets 24, but typically, the polymerization reaction is performed at a temperature of 60 to 80 ° C. for 6 to 10 hours. Done. During this polymerization reaction over a long period of time, appropriate agitation is performed so that the hydrophobic droplets 24 having a uniform particle size are not coalesced and crushed and the hydrophobic droplets 24 are in a uniformly dispersed state. It is necessary to give. Stirring conditions vary depending on the physical properties of the monomers constituting the manufactured hydrophobic droplets 24 and the diameter of the hydrophobic droplets 24, but the conditions are as optimum conditions for maintaining the uniformity of the particle size, It is decided uniquely.

When the polymerization reaction is completed, the solid polymer beads are separated from the aqueous medium 11 by a dehydration technique such as filtration and collected. The recovered polymer beads are then subjected to various treatments. The polymer beads obtained in this manner are smaller than the diameter of the hydrophobic droplets 24 before the polymerization reaction, but they prevent the coalescence and destruction of the hydrophobic droplets 24 to cause the polymerization reaction. The uniformity of particle size is maintained. For example, about 90% by volume of the polymer beads has a volume average of about 0.9-1.
It has a particle size in the range of one time, and it is possible to manufacture polymer beads having extremely high particle size uniformity. As shown in FIG. 2, the hydrophobic droplet manufacturing apparatus 25 described above is used instead of the hydrophobic droplet manufacturing apparatus 10.
The polymer beads can be manufactured by the same method as the polymer bead manufacturing apparatus 27 by the polymer bead manufacturing apparatus 30 using the.

The embodiment of the present invention has been described above.
The present invention is not limited to this embodiment,
For example, although the underwater acoustic device 17, for example, an underwater speaker is used as the vibrating means, a mechanical vibrating means such as a vibrator or an electromagnetic vibrating means such as a piezoelectric element may be used. Although the vibrating means is provided in either the hydrophobic droplet manufacturing tank 12 or the underwater acoustic device storage tank 26, it may be provided in each of the hydrophobic droplet manufacturing tank 12 and the underwater acoustic device storage tank 26. In addition, the vibrating means is a part (for example, a portion in the aqueous medium supplying means other than the underwater acoustic device storage tank 26).
It may be provided in the aqueous medium supply pipe 19). The vibration means is
It is more preferable to provide two or more in each of the hydrophobic liquid droplet production tank 12 and the aqueous medium supply means because vibration can be performed efficiently and effectively. However, when two or more vibrating means are used, resonance between the vibrating means or device resonance may occur, so it is preferable to devise a place to install each vibrating means. Although the present embodiment has been described by taking as an example the production method in which the polymer beads used for the ion exchange resin matrix or the like are produced by suspension polymerization, and the production apparatus,
The method for producing hydrophobic droplets and the apparatus for producing the same, and the method and apparatus for producing polymer beads of the present invention are not limited to the production of such resin particles, and are widely applicable to the production of uniform droplets and uniform polymer beads. Can be applied.

[0055]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Example 1 A polymer bead manufacturing apparatus 27 shown in FIG. 1 was used to manufacture polymer beads having a uniform particle size. Here, the hydrophobic droplet manufacturing tank 12 has an inner diameter of 0.3 m and a height of 0.4 m. Further, the nozzle member 16 provided in the hydrophobic liquid droplet production tank 12 is a disk having an outer diameter of 100 mm, and 345 ejection holes 20 having a diameter of 0.15 mm are provided at a hole interval of 2 mm. An underwater speaker, which is an example of the underwater acoustic device 17 provided in the hydrophobic liquid drop manufacturing tank 12, was available with an output of 15W. Polyvinyl alcohol 0.
The hydrophobic droplet manufacturing tank 12 and the polymerization reaction tank 28 are filled with an aqueous solution containing 05%. The aqueous polyvinyl alcohol solution is sent from the aqueous medium storage tank 18 through the aqueous medium supply pipe 19. The aqueous medium supply pipe 19 has an inner diameter of 15 mm, and its outlet is provided to face the center of the nozzle member 16 with a distance of 5 mm from the upper surface of the nozzle member 16. The aqueous solution containing polyvinyl alcohol, which is stored in the hydrophobic droplet manufacturing tank 12 and the polymerization reaction tank 28, is heated to 40 ° C. and held until the polymerization reaction starts.

A monomer phase consisting of 94 parts of styrene, 6 parts of divinylbenzene and a radical polymerization initiator is supplied from the hydrophobic liquid storage tank 14 to the hydrophobic liquid jetting storage tank 21 through the hydrophobic liquid supply pipe 15, and the nozzle member 16 ejection holes 2
From 0, it is jetted at a flow rate of 2.0 ml / min / hole. At that time, in order to break the jet flow of the monomer phase into monomer phase droplets having a uniform particle size, vibration of 1000 Hz is applied to the jet flow by an underwater speaker. The average diameter of the monomer phase droplets obtained at this time was 0.39 mm.
The volume abundance ratio of the monomer phase droplets contained in the range of the average diameter ± 10% was 98.0%. The generated monomer-phase droplets are transferred to the aqueous medium, and the hydrophobic droplet manufacturing tank 1
2 is transferred to the polymerization reaction tank 28 via the hydrophobic droplet transfer pipe 29. Then, the polymerization reaction tank 28 is stirred while stirring the monomer phase droplets under conditions that do not cause coalescence or destruction.
Is heated at 75 ° C. for 8 hours to polymerize to obtain polymer beads. The polymer beads obtained are separated using a conventional filtration technique and recovered in a state in which an aqueous solution containing polyvinyl alcohol is not contained. In this case, the average diameter of the obtained polymer beads was 0.36 mm, and the volume abundance ratio of the polymer beads included in the range of the average diameter ± 10% was 97.5%. For comparison, the polymer beads were produced under the same conditions as above with the underwater acoustic device 17 stopped, but the average diameter of the polymer beads was 0.52 mm, and the average diameter was ± 10%. The volume abundance ratio of the polymer beads included in the range was 39.7%.

[Example 2] An apparatus for producing polymer beads having substantially the same structure and shape as in Example 1 was used for producing polymer beads having a uniform particle size. However, the internal volume of the hydrophobic droplet manufacturing tank is 1.4 m ³ and is scaled up from the polymer bead manufacturing apparatus 27. The nozzle member provided in the hydrophobic droplet manufacturing tank has an outer diameter of 30
It is a 0 mm disk with 1405 ejection holes with a diameter of 0.15 mm.
It is provided individually. As the underwater speaker, which is an example of the underwater acoustic apparatus provided in the hydrophobic droplet manufacturing apparatus, one underwater speaker having a power output of 90 W was used. A hydrophobic droplet manufacturing tank and a polymerization reaction tank are filled with an aqueous solution containing 0.05% of polyvinyl alcohol. The aqueous polyvinyl alcohol solution is sent from the aqueous medium storage tank through the aqueous medium supply pipe. The outlet of the aqueous medium supply pipe is provided at the center of the nozzle member so as to face the nozzle member with a distance of 5 mm from the nozzle member. The aqueous solution containing polyvinyl alcohol, which is stored in the hydrophobic droplet manufacturing tank and the polymerization reaction tank, is heated to 40 ° C. and kept until the start of the polymerization reaction.

A monomer phase consisting of 94 parts of styrene, 6 parts of divinylbenzene and a radical polymerization initiator is supplied from a hydrophobic liquid droplet supply pipe to a hydrophobic liquid droplet jetting storage tank, and a flow rate from a jetting hole of a nozzle member is 2. Eject at 0 ml / min / hole. At that time, in order to break up the jet flow of the monomer phase into monomer phase droplets having a uniform particle size, vibration of a frequency of 1300 Hz is applied to the jet flow by an underwater speaker. The average diameter of the monomer phase droplets obtained at this time was 0.
It was 37 mm, and the volume abundance ratio of the monomer phase droplets included in the range of the average diameter ± 10% was 86.0%. Next, the polymerization reaction tank is heated at 75 ° C. for 8 hours with stirring under a condition that the monomer phase droplets are not coalesced or destroyed to polymerize to form polymer beads. The resulting polymer beads are separated using conventional filtration techniques,
It is recovered in a state where the aqueous solution containing polyvinyl alcohol is not included. In this case, the average diameter of the obtained polymer beads was 0.35 mm, and the volume abundance ratio of the polymer beads included in the range of the average diameter ± 10% was 85.9%.

[Example 3] The same apparatus for producing polymer beads as in Example 2 was used to produce polymer beads having a uniform particle size. However, two commercially available underwater speakers with an output of 90 W were used, and each underwater speaker was arranged so that the central axes of the respective vibrating surfaces intersect at an angle of 90 °. A monomer phase consisting of 94 parts of styrene, 6 parts of divinylbenzene and a radical polymerization initiator is jetted through a nozzle member at a flow rate of 2.0 ml / min / hole. Vibration of 1300 Hz is applied to each of the jet flows using two underwater speakers. At this time, the vibrations generated by the two underwater speakers were synchronized in frequency and phase. The average diameter of the monomer mixture droplets obtained at this time was 0.36 mm, and the average diameter ±
The volume abundance of the monomer phase droplets contained in the range of 10% was 97.2%. Next, the polymerization reaction tank is heated at 75 ° C. for 8 hours with stirring under a condition that the monomer phase droplets are not coalesced or destroyed to polymerize to form polymer beads. The polymer beads obtained are separated using a conventional filtration technique and recovered in a state in which an aqueous solution containing polyvinyl alcohol is not contained. The average diameter of the polymer beads obtained in this case is 0.34 mm,
The volume abundance of the polymer beads contained in the range of the average diameter ± 10% was 96.1%.

[Example 4] An apparatus for producing polymer beads having substantially the same configuration and shape as in Example 1 was used for producing polymer beads having a uniform particle size. However, the internal volume of the hydrophobic droplet manufacturing tank is 1.4 m ³ and is scaled up from the polymer bead manufacturing apparatus 27. The nozzle member provided in the hydrophobic droplet manufacturing tank has an outer diameter of 30
A 0 mm disk with 449 ejection holes with a diameter of 0.049 mm
One is provided. As the underwater speaker, which is an example of the underwater acoustic apparatus provided in the hydrophobic droplet manufacturing apparatus, one underwater speaker having a power output of 90 W was used. A monomer phase consisting of 94 parts of styrene, 6 parts of divinylbenzene, and a radical polymerization initiator is jetted through the nozzle member 16 at a flow rate of 0.45 ml / min / hole. By applying a vibration of 4400 Hz to this jet flow using an underwater speaker, a monomer phase droplet having a uniform particle size is generated. At this time, the average diameter of the obtained monomer phase droplets was 0.143 mm, and the volume abundance ratio of the monomer phase droplets included in the range of the average diameter ± 10% was 90.0%. Then, the polymerization reaction tank is heated to 75 ° C. at 8 ° C. with stirring under conditions that do not coalesce or destroy the monomer phase droplets.
Polymerization is performed by heating for a time to obtain polymer beads. The polymer beads obtained are separated using a conventional filtration technique and recovered in a state in which an aqueous solution containing polyvinyl alcohol is not contained. The average diameter of the polymer beads obtained in this case was 0.135 mm, and the average diameter was ± 10%.
The volume abundance ratio of the polymer beads included in the range of 89.
It was 9%.

[Example 5] To manufacture polymer beads having a uniform particle diameter, the same apparatus for manufacturing polymer beads as in Example 2 was used. However, we used three commercially available underwater speakers with an output of 90 W, and each underwater speaker was located outside the outer periphery of the nozzle member, with the center axis of the vibrating surface of each adjacent underwater speaker at an angle of 120 °. It was arranged to cross. A monomer phase composed of 94 parts of styrene, 6 parts of divinylbenzene and a radical polymerization initiator is jetted through a nozzle member at a flow rate of 2.0 ml / min / hole. Vibration of 4400 Hz is applied to each of the jet flows using three underwater speakers. At this time, the vibrations generated by the three underwater speakers were synchronized in frequency and phase. The average diameter of the monomer phase droplets obtained at this time was 0.143 mm, and the average diameter ±
The volume ratio of the monomer mixture droplets contained in the range of 10% was 95.2%. Next, the polymerization reaction tank is heated at 75 ° C. for 8 hours with stirring under a condition that the monomer phase droplets are not coalesced or destroyed to polymerize to form polymer beads. The polymer beads obtained are separated using a conventional filtration technique and recovered in a state in which an aqueous solution containing polyvinyl alcohol is not contained. The average diameter of the obtained polymer beads in this case was 0.134 mm, and the volume abundance ratio of the polymer beads included in the range of the average diameter ± 10% was 95.1%.

[Embodiment 6] To manufacture polymer beads having a uniform particle size, a polymer bead manufacturing apparatus 30 shown in FIG. 2 was used. The hydrophobic droplet manufacturing tank 12 and the nozzle member 1
6. The underwater acoustic device 17 is the same as that used in the first embodiment. The characteristic of the polymer bead manufacturing apparatus 30 shown in FIG.
That is, the underwater acoustic device 17 is attached to the inside of the device 6. An aqueous solution containing 0.05% of polyvinyl alcohol is filled in the hydrophobic droplet manufacturing tank 12, the underwater acoustic device storage tank 26, and the polymerization reaction tank 28. The aqueous polyvinyl alcohol solution is sent from the aqueous medium storage tank 18 through the aqueous medium supply pipe 19 provided with the underwater acoustic device storage tank 26. Aqueous medium supply pipe 19
Has an inner diameter of 15 mm, and its outlet is provided to face the center of the nozzle member 16 with a distance of 5 mm from the upper surface of the nozzle member 16. The aqueous solution containing polyvinyl alcohol, which is stored in the hydrophobic droplet manufacturing tank 12 and the polymerization reaction tank 28, is heated to 40 ° C. and held until the polymerization reaction starts.

A monomer phase consisting of 94 parts of styrene, 6 parts of divinylbenzene and a radical polymerization initiator is supplied from the hydrophobic liquid supply pipe 15 to the hydrophobic liquid jet storage tank 21.
Flow rate of 2.0 ml / min from the ejection hole 20
/ Eject at the hole. In order to break the monomer phase into uniform droplets, the jet stream is operated by the underwater acoustic device 17 at a frequency of 1000H.
Add z vibration. The generated droplets are sent to the polymerization reaction tank 28 with the flow movement of the continuous phase. The average diameter of the monomer phase droplets obtained at this time was 0.39 mm, and the volume abundance ratio of the monomer phase droplets included in the range of the average diameter ± 10% was 95.7%. Then, the polymerization reaction tank 28 is heated to 75 ° C. for 8 hours while stirring under conditions that do not coalesce or destroy the monomer phase droplets, thereby polymerizing to form polymer beads. The polymer beads obtained are separated using a conventional filtration technique and recovered in a state in which an aqueous solution containing polyvinyl alcohol is not contained. The average diameter of the obtained polymer beads in this case was 0.35 mm, and the volume abundance ratio of the polymer beads included in the range of the average diameter ± 10% was 95.6%.

Example 7 A monomer mixture consisting of 94 parts of styrene, 6 parts of divinylbenzene, and a radical polymerization initiator was used in Example 1 in the same manner as in the method for producing polymer beads of Example 1. It is jetted through the nozzle member 16 at a flow rate of 3.0 ml / min / hole. The underwater acoustic device 17 was used to
By applying a vibration of Hz, a monomer mixture droplet having a uniform particle diameter is generated. The average diameter of the droplets of the monomer mixture obtained at this time was 0.45 mm, and the average diameter was ± 1.
The volume abundance of the monomer mixture droplets included in the range of 0% was 90.3%. Then, the polymerization reaction tank 28 is heated at 75 ° C. for 8 hours with stirring under a condition in which the droplets of the monomer mixture are not coalesced or destroyed to polymerize to form polymer beads. The polymer beads obtained are separated using a conventional filtration technique and recovered in a state in which an aqueous solution containing polyvinyl alcohol is not contained. The average diameter of the polymer beads obtained in this case is 0.40 m.
The volume abundance ratio of the polymer beads contained in the range of average diameter ± 10% was 90.3%. For comparison, the polymer beads were produced under the same conditions as above with the underwater acoustic device 17 stopped, but the average diameter of the polymer beads was 0.60 mm, and the average diameter was ± 10%.
The volume abundance ratio of the polymer beads included in the range of 35.
It was 0%.

Example 8 The nozzle used in Example 1 was a monomer mixture consisting of 92 parts of styrene, 8 parts of divinylbenzene, and a radical polymerization initiator in the same manner as in the method for producing polymer beads of Example 1. It is jetted through the member 16 at a flow rate of 2.0 ml / min / hole. The frequency of the vibration applied to this jet is 700, 80
The monomer mixture droplets are generated while changing the frequency to 0, 950, 1100 Hz, and then 75 ° C. in the polymerization reaction tank 28.
Hold for 8 hours to polymerize to form polymer beads. The average particle diameter and the average diameter of each of the monomer mixture droplets obtained when the frequency of vibration was changed, and the polymer beads formed from these monomer mixture droplets ±
Table 1 shows the volume abundance ratios included in the range of 10%.

[0066]

[Table 1]

As is clear from Table 1, the particle size uniformity of the monomer mixture droplets and the polymer beads is maintained even when the frequency is changed, and the particle size uniformity is maintained before and after the polymerization reaction. It is understood that there is.

Example 9 In the same manner as in the method for producing polymer beads of Example 1, 2 parts of styrene, 37 parts of divinylbenzene, 58 parts of toluene, 3 parts of a polymer compound, and a radical polymerization initiator were used. Flow through the nozzle member 16 used in Example 1 with a monomer mixture consisting of 1.
Eject at 0 ml / min / hole. The frequency of vibration applied to this jet flow is 500, 750, 1000, 1
The monomer mixture droplets are generated while changing the frequency to 250 and 1500 Hz, and then the polymerization reaction tank 28 is operated at 80 ° C.
Hold for time to polymerize to form polymer beads.
Average particle size, average diameter ± 10 of each of the monomer mixture droplets obtained when the frequency of vibration was changed, and the polymer beads formed from these monomer mixture droplets
Table 2 shows the volume abundance ratios included in the range of%.

[0069]

[Table 2]

As is clear from Table 2, extremely high particle size uniformity is exhibited at each frequency. For comparison, the polymer beads were manufactured under the same conditions as above with the underwater acoustic device 17 stopped, but the average diameter of the polymer beads was 0.50 mm, and the average diameter was ± 10.
The volume abundance of polymer beads contained in the range of 4 is 4
It was 2.5%.

Example 10 A monomer mixture consisting of 51 parts of styrene, 6 parts of divinylbenzene, 43 parts of isooctane, and a radical polymerization initiator was prepared in the same manner as in Example 1 for producing polymer beads. Through the nozzle member 16 used in No. 1, flow rate 2.0 ml /
Eject at min / hole. This jet has a frequency of 500,
A vibration of 1000 Hz is applied to generate droplets of the monomer mixture, and then the mixture is held in the polymerization reaction tank 28 at 80 ° C. for 8 hours to be polymerized to form polymer beads. The average particle size of each of the monomer mixture droplets obtained when the frequency of vibration was changed, and the polymer beads formed from these monomer mixture droplets, and the volume abundance ratio included in the range of the average diameter ± 10% Is shown in Table 3.

[0072]

[Table 3]

For comparison, polymer beads were produced under the same conditions as described above with the underwater acoustic device 17 stopped, but the average diameter of the polymer beads was 0.51 mm.
The volume abundance ratio of the polymer beads contained in the range of the average diameter ± 10% was 76.1%.

[Example 11] The polymer beads having a uniform particle size were manufactured by the same method as the method for manufacturing the polymer beads used in Example 1 by using the polymer bead manufacturing apparatus 27 shown in FIG. The nozzle member 16 provided in the hydrophobic liquid droplet manufacturing tank 12 is a disc having an outer diameter of 100 mm, and the ejection hole 2
The hole diameter and the number of holes of 0 are as shown in Table 4.

[0075]

[Table 4]

As in Example 1, the hydrophobic droplet manufacturing tank 12 and the polymerization reaction tank 28 are filled with an aqueous solution containing 0.05% of polyvinyl alcohol. The aqueous polyvinyl alcohol solution is sent from the aqueous medium storage tank 18 through the aqueous medium supply pipe 19. The aqueous medium supply pipe 19 has an inner diameter of 15 mm, and its outlet is provided to face the center of the nozzle member 16 with a distance of 5 mm from the upper surface of the nozzle member 16.
The aqueous solution containing polyvinyl alcohol stored in the hydrophobic droplet manufacturing tank 12 and the polymerization reaction tank 28 is 40 ° C.
It is heated to and held until the start of the polymerization reaction. A monomer phase composed of 94 parts of styrene, 6 parts of divinylbenzene and a radical polymerization initiator is ejected as an ejection flow from each nozzle having a pore size shown in Table 4. Table 4 also shows the flow rate and the frequency of the applied vibration at that time. As is clear from Table 4, even if the diameter of the ejection holes 20 changes, polymer beads having a particle diameter corresponding to the ejection hole diameter can be obtained, and the uniformity of the particle diameter is also high.

Comparative Example 1 As a comparative example of Examples 1 and 4, a monomer mixture consisting of 92 parts of styrene, 8 parts of divinylbenzene, and a radical polymerization initiator was passed through a nozzle member and a flow rate of 2.0 ml / min. / Eject at the hole. At this time, vibration is applied to the monomer mixture by using the piezoelectric element device, and the frequencies are set to 700, 800, 950,
Monomer mixture droplets were generated while changing the frequency to 1100 Hz. Table 5 shows the average diameter of the obtained monomer mixture droplets, and the volume abundance ratio of the monomer mixture droplets included in the range of the average diameter ± 10%.

[0078]

[Table 5]

Comparing Tables 1 and 5, the homogeneity of the particle size of the monomer mixture droplets is higher when the aqueous medium is vibrated than when the monomer mixture is vibrated. I understand.

[Comparative Example 2] As a comparative example of Example 9, 2
A monomer mixture consisting of 1 part styrene, 37 parts divinylbenzene, 58 parts toluene, 3 parts polymer compound, and radical polymerization initiator was passed through the nozzle member 16 used in Example 1 and a flow rate of 2.0 ml / min. / Eject at the hole. At this time, vibration is applied to the monomer mixture side by using a piezoelectric element device, and 500, 750, 1000,
The monomer mixture droplets are generated while changing the frequency to 1250 and 1500 Hz. Table 6 shows the average diameter of the obtained monomer mixture droplets, and the volume abundance ratio of the monomer mixture droplets included in the range of the average diameter ± 10%.

[0081]

[Table 6]

Comparing Tables 2 and 6, it can be seen that the particle size uniformity of the droplets of the monomer mixture is higher when the aqueous medium is vibrated than when the monomer mixture is vibrated. I understand.

[0083]

In the method for producing hydrophobic liquid droplets according to claims 1 to 10, the hydrophobic liquid is ejected from the nozzle member while applying mechanical vibration to the aqueous medium. Therefore, the hydrophobic liquid is generated by frictional heat of vibration. It is possible to safely manufacture hydrophobic droplets without being heated. Moreover, by vibrating the aqueous medium side, hydrophobic droplets having a significantly uniform vibrating effect as compared with the case of vibrating the hydrophobic liquid side can be used in a wide range without being restricted by the kind of the hydrophobic liquid. It becomes possible to manufacture stably under the range of operating conditions.

Particularly, in the method for producing hydrophobic droplets according to claim 2, since the hydrophobic liquid is an ethylenic monomer containing a polymerization initiator, various kinds of monomers, hydrophobic solvents and polymer compounds can be used. It can be used in combination with any one or two or more, and it becomes possible to produce a composite hydrophobic droplet. As a result, by polymerizing the obtained hydrophobic droplets, it becomes possible to manufacture polymer beads having various characteristics.

In the method for producing hydrophobic droplets according to claim 3, since mechanical vibration is applied by using an underwater acoustic device,
The mechanical vibration source can be brought into direct contact with the aqueous medium to efficiently vibrate the aqueous medium, and the initial turbulence generated in the liquid column of the hydrophobic liquid can be accurately and stably generated and forced from the liquid column. It becomes possible to form uniformly uniform droplets.

In the method for producing hydrophobic droplets according to the fourth aspect, mechanical vibration is applied in the hydrophobic droplet production tank holding the aqueous medium, so that the hydrophobic droplet production tank is subjected to mechanical vibration. It is possible to prevent the absorption of water and to efficiently vibrate the aqueous medium, thereby more accurately and stably generating the initial turbulence generated in the liquid column of the hydrophobic liquid. As a result, it becomes possible to forcibly form uniform droplets from the liquid column of the hydrophobic liquid. In the method for producing hydrophobic droplets according to claim 5, mechanical vibration is applied in the aqueous medium supply means for supplying the aqueous medium to the hydrophobic droplet production tank holding the aqueous medium. The aqueous medium can be directly supplied to the hydrophobic droplet manufacturing tank, and the initial turbulence generated in the liquid column of the hydrophobic liquid can be generated more accurately and stably. As a result, it becomes possible to forcibly form uniform droplets from the liquid column of the hydrophobic liquid.

In the method for producing hydrophobic droplets according to the sixth aspect, the frequency of mechanical vibration exceeds 0 and 10,000 Hz.
Since it is the following, it becomes possible to efficiently manufacture hydrophobic droplets having a uniform particle size.

In the method for producing hydrophobic droplets according to claim 7, the hydrophobic liquid has a specific gravity of 0.8 to 1.4. Therefore, in the method for producing hydrophobic droplets according to claim 8, , The difference between the specific gravity of the aqueous medium and the specific gravity of the hydrophobic liquid is more than 0 and 0.5 or less, so that the formed hydrophobic droplets are levitated in the aqueous medium or stably suspended in the aqueous medium. The hydrophobic droplet can be separated from the aqueous medium or can be stably present in the aqueous medium. As a result, it becomes easy to collect the hydrophobic droplets without destroying them and to preserve the shape.

In the method for producing hydrophobic droplets according to the ninth aspect, since the viscosity of the hydrophobic liquid is 0.1 to 200 cps, hydrophobic droplets having a uniform particle size are easily formed and uniform. It is possible to improve the production yield of hydrophobic droplets having a particle size.

In the method for producing hydrophobic droplets according to claim 10, the hydrophobic liquid has a molecular weight of 1,000 to 10,000.
Since it contains 0 polymer compound, polymer beads having a porous structure can be produced. As a result, it becomes possible to newly impart properties such as adsorptivity to the polymer beads.

In the hydrophobic droplet manufacturing apparatus according to any one of claims 11 to 17, a hydrophobic droplet manufacturing tank for holding an aqueous medium forming a continuous phase, and a hydrophobic liquid holding a hydrophobic liquid immiscible with the aqueous medium. Liquid storage tank, a hydrophobic liquid supply means for supplying the hydrophobic liquid stored in the hydrophobic liquid storage tank to the hydrophobic droplet manufacturing tank, and a hydrophobic liquid supplied from the hydrophobic liquid supply means in contact with an aqueous medium. Since the nozzle member having the ejection holes for ejecting the liquid into the aqueous medium and the vibrating means for vibrating the hydrophobic liquid ejected from the nozzle member are provided, the hydrophobic liquid is heated by the frictional heat of the vibration. It is possible to safely manufacture a manufacturing device that can manufacture hydrophobic droplets without causing any trouble. Further, since the aqueous medium side is mechanically vibrated, the structure of the manufacturing apparatus is simplified, and even if the apparatus deteriorates due to continuous operation, it can be easily repaired in a short time. It is possible to reduce the maintenance cost of the manufacturing apparatus for the sexual droplets.

In particular, in the apparatus for producing hydrophobic droplets according to the twelfth aspect, an aqueous medium storage tank for storing an aqueous medium separately from the hydrophobic droplet production tank, and an aqueous solution stored in the aqueous medium storage tank. Since the medium is provided with the aqueous medium supply means for supplying the medium to the hydrophobic droplet manufacturing tank, the hydrophobic droplets generated by forming the flow of the aqueous medium in the hydrophobic droplet manufacturing tank can be moved. It is possible to prevent coalescence and breakage of the formed hydrophobic droplets.

In the apparatus for producing hydrophobic droplets according to the thirteenth aspect, the vibrating means is either in the hydrophobic droplet producing tank, inside the tank wall of the hydrophobic droplet producing tank, or in the aqueous medium supplying means. Since it is provided in one or two or more parts, a manufacturing device capable of manufacturing hydrophobic droplets having a uniform particle size most efficiently, a manufacturing device having a simpler device structure, and a nozzle member can be replaced. The manufacturing apparatus can be configured according to the purpose such as an easy manufacturing apparatus.

In the apparatus for producing hydrophobic droplets according to claim 14, the vibrating means is at least in the hydrophobic droplet producing tank, inside the vessel wall of the hydrophobic droplet producing tank, and in the aqueous medium supplying means. Since two or more are provided in one site, a wide range of aqueous medium is uniformly vibrated, so that the hydrophobic liquid existing in a wide range can be more effectively and efficiently vibrated. It will be possible. As a result, it becomes possible to configure a manufacturing apparatus capable of manufacturing hydrophobic droplets having a more uniform particle diameter with the most efficiency and in a large amount.

In the hydrophobic droplet manufacturing apparatus of the fifteenth aspect, since the vibrating means is the underwater acoustic device, a mechanical vibration source can be directly applied to the aqueous medium, and the aqueous medium can be effectively vibrated. It becomes possible. As a result, it becomes possible to efficiently manufacture hydrophobic droplets having a uniform particle size.

In the hydrophobic droplet manufacturing apparatus according to the sixteenth aspect, the diameter of the ejection hole provided in the nozzle member is 20 to 20.
Since it is in the range of 500 μm, it becomes possible to easily prepare hydrophobic droplets having a desired particle size. as a result,
By polymerizing the obtained hydrophobic droplets, it becomes possible to easily produce polymer beads having a desired particle size.

In the hydrophobic droplet manufacturing apparatus according to the seventeenth aspect, the frequency of the vibrating means exceeds 0 and 10,000 Hz.
Since it is variable within the following range, it becomes possible to always stably form hydrophobic droplets having a uniform particle size.

In the method for producing polymer beads according to claim 18, hydrophobic droplets made of an ethylenic monomer are transferred to a polymerization reaction tank together with an aqueous medium, and the hydrophobic droplets are substantially coalesced in the aqueous medium. Alternatively, the polymerization reaction is allowed to proceed while preventing crushing to change the hydrophobic droplets into polymer beads, so that polymer beads having a uniform particle size can be easily produced. Furthermore, since it is possible to form hydrophobic droplets without being restricted by the type of hydrophobic liquid, polymer beads of various materials can be easily manufactured.

In the apparatus for producing polymer beads according to any one of claims 19 to 21, a hydrophobic liquid droplet production tank for holding an aqueous medium forming a continuous phase and a hydrophobic liquid for holding a hydrophobic liquid immiscible with the aqueous medium. A storage tank, a hydrophobic liquid supply means for supplying the hydrophobic liquid stored in the hydrophobic liquid storage tank to the hydrophobic droplet manufacturing tank, and a hydrophobic liquid supplied from the hydrophobic liquid supply means in contact with the aqueous medium. A nozzle member having ejection holes for ejecting into the aqueous medium, a vibrating means for vibrating the hydrophobic liquid ejected from the nozzle member, and hydrophobic droplets in the hydrophobic droplet manufacturing tank together with the aqueous medium. A polymerization reaction tank capable of preventing the coalescence or crushing of the transferred hydrophobic droplets to proceed with the polymerization reaction, and transferring the hydrophobic droplets from the hydrophobic droplet manufacturing tank to the polymerization reaction tank together with the aqueous medium. Hydrophobic droplet transfer means Since it has, the hydrophobic droplets produced in the hydrophobic droplet production tank can be transferred to the polymerization reaction tank without causing coalescence and crushing and polymerized, and polymer beads having a uniform particle size can be produced. It becomes possible to do.

Particularly, in the apparatus for producing polymer beads according to claim 20, the aqueous medium storage tank for storing the aqueous medium and the aqueous medium stored in the aqueous medium storage tank are further supplied to the hydrophobic droplet production tank. Since it is provided with the aqueous medium supply means, it becomes possible to continuously transfer the hydrophobic droplets to the polymerization reaction tank without causing coalescence and destruction.

In the polymer bead manufacturing apparatus according to the twenty-first aspect, the vibrating means is any one of the inside of the hydrophobic droplet manufacturing tank, the inside of the tank wall of the hydrophobic droplet manufacturing tank, and the aqueous medium supply means. Alternatively, since one or more parts are provided in each of the plurality of parts, the wide range of the aqueous medium is uniformly vibrated, so that the hydrophobic liquid existing in the wide range is more effectively and efficiently vibrated. It becomes possible. Therefore, hydrophobic droplets having a more uniform particle size can be produced most efficiently and in a large amount, and as a result, polymer beads having a more uniform particle size can be produced most efficiently and It is possible to configure a manufacturing apparatus capable of manufacturing in large quantities.

[Brief description of drawings]

FIG. 1 is a side sectional view showing an outline of a polymer bead manufacturing apparatus having a hydrophobic droplet manufacturing apparatus according to an embodiment of the present invention.

FIG. 2 is a side sectional view showing a modified example of the polymer bead manufacturing apparatus.

[Explanation of symbols]

10: Apparatus for producing hydrophobic droplets, 11: Aqueous medium, 12:
Hydrophobic droplet manufacturing tank, 13: Hydrophobic liquid, 14: Hydrophobic liquid storage tank, 15: Hydrophobic liquid supply pipe, 16: Nozzle member,
17: Underwater audio equipment, 18: Aqueous medium storage tank, 19: Aqueous medium supply pipe, 20: Jet hole, 21: Hydrophobic liquid jet storage tank, 22, 23: Supply pump, 24: Hydrophobic droplet, 2
5: Hydrophobic Droplet Manufacturing Device, 26: Underwater Acoustic Device Storage Tank, 27: Polymer Bead Manufacturing Device, 28: Polymerization Reaction Tank, 29: Hydrophobic Droplet Transfer Pipe, 30: Polymer Bead Manufacturing Device

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hiroaki Nagai             1-1 Kurosaki Shiroishi, Hachiman Nishi Ward, Kitakyushu City, Fukuoka Prefecture               Within Mitsubishi Chemical Corporation (72) Inventor Ryuzo Semura             1-1 Kurosaki Shiroishi, Hachiman Nishi Ward, Kitakyushu City, Fukuoka Prefecture               Within Mitsubishi Chemical Corporation (72) Inventor Yoshio Yoneda             1-1 Kurosaki Shiroishi, Hachiman Nishi Ward, Kitakyushu City, Fukuoka Prefecture               Within Mitsubishi Chemical Corporation (72) Inventor Junya Watanabe             1-1 Kurosaki Shiroishi, Hachiman Nishi Ward, Kitakyushu City, Fukuoka Prefecture               Within Mitsubishi Chemical Corporation (72) Inventor Takayuki Tashiro             1-1 Kurosaki Shiroishi, Hachiman Nishi Ward, Kitakyushu City, Fukuoka Prefecture               Within Mitsubishi Chemical Corporation F-term (reference) 4F070 DA27 DA34 DC07                 4J011 AA08 AC05 BA08 BB01 BB09                       BB15 DA03 DB03 DB04

Claims (21)

[Claims] 1. A hydrophobic liquid immiscible with the aqueous medium is jetted through a nozzle member having jet holes into the aqueous medium forming a continuous phase, and the liquid of the hydrophobic liquid is jetted into the aqueous medium. A method for producing a hydrophobic droplet, which comprises forming a droplet by ejecting the hydrophobic liquid from the nozzle member while applying mechanical vibration to the aqueous medium. 2. The method for producing hydrophobic droplets according to claim 1, wherein the hydrophobic liquid is an ethylenic monomer containing a polymerization initiator. Manufacturing method. 3. The method for producing hydrophobic droplets according to claim 1, wherein the mechanical vibration is applied by using an underwater acoustic device. Method. 4. The method for producing hydrophobic droplets according to claim 1, wherein the mechanical vibration is applied in a hydrophobic droplet producing tank that holds the aqueous medium. A method for producing hydrophobic droplets, comprising: 5. The method for producing hydrophobic liquid droplets according to claim 1, wherein the mechanical vibration is applied to a hydrophobic liquid droplet production tank that holds the aqueous medium. The method for producing hydrophobic droplets is characterized in that the liquid droplets are supplied in an aqueous medium supplying means for supplying the liquid droplets. 6. The hydrophobic liquid according to any one of claims 1 to 5, wherein the frequency of the mechanical vibration is more than 0 and 10,000 Hz or less. Method of making drops. 7. The method for producing hydrophobic droplets according to claim 1, wherein the hydrophobic liquid has a specific gravity of 0.8 to 1.4. Droplet manufacturing method. 8. The method for producing hydrophobic droplets according to claim 1, wherein the difference between the specific gravity of the aqueous medium and the specific gravity of the hydrophobic liquid is more than 0 and 0.5 or less. And a method for producing a hydrophobic droplet. 9. The method of manufacturing a hydrophobic droplet according to claim 1, wherein the hydrophobic liquid has a viscosity of 0.1 to 200 cps. Manufacturing method. 10. The method for producing hydrophobic droplets according to claim 1, wherein the hydrophobic liquid contains a polymer compound having a molecular weight of 1,000 to 100,000. Droplet manufacturing method. 11. (a) a hydrophobic droplet production tank holding an aqueous medium forming a continuous phase, (b) a hydrophobic liquid storage tank holding a hydrophobic liquid immiscible with the aqueous medium, and (c)
A hydrophobic liquid supply means for supplying the hydrophobic liquid stored in the hydrophobic liquid storage tank to the hydrophobic liquid droplet production tank;
(D) a nozzle member having ejection holes that come into contact with the aqueous medium and eject the hydrophobic liquid supplied from the hydrophobic liquid supply means into the aqueous medium; and (e) eject the nozzle from the nozzle member. And a vibrating means for vibrating the hydrophobic liquid present therein. 12. The apparatus for producing hydrophobic droplets according to claim 11, further comprising (f) an aqueous medium storage tank for storing the aqueous medium separately from the hydrophobic droplet production tank, and (g) the aqueous solution. An apparatus for producing hydrophobic droplets, comprising: an aqueous medium supply means for supplying the aqueous medium stored in the medium storage tank to the hydrophobic droplet production tank. 13. The apparatus for producing hydrophobic droplets according to claim 12, wherein the vibrating means includes (h) the inside of the hydrophobic droplet production tank, and (i) the vessel wall of the hydrophobic droplet production tank. An apparatus for producing hydrophobic liquid droplets, which is provided inside, and (j) at any one or two or more locations within the aqueous medium supply means. 14. The apparatus for producing hydrophobic droplets according to claim 12, wherein the vibrating means includes (h) the inside of the hydrophobic droplet production tank, and (i) the vessel wall of the hydrophobic droplet production tank. Two or more hydrophobic droplet manufacturing apparatuses are provided inside and (j) at least one site in the aqueous medium supply means. 15. The hydrophobic droplet manufacturing apparatus according to claim 11, wherein the vibrating means is an underwater acoustic device. 16. The hydrophobic droplet manufacturing apparatus according to claim 11, wherein the diameter of the ejection hole provided in the nozzle member is in the range of 20 to 500 μm. An apparatus for producing hydrophobic droplets. 17. The hydrophobic droplet manufacturing apparatus according to claim 11, wherein the frequency of the vibrating means is variable in a range of more than 0 and 10,000 Hz or less. A device for manufacturing hydrophobic droplets. 18. The hydrophobic droplets made of an ethylenic monomer obtained by the method for producing hydrophobic droplets according to claim 1 are transferred to a polymerization reaction tank together with the aqueous medium. A polymer, wherein the hydrophobic droplets are converted into polymer beads by proceeding with a polymerization reaction while preventing the hydrophobic droplets from substantially coalescing or crushing in the aqueous medium. Bead manufacturing method. 19. A hydrophobic liquid drop production tank holding (a) an aqueous medium forming a continuous phase, (b) a hydrophobic liquid storage tank holding a hydrophobic liquid immiscible with the aqueous medium, and (c).
A hydrophobic liquid supply means for supplying the hydrophobic liquid stored in the hydrophobic liquid storage tank to the hydrophobic liquid droplet production tank;
(D) a nozzle member having a jet hole that comes into contact with the aqueous medium and jets the hydrophobic liquid supplied from the hydrophobic liquid supply means into the aqueous medium; and (e) jets from the nozzle member. Vibrating means for vibrating the hydrophobic liquid, and (k) the hydrophobic droplets in the hydrophobic droplet manufacturing tank are transferred together with the aqueous medium to prevent coalescence or fragmentation of the hydrophobic droplets. A polymerization reaction tank capable of advancing the polymerization reaction, and (l) a hydrophobic droplet transfer means for transferring the hydrophobic droplets together with the aqueous medium from the hydrophobic droplet manufacturing tank to the polymerization reaction tank. An apparatus for producing polymer beads, comprising: 20. The apparatus for producing polymer beads according to claim 19, further comprising (f) an aqueous medium storage tank for storing the aqueous medium, and (g) an aqueous medium storage tank for storing the aqueous medium in the hydrophobic medium. An apparatus for producing polymer beads, comprising: an aqueous medium supply means for supplying the polymer droplets to the liquid droplet production tank. 21. The polymer bead manufacturing apparatus according to claim 20, wherein the vibrating means comprises: (h) the inside of the hydrophobic droplet manufacturing tank, (i) the inside of the tank wall of the hydrophobic droplet manufacturing tank,
And (j) any one or two in the aqueous medium supply means
An apparatus for producing polymer beads, characterized in that one or a plurality of them are provided at each of the above sites.